ISIJ International, Vol. 44 (2004), No. 1, pp.

37–42

Physical Simulation of Impurity Removal through Submerged

Liquid Slag Injection in Steel Melt

Satadal GHORAI, G. G. ROY and S. K. ROY

Department of Metallurgical and Materials Engineering, Indian Institute of Technology, Kharagpur 721 302 India.
Email: ggroy@metal.iitkgp.ernet.in
(Received on May 26, 2003; accepted in final form on July 24, 2003 )

With the increase in demand for quality steel having very stringent compositional control, the secondary
steelmaking has become one of the significant developments in the steel making technology during the
past few decades. Injection of powder with inert carrier gas is commonly practiced in industry to decrease
the impurity contents of steel in a more economical way. Such high temperature metallurgical operations
are mass transfer controlled and accordingly the design and operating parameters have significant roles to
play. However, powder particles can only penetrate partially to the liquid melt while most of the particles as-
cend through the melt as “particles inside the bubble” in the semi-solid state without contributing much to
mass transfer. In this regard submerged liquid slag injection may be considered as a potential area of inves-
tigation. In the present study, simulation of the submerged liquid slag injection in steel melt has been car-
ried out using a cold model in the laboratory. Relative contributions of the transitory to permanent contact
reactions have been estimated from several experimental data in conjunction with the mathematical model
proposed by Ohguchi and Robertson. The present results show that mass transfer rate increases with in-
crease in gas flow rate, liquid injection rate and lance depth. An empirical correlation for overall mass trans-
fer rate constant as a function of gas flow rate, oil injection rate and lance depth has been developed. The
present result also indicates that transitory contribution increases significantly with increase in gas flow
rate.
KEY WORDS: ladle steel making; submerged liquid injection; physical modeling; mass transfer.

a result those particles move up in semi solid state, with

1. Introduction
The secondary steelmaking is an essential and indispens-
able part in modern day steel making. Energy optimization,
higher productivity, and demand for quality steel with very
stringent compositional control and extra low impurity con-
tent, have led to the development of the ladle steel making
or the so called secondary steel making in the past few
decades. Since metallurgical operations involved in steel
making are generally conducted at relatively high tempera-
tures, mass transfer between the two immiscible liquids,
namely slag and metal, plays a significant and important
role in reducing the impurity level. Predominantly, sub-
merged injection of gas and powder in ladle is commonly
practiced in the industry to decrease the impurity level in a
more economical way. This powder injection process offers
one more reaction zone, the transitory contact zone, apart
from the permanent contact zone at the top slag–metal in-
terface. In transitory contact zone, the powder particles
react during their ascent through the melt. The turbulence
caused by the carrier gas also enhances the reaction kinet-
ics. However, the success of powder injection remains lim-
ited by the fact that only 30 to 40 % of the powder particles
can penetrate into the melt and the remaining ascend as
“particle inside the bubble”.1) Gas film layer around those
particles offer resistance both to heat and mass transfer. As
very little participation to mass transfer process. Therefore,
liquid slag injection instead of powder injection could be
considered as a potential technique to improve mass trans-
fer remarkably during the rise of slag droplets through melt
from the bottom by submerged injection.
In order to have a better understanding of the influence of
various design and operating parameters on the kinetics of
submerged liquid injection, a large number of experiments
are required to be conducted at pretty high temperatures
(1 300–1 500°C), which is not only cumbersome but also
a costly affair. On the other hand, mathematical modeling in
conjunction with physical model study appears to be an al-
ternative approach for studying the operational parameters
of liquid metal processing. With this idea in view, the pre-
sent work aims at elucidating the effect of various operating
parameters on the refining of steel through submerged liq-
uid slag injection in steel melt.
Till now there are no literature reporting on submerged
injection of liquid slag through steel melt, possibly due to
inherent problems associated with the process. However,
several investigations relating to powder injection refining
of steel at high temperature are reported.2–8) But the drawn
inferences are not at all consistent; while some claimed a
major contribution from reactions occurring at the transito-
ry contact zone and others advocated predominance of

37 © 2004 ISIJ
 ISIJ International, Vol. 44 (2004), No. 1
the permanent contact reaction. Some water model experi-
ments9–13) have also been reported on mixing, bubbling-jet-
ting phenomena during powder injection and slag–metal
mass transfer in gas stirred ladles.
Simulation of liquid slag injection in steel melt has been
studied in the laboratory by injecting oil along with air in
aqueous solution of benzoic acid by a submerged lance. In
such a cold model study, the analogy of distilled water to
the liquid metal and paraffin oil to the liquid slag, and ben-
zoic acid to the transferring impurity in the steel melt, have
been chosen in defining the system. Separate contributions
of the transitory and permanent contact reactions have been
estimated by analyzing experimental data in combination
with an existing mathematical model proposed by Ohguchi
and Robertson.8) Effect of various parameters like gas flow
rate, lance position, oil injection rate have so far been stud-
ied and are presented in the following section.
2. Experimental
2.1. Set Up
The experimental setup is shown in Fig. 1. The experi-
ments were conducted in a cylindrical perspex vessel of di-
Fig. 1. Schematic representation of the experimental setup.
Table 1. Various relevant parameters used in industry and those used in the laboratory scale experiments.
© 2004 ISIJ
ameter 0.20 m. An air compressor was used to inject air
into the liquid bath. The air flow rate was monitored with
the help of a rotameter (in case of high flow rate
16.34105 Nm3/s) and a capillary flow meter (in case of
low air flow rate 16.34105 Nm3/s). The lance was de-
signed for submerged injection of gas and oil simultaneous-
ly through a nozzle of 2 mm diameter. The oil flow rate was
controlled by maintaining a constant air pressure in the oil
reservoir. The aqueous sample was taken periodically from
the center of the bath through a tap.
2.2. Similarity Criteria
All necessary similarity criteria were considered while
designing cold model setup in the laboratory.14) All relevant
data pertaining to properties of slag and metal, vessel
geometry etc. relevant to industrial practice and those used
in the present laboratory scale experiments are presented in
Table 1. Since submerged liquid slag injection is not yet a
regular industrial practice, the slag/metal volume ratio has
been taken at 0.1, which is normally maintained at around
0.1 for ladle treatment.15)
2.3. Types of Experiments Performed
2.3.1. Experiments with Top Oil Layer
Some experiments were carried out with the top oil layer
and gas injection alone from the bottom of the vessel to
compare the results with the combined injection of oil and
gas through the submerged lance. A typical experiment
with top oil layer was conducted by taking 5 L aqueous so-
lution of benzoic acid in the vessel to which 500 mL of oil
was carefully poured down the sidewall of the vessel. The
pouring time was less than 5 s. The lance was kept sub-
merged at a level of 95 % of the bath height and air was
injected at a definite rate. The duration of each run was
22 min.
2.3.2. Combined Injection of Oil and Air
For a combined injection experiment, 5 L aqueous solu-
tion of benzoic acid was taken in the perspex vessel.
Subsequently, 500 mL oil was poured into the oil reservoir,
which was subjected to an air pressure to push the oil at a
particular rate through the lance. Simultaneously, air was
also injected into the aqueous phase at various rates through
the submerged lance. Experiments were conducted for dif-
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 ISIJ International, Vol. 44 (2004), No. 1

ferent lance position, oil injection rate and gas flow rate.
During each experiment, 20 mL of benzoic acid solution
was taken out of the vessel at a definite interval of time
through a tap placed at the center of the bath. Subsequently,
the concentration of the solution was measured by titration
against a standard NaOH solution using phenolpthalein in-
dicator. These concentration values were utilized to deter-
mine the mass transfer rate constant, k (min1).
3. Data Analysis
3.1. Determination of Overall Mass Transfer Rate
Constant
Assuming the mass transfer on the aqueous side (metal
side) to be rate controlling,12,13) the rate may be expressed
as:
dC t
V  β A( C t C e ) .......................(1)
dt
On integration and simplification, the above equation
takes the form:
ln C*kt..................................(2)
where,
C t C e
C *
C0 C e
Equation (3) can be rearranged in the following form:
dy   1  a
  a 1  E  y  ..................(4)
dt *   τ  τ
From Eq. (4), it is seen that when (dy/dt *) is plotted as a
function of “y”, a straight line would be obtained and the
values of “a” and “E” can be estimated from the intercept
and the slop of the line, respectively. A typical plot is
shown in Fig. 2.
Now, the total rate of mass transfer from the aqueous
phase to the oil phase can be calculated by putting the value
of “a” and “E” in Eq. (4). The total amount of benzoic acid
transferred from the aqueous phase to oil can be obtained
by estimating the area under the curve of the plot of
(dy/dt *) against t *. On the other hand, the total amount of
benzoic acid transferred from the aqueous phase to oil
phase through permanent contact reaction can only be ob-
tained by putting “E0” in Eq. (3). A typical such plot for
the combined injection of oil and air at a constant flow rate
is presented in Fig. 3.
Such plots obtained under different experimental condi-
tions have been utilized to estimate the relative contribution
of transitory and permanent contact reactions. The contri-
bution of transitory contact reaction has been obtained by
subtracting the area under the curve for permanent contact
reaction from that for the overall reaction.

βA
k
V
The plot of the ln C * against time should yield a straight
line and the value of “k” could be obtained from the slope
of this line.
3.2. Estimation of Relative Contribution of Permanent
and Transitory Contact Reaction
The liquid slag injection process may be viewed as two
reactions taking place parallelly; one at the top slag–metal
interface, called the permanent contact zone and the other
at transitory contact zone, during the rise of the slag
droplets through the melt. Ohguchi and Robertson derived
a mathematical model8) to describe the kinetics of refining
of steel by powder injection in terms of two empirical di-
mensionless mass transfer rate constants; one at the perma-
nent contact zone (a) and the other at the transitory contact
zone (E). In this sense, this model is quite general with re- Fig. 2. Plot of (dy/dt *) vs. y at a constant gas flow rate.
spect to refining processes through submerged injection (ir-
respective of powder or liquid injection from the bottom);
and these rate constants may be estimated empirically for
any specific injection process. Therefore, this model has
been successfully used to represent the present case of sub-
merged liquid slag injection.
Assuming the aqueous bath to be well mixed condition
and the aqueous phase mass transfer as the rate controlling
step, the non-dimensional form of oil injection process may
be expressed as:

dy  1 y 
 a  y  Ey .....................(3)
dt *  τ 
Fig. 3. Plot dy/dt * vs. t * at a constant gas flow rate.

39 © 2004 ISIJ
 ISIJ International, Vol. 44 (2004), No. 1
4. Results
4.1. Experiments with Top Oil Layer
Liquid–liquid mass transfer with top oil layer and gas ag-
itation from the bottom is well reported in literature. Here a
few experiments with top oil layer have been carried out to
compare the results of combined injection experiments. In
Fig. 4, the mass transfer rate constants have been plotted
against gas flow rates (Q), for experiments with top oil layer.
It reveals that the rate of mass transfer initially increases
with the increase in gas flow rate but subsequently, decreas-
es again at higher flow rates. This result is in well agree-
ment with the data published in literature.15,16) Such behav-
ior was attributed to improved mixing of the bath, decrease
in size of oil droplet and its penetration deep into the water
bath. Later, the effect of stronger agitation on the mass trans-
fer rate begins to fall because the size and number of oil
droplets start approaching steady state.15,16)
A plot of the volumetric mass transfer coefficient (b · A)
against gas flow rate (Q) in a natural logarithmic scale is
depicted in Fig. 5. It is seen that b · A and Q yields a rela-
tionship of the form:
b · A Qn ...................................(5)
where, “n” is the exponent of gas flow rate characterizing
the intensity of bath mixing. The figure depicts that at lower
gas flow rates the volumetric mass transfer coefficient slow-
Fig. 4. Variation of mass transfer rate constant with gas flow rate
for experiments with top oil layer.
Fig. 5. Variation of volumetric mass transfer coefficient with gas
flow rate for experiments with top oil layer.
© 2004 ISIJ
ly increase, but a sharp rise is observed beyond a certain
gas flow rate (9.73105 Nm3/s). The values of the expo-
nent “n” (0.3839 and 1.2454) for two different flow regimes
also indicate the abrupt change in the volumetric mass
transfer coefficient. This result is in agreement with the lit-
erature data, where it has been reported that the value of
“n” varies between 0.25 and 3.0 for both cold and high tem-
perature model experiments.12,15–17) During experiment it
was observed that entire top oil layer breaks down into
droplets at and around gas flow rate of 9.73105 Nm3/s.
4.2. Combined Injection of Oil and Air
4.2.1. Effect of Gas Flow Rate
The variation of mass transfer rate constants with gas
flow rate for the combined injection experiments is depicted
in Fig. 6. This figure illustrates a continuous rise in the
mass transfer rate constant with increase in the gas injec-
tion rate. However, unlike in experiments with top oil layer,
the relationship is found to be a linear one. A comparison
of the mass transfer rates between experiments conducted
with top oil layer and combined injection (Figs. 4 and 6) re-
veals that there prevails a higher rate of mass transfer at
comparatively lower gas flow rates during combined injec-
tion experiments. This may be attributed to the added mass
transfer contributed by the transitory reactions. However, at
higher gas flow rates, experiments with top oil layer demon-
strated higher mass transfer rates. This may be attributed to
emulsification of the whole amount of oil available at the
top from the start of the experiment, contributing to more
surface area and leading to higher rate of mass transfer.
The effect of gas flow rate on the relative contribution of
permanent and transitory contact reactions during com-
bined injection is depicted in the Fig. 7. This diagram
demonstrates the changes in the relative contribution of the
permanent contact reaction and transitory contact reaction
with gas flow rate. It is clearly revealed that as the gas flow
rate increases, the relative contribution of permanent con-
tact reaction decreases, whereas that of the transitory con-
tact reaction increases. This may be due to enhanced turbu-
lence in the bath and breakup of oil droplets with increase
in gas flow rate. Decrease in mean droplet diameter with in-
crease in turbulence in the bath in a liquid-liquid system
has been well reported in literature.18–21) Such a situation
leads better mixing in the bath and larger exposed surface
area of oil droplets, favorable to mass transfer in the transi-
Fig. 6. Variation of mass transfer rate constant as a function of
gas flow rate for combined injection experiments.
40
 ISIJ International, Vol. 44 (2004), No. 1
Fig. 7. Relative contributions of transitory and permanent con-
tact reactions at different gas flow rates.
Fig. 8. Variation of mass transfer rate constant as a function of
gas flow rate at different oil injection rate.
tory reaction zone. A decrease in the contribution of perma-
nent contact zone is evident since the oil droplets which are
loaded with more amount of benzoic acid would eventually
join the top oil layer, and thereby, creating a lower concen-
tration gradient for the mass transfer process in permanent
contact zone.
4.2.2. Effect of Oil Injection Rate
The influence of oil injection rate on the mass transfer of
benzoic acid from the water to oil is depicted in Fig. 8. This
figure clearly demonstrates that an increase in oil injection
rate leads to an increase in the mass transfer rate. It is obvi-
ous that an increase in the oil injection rate would increase
the volume of oil per unit volume of the bath per unit time,
resulting in a higher rate of mass transfer. As long as the oil
droplets are wide apart to interact very closely to coales-
cence, increase in oil injection rate is expected to increase
in mass transfer rate. It is further noticed that this effect is
more pronounced at higher gas flow rates, which may be at-
tributed to better mixing and decrease in droplet size18–21)
and subsequently, higher mass transfer rate at higher gas
flow rates.
4.2.3. Effect of Lance Position
The influence of lance position on the mass transfer rates
at different gas flow rates and at a constant oil injection rate
41
Fig. 9. Variation of mass transfer rate constants with gas flow
rate at different lance position.
Fig. 10. Plot of the observed and predicted values of the overall
mass transfer rate constant for combined injection of oil
and air.
of 2.78106 m3/s is shown in Fig. 9. This figure demon-
strates that the mass transfer rate constant decreases as the
lance position is raised from 0.95 to 0.5 of the bath height.
With rising of the lance position, distance traversed by bub-
bles through the bath decreases as well as the residence
time of the oil droplets in the bath also decreases. There-
fore, the volume work done by the bubbles during their rise
through the bath decreases that results in lower agitation,
poor mixing and lower mass transfer in the bath. Similarly,
decreased residence time of oil droplets in the bath also re-
sults in lower rate of mass transfer through transitory con-
tact reaction. It is further observed that the effect of lance
height on the mass transfer becomes prominent at higher
gas flow rates, which is attributed to better mixing in the
bath.
4.3. Correlation
A statistical correlation has been developed to calculate
the overall mass transfer rate constant of the liquid slag in-
jection process as a function of gas flow rate, lance depth
and oil injection rate. The correlation is given by the Eq.
(6),
k 3.57107Q0.73q0.87h0.62 ......................(6)
where, k is the mass transfer rate constant (min1), Q is the
gas flow rate (3.37105 to 24.18105 Nm3/s), q is the
oil injection rate (2.08106 to 2.78106 m3/s) and h is
lance depth (0.09 to 0.171 m).
The experimental values and the observed values of mass
transfer rate constants are plotted in Fig. 10. The goodness
© 2004 ISIJ
 ISIJ International, Vol. 44 (2004), No. 1
of fit of the correlation has been found to be 98 % where all
the data lie within 10 % envelope around the perfect match-
ing line (line passing through origin with a slope of one).
5. Conclusions
t *in
The cold model study envisaged for secondary refining
of steel by liquid slag injection led to the following conclu-
sions:
(1) A sharp rise in the volumetric mass transfer coeffi-
cient is observed above a certain gas flow rate (9.73
105 Nm3/s) for experiments with top oil layer.
(2) Unlike the experiments with top oil layer, combined
submerged injection of oil and air has demonstrated an in-
crease in the mass transfer rate with gas flow rate obeying a
linear relationship.
(3) An increase in the oil injection rate led to an in-
crease in the mass transfer rate.
(4) The mass transfer rate was found to decrease with
decrease in the lance depth.
(5) The relative contribution of transitory contact reac-
tion has been found to increase with the increase in the gas
flow rate for combined injection experiments.
(6) An empirical correlation has been developed to es-
timate the overall rate constant for the liquid slag injection
process as a function of gas flow rate, oil injection rate and
the lance depth.
Nomenclature
A : Cross sectional area of the laboratory vessel (m2)
a : Dimensionless rate constant for permanent contact
reaction
Ct : Concentration of benzoic acid in water (kg/m3) at
any time, t
C0 : Initial benzoic acid concentration in water (kg/m3)
Ce : Equilibrium concentration of benzoic acid in water
(kg/m3) at equilibrium with paraffin oil
C * : Dimensionless aqueous phase concentration of
benzoic acid, defined as: [(CtCe)/(C0Ce)]
E : Dimensionless rate constant for transitory reaction
H : Bath height (m)
h : Lance position (m)
k : Mass transfer rate constant (min1)
Lvol : Partition coefficient on volumetric basis
Q : Gas flow rate (Nm3/s)
q : Oil injection rate (m3/s)
© 2004 ISIJ
V: Bath volume (m3)
t* : Dimensionless time, defined as: t *(Lvolq/V ) t
t *in :
Dimensionless injection period
t: Defined in terms of t *, as follows:
t t * when 0 t * t in*
t t in* when t *
y : Dimensionless aqueous phase concentration of
benzoic acid, defined as: yCt /C0
b : Mass transfer coefficient (m/s)
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