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Effect of plug location on desulfurization characteristics of slag during Ladle

Furnace operation

Article  in  Canadian Metallurgical Quarterly · January 2006

DOI: 10.1179/000844306794408986

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 175
Canadian Metallurgical Quarterly, Vol 45, No 2 pp 175-180, 2006
© Canadian Institute of Mining, Metallurgy and Petroleum
Published by Canadian Institute of Mining, Metallurgy and Petroleum
Printed in Canada. All rights reserved

EFFECT OF PLUG LOCATION ON DESULFURIZATION

CHARACTERISTICS OF SLAG DURING
LADLE FURNACE OPERATION
M.K. SARDAR, S. MUKHOPADHYAY, S. MAJUMDER,
S. MALLICK and R.K. SINGH

Research and Development Centre for Iron and Steel, Steel Authority of India Limited,
Jharkhand, India.

(Received in revised form January, 2006)

Abstract — Three hundred ton steel ladles at the steel melting shop (SMS-II) at Bokaro Steel Limited
(BSL) are equipped with two porous plugs located at adjacent quadrants of the ladle bottom. High stirring
rates are used to affect a high production rate and quick deep desulfurization. Wide spout eye formation
and the resultant reoxidation of metal has been observed at high purging rates because of this typical plug
location. The degree of reoxidation indexed with increase in wt% Al2O3 in slag was found to be
proportional with the stirring rate. The equilibrium sulfide capacity (Cs) and alumina activity of slag
(aAl2O3) were related with the sulfur partition (Ls) achieved in actual practice. It was found that while
actual Ls vary directly with Cs, an inverse relationship exists between Ls and aAl2O3. Based on
mathematical modelling, the installation of porous plugs in all three quadrants of the ladle bottom has
been recommended to promote increased slag metal interaction at lower argon stirring rates and thereby
control the reoxidation of steel.

Résumé — Les poches de coulée d’acier de 300 tonnes à l’atelier de fonte d’acier (SMS-II) de Bokaro
Steel Limited (BSL) sont équipées de deux tampons poreux situés dans des quadrants adjacents au fond
de la poche. On utilise des taux élevés d’agitation pour obtenir un taux élevé de production et une
désulfuration rapide et profonde. Aux taux élevés de purge, on a observé la formation d’un gros oeil de
bec de coulée et la réoxydation du metal qui en résultait à cause de ce positionnement typique du tampon.
On a trouvé que le degré de réoxydation indexé par l’augmentation du % en poids d’Al2O3 dans la scorie
était proportionnel au taux d’agitation. La capacité d’équilibre du sulfure (Cs) et l’activité de l’alumine de
la scorie (aAl O ) étaient reliées par le partage du soufre (Ls) obtenu en pratique. On a trouvé qu’une
2 3
relation inverse existait entre Ls et aAl O , bien que le Ls actuel variait directement en fonction du Cs. Basé
2 3
sur la modélisation mathématique, on a recommandé l’installation de tampons poreux dans les trois
quadrants au fond de la poche de coulée afin de favoriser l’interaction accrue de la scorie de métal à des
taux plus bas d’agitation à l’argon et ainsi de contrôler la réoxydation de l’acier.

INTRODUCTION slag metal interaction and an adequate temperature are

SMS-II of Bokaro Steel Limited (SMS-II BSL) produces ~2.0
MT of Low Carbon Aluminum Killed (LCAK) grades per
annum in the form of Cold Rolled/Hot Rolled (CR/HR) coils.
The designated liquid steel is produced through a Basic
Oxygen Furnace (BOF) - Ladle Furnace (LF) - Continuous
Casting (CC) route. In general, the LF treatment cycle is
squeezed between a late BOF tapping and an early metal
demand from CC and thereby a treatment duration of less
than 30 minutes is imperative. Within this stipulated LF cycle
time, the process of deep desulfurization to <100 ppm sulfur
is a specification demand. The prerequisites of a deep
desulfurization process like fluid and reactive slag with high
sulfide capacity, a low oxygen potential in metal, an intensive
targeted in LF.
In 300 ton steel ladles of SMS-II BSL, two porous bricks
meant for gas stirring during LF operation are located at 0.7
radius of the ladle bottoms in adjacent quadrants. At low stirring
rates, the typical location of these porous bricks results in the
formation of two plume eyes in one half of the ladle and the top
slag in the other half remains inactive. High argon stirring rates
are used to bring in intensive slag/metal interaction involving
full top slag volume. As a result, the plume eye areas become
wider. These wide plume eyes result in metal reoxidation and
increased aAl2O3 in the slag. Optical basicity (l) [1], aAl2O3 [2],
equilibrium Cs [3] and Mannesman coefficient [4] were used to
analyze the top slag characteristics and related with sulfur
partition achieved at the end of the LF treatment.

CANADIAN METALLURGICAL QUARTERLY, VOL 45, NO 2

176 M.K. SARDAR, S. MUKHOPADHYAY, S. MAJUMDER, S. MALLICK and R.K. SINGH

Two-phase cold model studies [5] on the intensity of the

slag/metal interactions with respect to different porous plug
locations have recommended diagonal locations of the porous
plug for improved slag/metal interaction with smaller plume
eyes. In line with these observations and to contain
reoxidation through plume eyes, fluid flow characteristics
were identified and an additional porous brick in the vacant
third quadrant of ladle bottom was recommended.

INDUSTRIAL PRACTICE
Fig 1. Schematic diagram of existing and recommended porous plug loca-
LF treatment of SMS-II BSL includes process steps like slag tions with slide gate nozzle in 300 ton ladle bottom.
formation, heating, deoxidation, desulfurization, calcium
treatment and cleansing purging. LF productivity is directly
dependent on the process of deep desulfurization. To achieve
high sulfur partition within stipulated LF treatment time
desired slag characteristics, low oxygen potential in melts and
( ) [
log a Al2 O3 = {-0.275(%CaO) + 0.167(%MgO)} / (%SiO2 ) ] (1)
proper stirring conditions were required to be maintained +0.033(%Al 2 O 3 ) - 1.560
throughout the LF cycle.
In practice, major quantities of deoxidant (aluminum log Cs = -0.6261 + 0.4808l + 0.7197l2 + 1697 / T
1.5-1.7 kg/ton) with 5-7 kg/ton of lime and other alloying (2)
elements are added during tapping. Pretap and conventional -(2587l / T ) + 0.0005144(%FeO)
slag arresting devices are used to restrict carryover slag to
where T= temperature in Kelvin, l = Optical basicity and
~ 8-10 kg/ton. Slag formation in LF is complete within the
(%CaO), (%MgO),(%Al2O3), (%SiO2) and (%FeO) are slag
initial 3 to 5 minutes of arcing and stirring. Initial dissolved
constituents in wt%.
oxygen content is conventionally <10.0 ppm. Additional
Achieved sulfur partition (Ls), ratio of (S) in slag and [S]
quantities of lime, spar and bauxite are added after an
in metal were calculated by analyzing simultaneously
assessment of initial ‘S’ content in the melt. Throughout the
sampled metal and slag before calcium treatment.
LF treatment, dissolved oxygen content in metal is controlled
to <3.0 ppm with intermittent aluminum additions. Argon
stirring is done through twin porous plugs located at 0.7
RESULTS AND DISCUSSION
radius of the ladle bottom and the average argon purging rate
is >400 NL/min/plug. As shown in Figure 1, twin porous
Compositions of slag samples collected during the concluding
bricks are located at adjacent quadrants of the ladle bottom.
stage of LF operations (before calcium treatment) have been
presented in Table I. Optical basicity (l), equilibrium Cs,
equilibrium aAl2O3 and Mannessman coefficient (a ratio of slag
THERMODYNAMIC CALCULATIONS
basicity and wt% Al2O3 in slag) [4] of these slags were
calculated along with the sulfur partition (LS) achieved in
Desulfurization reaction during LF operation has been
practice and shown in Table I. In Figure 2, typical change in
investigated with thermodynamic tools like sulfide capacity,
slag composition during LF treatment was plotted over a
alumina activity of the top slag and related to stirring
sulfide capacity diagram of CaO-Al2O3-SiO2 ternary.
conditions prevailing with twin porous plugs located at
Between LF initial and LF final, an increase in % Al2O3 vis-
adjacent quadrants of the ladle bottom.
à-vis aAl2O3 in slags was observed. This increase in wt% Al2O3
Sulfide capacity of a homogeneous molten slag was
was related to the stirring rate in Figure 3 and thereby could
defined as the potential ability of the top slag to remove sulfur
be attributed to the reoxidation of metal or aluminum fading
from the molten metal. Several [1-3] empirical relations have
through plume eyes.
been presented to estimate the sulfide capacity in relation to
Figure 2 showed that initial LF slags were of high
slag compositions and temperature. In these expressions,
sulfide capacity composition and conducive to high Ls, thus, a
composition dependence of sulfide capacity has been
high degree of desulfurization was expected in LF when other
expressed in terms of optical basicity (l). In the present work,
conditions of desulfurization were maintained. However, at
optical basicity, alumina activity (aAl2O3) and equilibrium
SMS-II BSL, in spite of favourable LF initial slag
sulfide capacity (Cs) of the LF final slag (before calcium
compositions, low to moderate sulfur partition (Ls) between
treatment) for LCAK grade steels have been calculated using
20-100 was achieved. To analyze the causes of moderate
expressions derived by Duffy et al. [1], Ohita and Suito [2] and
desulfurization in LF, achieved sulfur partition (Ls) was
Young et al. [3], respectively. The expressions for alumina
correlated with equilibrium Cs and aAl2O3 (Figures 4 and 5).
activity (aAl2O3) [2] and equilibrium sulfide capacity (Cs) [3] are:

CANADIAN METALLURGICAL QUARTERLY, VOL 45, NO 2

 EFFECT OF PLUG LOCATION ON DESULFURIZATION CHARACTERISTICS OF SLAG DURING LADLE FURNACE... 177

Table I – Analysis of LF final slag (before Ca treatment) for optical basicity, equilibrium Cs, equilibrium aAl2O3 and
Mannesman coefficient
Heat FeO- MnO- SiO2- CaO-* Al2O3- MgO- (S)- [S] Temp. Optical Cs-(Young) log aAl2O3 Actual S Mannesman
No. °C Basicity Partition, Co-efficient
Ls
1 1.11 0.21 3.38 58.07 31.34 4.91 0.59 0.01 1590 0.8636 0.9741 -47.5254 59.000 0.5482
2 1.26 0.28 4.69 55.37 30.48 7.09 0.39 0.01 1592 0.8543 0.9734 -32.7637 39.000 0.3873
3 0.74 0.41 2.16 55.21 34.26 6.08 0.78 0.009 1597 0.8558 0.9753 -70.2458 86.667 0.7461
4 1.18 0.79 7.13 51.36 31.12 7.43 0.31 0.011 1601 0.8345 0.9738 -20.1612 28.182 0.2315
5 1.33 0.50 2.55 49.33 40.92 5.06 0.20 0.017 1582 0.8394 0.9667 -53.0758 11.765 0.4728
6 1.04 1.36 4.42 51.18 33.93 6.97 0.42 0.014 1584 0.8358 0.9668 -32.0121 30.000 0.3413
7 0.72 0.65 2.97 56.07 32.41 6.24 0.52 0.017 1588 0.8594 0.9719 -52.0518 30.588 0.5825
8 1.99 2.71 3.97 58.17 27.76 3.74 0.41 0.013 1569 0.8453 0.9626 -40.7691 31.538 0.5278
9 0.79 0.26 3.31 52.77 36.07 5.78 0.43 0.02 1579 0.8514 0.9664 -43.9132 21.500 0.4420
10 1.16 0.83 3.54 41.77 43.45 8.43 0.40 0.02 1584 0.8087 0.9651 -32.1709 20.000 0.2716
11 1.20 1.07 2.72 54.23 34.76 4.84 0.47 0.013 1587 0.8492 0.9702 -54.9357 36.154 0.5736
12 2.10 2.60 3.26 60.39 25.02 4.78 0.65 0.013 1601 0.8508 0.9777 -51.4219 50.000 0.7404
13 1.92 0.65 4.40 55.15 30.02 6.61 0.31 0.016 1595 0.8499 0.9746 -34.7778 19.375 0.4175
14 0.83 0.50 3.10 58.09 31.12 4.77 0.77 0.016 1585 0.8620 0.9711 -51.7990 48.125 0.6021
15 1.38 0.65 3.34 49.88 37.84 5.64 0.24 0.016 1585 0.8391 0.9680 -41.0851 15.000 0.3947
(* Slag constituents are in wt%)

From these figures, it could be seen that actual sulfur partition
increases with an increase in Cs and decreases with an
increase in aAl2O3. Similar observations were also noted by
Anderson et al. [6]. In Figure 6, Mannesman coefficient was
plotted against the achieved sulfur partition and the aAl2O3 of
LF final slag. It was observed that with an increase in the
Mannesman coefficient, actual Ls increases and aAl2O3
decreases. It could therefore be concluded that with existing
slag compositions (Table I), a further increase in % Al2O3
through plume eye formation (reoxidation) would result in
reduced Ls and thus impede the process of desulfurization.
This fact was further corroborated when the Mannesman
coefficient was related to equilibrium Cs in Figure 7. In Figure
7, the array of data points in industrial conditions exhibited a
peak of Cs around the Mannesman coefficient of 0.4.
In the 300 ton ladles of SMS-II BSL, an imbalance in
stirring and slag/metal interaction between the two halves of
the ladle was observed because of adjacent quadrant plug
location. Low turbulence in one half of the ladle top slag was
observed and the slag remained inactive at low stirring rates
(£250 NL/min/plug). Intensive slag metal interactions
involving full slag quantity could only be observed at higher
purging rates (~500 NL/minutes/plug). But at higher purging
rates (>300 NL/minute/plug) wide plume eye formations
were observed. This resulted in an uncontrolled increase in
%Al2O3 in slag and widespread aluminum fading. Increased
%Al2O3 in slag adversely affected the equilibrium sulfide
capacity of the slag resulting in a low and inconsistent sulfur
partition at the end of the LF treatment (Figures 4-6).

Fig 2. LF initial and final slag composition plotted on CaO-Al2O3-SiO2 Fig. 3. Effect of stirring rate on increase in Al2O3 percentage in slag.
ternary.

CANADIAN METALLURGICAL QUARTERLY, VOL 45, NO 2

178 M.K. SARDAR, S. MUKHOPADHYAY, S. MAJUMDER, S. MALLICK and R.K. SINGH
Fig. 4. Influence of equilibrium Cs on actual sulfur partition (Ls).
Fig. 5. Effect of aAl2O3 on achieved sulfur partition.
Fig. 6. Influence of Mannesman coefficient on achieved sulfur partition and
equilibrium alumina activity.
Dual phase (water-mustard oil) cold model studies
conducted by Majumdar et al. [5] with porous plug locations
at diagonal quadrants demonstrated effective slag/metal
interaction and a uniform metal stirring pattern in the ladle at
low gas stirring rates. This model also showed that higher
purging rates are necessary to achieve a similar level of
slag/metal interactions when porous bricks are located at
adjacent quadrants. In line with these observations, a
mathematical modelling was done to understand the fluid
CANADIAN METALLURGICAL QUARTERLY, VOL 45, NO 2
Fig. 7. Effect of Mannesman coefficient on sulfide capacity.
flow characteristics in 300 ton steel ladles of SMS-II BSL.
Figure 8 shows the results of mathematical modelling where
fluid flow velocity vectors were plotted for a 300 ton steel
ladle with the two existing porous plugs and the three
proposed porous plugs at gas flow rates of 300
NL/minute/plug. By the critical analysis of these plots, the
ladle refractory erosion pattern, areas of high velocity
vectors and mixing/metal circulation zones could be
identified for both two and three porous plug equipped
ladles (Figures 9 and 10). As predicted by mathematical
modeling, high refractory erosions in the ladle were also
observed at similar zones in existing (with two porous
plugs) practice. From the array of fluid flow velocity vectors
in Figures 8b and 10, reduction in the extent of the plume
eye formation, the shift of metal circulation/ mixing zones
deeper into metal, the uniform fluid flow pattern and the
reduction in preferential refractory erosion in ladle could be
predicted. Based on the results of mathematical modeling,
the installation of a third porous plug in the vacant quadrant
of the ladle bottom was recommended (Figure 1) to SMS-II
BSL to improve upon slag characteristics that was
conducive to improved desulfurization, increased LF
productivity and a cleaner final product.
a) b)
Fig 8. Mathematical modelling of 300 ton ladle with a) existing and b) mod-
ified porous plug locations showing fluid flow velocity vectors in metal at
central plane of ladle.
 EFFECT OF PLUG LOCATION ON DESULFURIZATION CHARACTERISTICS OF SLAG DURING LADLE FURNACE... 179

CONCLUSIONS
Areas of high slag

Slag zone
line refractory 1. Increases in %Al2O3 in slag beyond an optimum limit
erosion
adversely affects the equilibrium sulfide capacity and
thereby the sulfur partition at the LF final stage.
2. Mathematical modelling of the existing practice has
established that two porous bricks located at an adjacent
quadrant of the ladle bottom result in improper
slag/metal interaction at low stirring rates, imbalance in
stirring pattern, wide plume eye formations at high
stirring rates and preferential refractory erosion. Wide
plume eyes result in the widespread reoxidation of steel,
change top slag characteristics, impede desulfurizaion
reactions and thereby hinder LF productivity.
3. Liquid flow characteristics identified with mathematical
modelling of the 300 ton ladles equipped with three
porous plugs predict a reduction in plume eye
formation, a shifting of metal circulation zone deeper
into metal and a uniform fluid flow pattern and thereby
Fig 9. Schematic diagram of ladle with existing plug locations showing a reduction in preferential refractory erosion in the ladle.
zones of high velocity vectors in metal and refractory erosion pattern. 4. The proposed introduction of a third porous plug in the
vacant quadrant of the ladle bottom at SMS-II BSL
would result in an improved sulfur partition and product
cleanliness by imparting improved slag metal
interactions at lower stirring rates within a stipulated LF
cycle time.

REFERENCES
1. J.A. Duffy and M.D. Ingham, J. Non-cryst. Solid, 1976, vol. 21, p. 373.
2. H. Ohita and H. Suito, Met. Trans. B, 1998, vol. 29B, p. 119.
3. R.W. Young, J.A. Duffy et al., IM & SM, 1992, vol. 19, p. 201.
4. J. Eguchi et al., 4th Int. Conf. Proc. On Molten Slag and Fluxes, 1999,
Sendai, p. 213.
5. D. Majumder, Private Communications, Metallurgical Engineering
Dept, IIT Kanpur, India.
6. M.A.T. Anderson et al., ISIJ international, 1999, vol. 39, p. 1140.

Fig 10. Schematic diagram of ladle with three plugs showing moderate
velocity vector zones in metal and shift in metal circulation zone.

CANADIAN METALLURGICAL QUARTERLY, VOL 45, NO 2

180

CANADIAN METALLURGICAL QUARTERLY, VOL 45, NO 2

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