ISSN 09670912, Steel in Translation, 2011, Vol. 41, No. 2, pp. 99–101. © Allerton Press, Inc., 2011.

Original Russian Text © R.A. Gizatulin, O.I. Nokhrina, I.D. Rozhikhina, V.I. Dmitrienko, 2011, published in “Izvestiya VUZ. Chernaya Metallurgiya,” 2011, No. 2, pp. 21–23.

Assessment of Melt Desulfurization in a Ladle–Furnace Unit

R. A. Gizatulin, O. I. Nokhrina, I. D. Rozhikhina, and V. I. Dmitrienko
Siberian State Industrial University
Received April 14, 2010

DOI: 10.3103/S0967091211020082

We will estimate the distribution of sulfur and its

final concentration in melt that is in equilibrium with
∑ where 32 is the atomic mass of sulfur, g/mole; n is ∑
the molar sum of the components in 100 g of slag.
slag, by simulation of the reducing properties of metal
and slag during ladle treatment [1, 2]. From Eqs. (2) and (3), we obtain a formula for the
equilibrium sulfur distribution coefficient LS = (S)/[S]
In ladle–furnace treatment of steel, the addition of
reducing agent (silicon) to the ladle reduces the oxida
tion of the slag. The added silicon also reduces the oxi
x CaO γ CaO n f S ∑
L S = 32K 1  
. (4)
γ CaS [ O ]f O
dation of the melt and increases the activity of the sul
fur. At the same time, lime is added to the ladle, to Taking logarithms in Eq. (4), we obtain
bind the silicon dioxide that forms and increase the
basicity of the slags. The slag evidently absorbs sulfur, x CaO γ CaO n ∑ fS
log L S = log 32K 1  + log 
. (5)
as follows from these results and the analysis of exper γ CaS [ O ]f O
imental and modeling data regarding the slag compo
sition [3]. In the refining of liquid iron, fO ≈ 1 and fS ≈ 1. Then
In the calculations, we make the following assump
tions.
Fe x CaO γ CaO n ∑
log L S = log 32K 1  – log [ O ] Fe . (6)
γ CaS
(1) The mass transfer in the slag is the limiting factor.
Fe
(2) At a high mixing rate, equilibrium is established An empirical formula for L S with the same struc
in desulfurization. ture as Eq. (6) was obtained in [6]
We consider the interaction of the liquid oxide melt Fe
and the metal and estimate the depth of desulfuriza log L S = – 2.78
tion on the basis of data from [4–6] ( CaO ) + 0.05 ( MgO ) (7)
+ 0.86  – log [ O ] Fe .
[ S ] + ( CaO ) = ( CaS ) + [ O ]; (1) ( SiO 2 ) + 0.6 ( Al 2 O 3 )
The relation between the sulfur distribution coeffi
a CaS a O x CaS γ CaS [ O ]f O Fe all
K 1 = 
 = 
, (2) cients in iron ( L S ) and in the alloy ( L S ) is obtained
a CaO a S x CaO γ CaO [ S ]f S
by writing expressions for the equilibrium constant in
where K1 is the equilibrium constant for Eq. (1); a is desulfurization of the iron and the alloy
the activity of the component; x is the molar content Fe Fe Fe Fe Fe
of the component; γ and f are the activity coefficients K Fe = ( x CaS γ CaS a O )/ ( a CaO a S ); (8)
of the component in the slag and the metal. all all all all all
K all = ( x CaS γ CaS a O )/ ( a CaO a S ). (9)
Obviously, high activity of the lime in the slag, high
activity of the sulfur in the metal, and low oxidation of Since KFe = Kall, we may write
the metal will increase the distribution of sulfur Fe Fe Fe Fe Fe
between the metal and slag and thereby ensure more ( x CaS γ CaS a O )/ ( a CaO a S )
complete desulfurization. (10)
all all all all all
= ( x CaS γ CaS a O )/ ( a CaO a S ).
We now express xCaS in terms of the sulfur concen
Fe all Fe all
tration in the slag Assuming that a CaO = a CaO and γ CaO = γ CaO and
( S ) , substituting Eq. (4) into Eq. (10), we obtain
x CaS =  (3)
32 n ∑ all Fe all Fe
L S = L S [ ( f S a O )/ ( f S a O ) ].
Fe all
(11)

99
100 GIZATULIN et al.

Mn
LS = (S)/[S] a O = 1/( K [ Mn ] f Mn ); (22)

25
FeO(li) = [Fe] + [O], (23)

aO fO [ O ] 6320
20 log L O = log 
 = log 
 = –  + 2.734. (24)
a FeO a FeO T
15
The assumption of equilibrium oxygen distribution
10 between the metal and slag is also based on the high
mixing rate of the melts.
5 If the reactions occur independently, activity of
oxygen in the melt (melt oxidation) is determined by
0 the element that ensures the lowest aO value (carbon,
0 10 20 30 40 50 τ, min silicon, or manganese).
Dependence of the sulfur distribution coefficient between When the silicon and manganese contents in the
the slag and metal on the treatment time in the ladle–fur steel and the ferrousoxide content in the slag are typ
nace unit. ical for metal discharge from the furnace, the oxida
tion of the melt is evidently determined by the carbon
content.
Given that fO ≈ 1 and fS ≈ 1 and taking logarithms in
Eq. (11), we find that Using the mathematical model, we determine the
all Fe all all
optimal conditions of steel desulfurization in ladle–
log L S = log L S + log f S + log [ O ] Fe – log a O . (12) furnace treatment and the optimal quantity of lime in
the ladle, as well as the appropriate time to introduce
Substituting Eq. (7) into Eq. (12), we obtain the reducing agent.
all ( CaO ) + 0.05 ( MgO )
log L S = – 2.78 + 0.86  In the figure, we plot the sulfur distribution coeffi

( SiO 2 ) + 0.6 ( Al 2 O 3 ) (13) cient between the slag and metal as a function of the
all all treatment time of the metal in the ladle–furnace unit.
– log a O + log f S .
The activity of the metal components is calculated
using reaction parameters of the first kind [4]. The CONCLUSIONS
activity of the slag components is calculated using data
from [3]. The optimal slag composition for desulfurization
during ladle–furnace treatment of metal is that which
To determine the activity of oxygen in the melt, we ensures maximum reduction of the metal from the slag
proceed as follows. The oxygen content in the steel is oxide in the melt. This may be explained in that
determined by the content of carbon, silicon, and increase in the lime content in the slag, which should
manganese and also from the equilibrium with slag, in increase the sulfur distribution coefficient between
accordance with the following reactions metal and slag, according to Eq. (13), increases the
[ C ] + [ O ] = CO ( g ) , (14) slag viscosity and slows the diffusion processes. When
the lime content in the slag is slightly above the opti
p CO 1168 mal value for the reduction of metal from its oxide, the
log K = log 
 =  + 2.07, (15) sulfur distribution coefficient increases (by about
aC aO T
40%), and the treatment time is also significantly
C
a O = 1/ ( K [ C ]f C ); (16) increased. Changing the amount of ferroalloy added
has little influence. In ladle–furnace treatment of the
[ Si ] + 2 [ O ] = SiO 2 ( so ) , (17) steel, optimal conditions for its desulfurization are
created. Our calculations indicate that, without any
a SiO additional measures, at least 10% of the sulfur in the
log K = log 22 = 31100
 – 12.0, (18) steel may be removed.
a Si a O T
Si
aO = 1/ ( K [ Si ]f Si ); (19) ACKNOWLEDGMENTS
[ Mn ] + [ O ] = MnO ( li ) , (20) Financial support was provided by the Russian
a MnO Ministry of Education, within the framework of the
12770 federal program for innovative Russian scientists and
log K = log 
 =  – 5.7, (21)
a Mn a O T teachers (2009–2013).

STEEL IN TRANSLATION Vol. 41 No. 2 2011

 ASSESSMENT OF MELT DESULFURIZATION IN A LADLE–FURNACE UNIT 101

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