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STEELMAKING PROCESSES
E.B. Pretorius and R. Marr
Applications Technology Group
Baker Refractories
York, PA 17405-1189
ABSTRACT
This paper attempts to illustrate the benefits of using slag models based on the
thermodynamics of steelmaking reactions and the multi-dimensional modeling of phase
equilibria.
The use of mass balance calculations and the application of these
personal computer-based slag models to the refinement of standard operating procedures can
simultaneously result in shorter process times, more predictable metallurgical results, and
lower refractory costs.
1. INTRODUCTION
The drive in recent years by the iron and steelmaking industry to cut costs and still produce
high quality steels, has illuminated the importance of good slag practices in primary and
secondary steelmaking processes. There has been a gradual realization that the slag phase in
steelmaking is not a necessary evil but a crucial part of modern steelmaking practices. The
goals of producing high quality steel and low costs can not be realized by poor slag practices.
The concept of "slag engineering" or "slag optimization" is becoming more common in many
steelmaking works, as the need to implement these concepts is driven by more stringent steel
quality requirements.
One of the advantages of slag engineering is that customized slags can be designed to fulfill
the metallurgical requirements of specific steel grades. An essential requirement here is the
steelmakers ability to estimate the composition of the slag at any stage of the process. This can
only be done by a mass-balance approach where all the factors contributing to the slag are
considered, viz.: carryover slag, taphole material, deoxidation products, alloy oxidation
products, refractory material, and flux additions. By controlling and manipulating slag
composition and slag formation rates, the efficiency of the steelmaking process can be
optimized.
This paper attempts to illustrate the benefits of using slag models based on the
thermodynamics of steelmaking reactions and the multi-dimensional modeling of phase
equilibria, in conjunction with mass-balance calculations. The application of these computerbased slag models to the refinement of standard operating procedures can simultaneously
result in shorter process times, more predictable metallurgical results and lower refractory
costs. Although the models discussed represent an advance over previous models available
for in-plant use, they are still subject to the primary limitation of requiring conditions close to
equilibrium (high fluidity and/or stirring). Thus while the models are very applicable to
EAF/BOF refining slags, ladle furnace slags, and stainless steel reduction slags; they do not
apply to stainless steel decarburization slags.
function of temperature and composition for basic slags that are compatible with magnesia and
dolomite refractories [5,6].
The liquidus surface has been mathematically modeled in 3D space by a combination of
geometric and thermodynamic estimates. At a given temperature, for any composition, the
models seek the CaO/MgO saturated liquidus boundary (Point O on Figure 1). The
adjustment of CaO/MgO levels to achieve the 100% fluid boundary is shown, and
desulfurization (for reduced slags) is estimated for the 100% fluid slags using published
optical basicity correlations [7,8].
SiO2
S = SiO2
10
90
M = MgO
20
M2S = Mg2SiO4
C2S = Ca2SiO4
S+L
80
30
L = liquid
All liquid
All solid
70
Liquid + solid(s)
40
60
50
50
M2S + L
60
C2S + L
Ca2SiO4
70
Mg2SiO4
40
M2S + L + M
M+L
30
C2 S + L + M
80
20
90
CaO
10
10
20
30
40
50
60
70
80
90
MgO
Table I. Changes in ladle slag composition using various slag deoxidation agents.
(Units in pounds)
Carryover
slag
8
43
21
5
18
6
Deoxidized
slag using Al
7.9
42.5
Deoxidized
slag using FeSi
8.0
43.2
Deoxidized slag
using CaC2
8.4
52.1
% MgO
% CaO
% FeO
Mass-balance % Al2O3
17.2
5.0
5.2
application
% SiO2
32.4
43.8
34.3
% MnO
Al added
65.4
FeSi added
67.8
CaC2 added
77.6
Slag model CaO required*
214
107
0
application
MgO required*
68
108
0
*
The amounts of CaO and MgO required for refractory protection, calculated using the
reduced" slag model at 1600C (2912F). This slag is already CaO and MgO saturated.
From Table I, the mass balance portion, an estimated slag composition is obtained; to which
the slag model may be applied as shown. The results indicate that the CaC2 reduced slag is
over-saturated with respect to the basic oxides, while the other slags are under-saturated. The
model also allows the accurate prediction of desulfurization from these slags as will be seen in
a later example. Utilizing mass balances and the "reduced" slag model the necessary additions
of lime, dolomite, fluorspar, and/or Ca-aluminate for optimum metallurgical and refractory
slags, can be calculated and incorporated in the flux mix.
Example II: Application of the model to the desulfurization of C-Steel
Two grades of steel for which balancing the slag metallurgical requirements against refractory
compatibility is difficult are: Low carbon aluminum- killed and high carbon silicon-killed
steels. In the case of the low carbon aluminum-killed steels, the situation is often one of
under-saturation with the basic oxides (especially lime), while for high carbon silicon-killed
steels the opposite (lime over-saturation) is frequently the case.
a) Low Carbon Al-killed steels:
If the amount of slag carryover is carefully controlled (a requirement for AK-steel) but the
extent of oxygen blown into the steel is not, the slags that form in the ladle could have a wide
composition range. The following mass balance example (Table II) shows the effect of the O
content in the steel during tap on the composition of the ladle slag and other metallurgical
parameters.
100 tons steel tapped from the furnace
227 kg (500 pounds) of carryover slag (EBT)
455 kg (1000 pounds) of a 80/20 lime-spar mixture during tap
Al addition based on an oxygen probe reading just prior to tap.
Table II. Changes in ladle slag composition as a function of steel oxygen content
O in steel
Al added (lb.)
Deoxidation
efficiency*
MgO
CaO
Al2O3
SiO2
CaF2
400
89
100
600
141
95
800
198
90
1000
263
85
1200
335
80
1400
447
70
5.6
66.5
16
5.6
6.2
5.3
62.7
20.8
5.3
5.9
5.6
58.3
25.6
5.0
5.5
7.0
53.9
29.3
4.6
5.1
8.6
49.3
33.3
4.3
4.6
9.6
44.0
38.4
3.8
4.1
40
100
% Al2O3
80
30
25
60
20
Slag
Desulfurization
% Desulfurization
35
40
15
40
45
50
55
60
65
70
% CaO
Figure 2. Plot of % CaO versus % Al2O3 in the slags and the
desulfurizing efficiency of the slags
This figure shows why poor desulfurization can be observed for some heats of the same steel
grade even though the oxygen content in the steel is very low (< 5 ppm). The slags with very
high CaO content on the right side of the plot are not completely fluid so that the amount of
liquid that can desulfurize is limited. On the other side of the spectrum (high Al2O3 slags), the
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slags are completely liquid but have lower sulfide capacities and are not refractory compatible.
Applying a mass-balance approach and the "reduced" slag model to the above example will
immediately highlight the necessary adjustments in the flux mix, in order to form slags in the
ladle according to the steelmaking requirements (low or high sulfide capacities) that are also
compatible with the ladle refractories. For example, additions of lime, dolomite, Caaluminate, and fluorspar could be balanced to form 100% fluid, consistent slags (composition
and volume) in the ladle for any Al addition. The model allows for the selection of slag
volume, sulfide capacity and refractory compatibility simultaneously.
b) High carbon Si-killed grades
Typical problems that are encountered when high carbon Si-killed steel grades are produced
are poor desulfurization in the ladle and clogging at the caster. Both of these problems can be
corrected if a mass-balance approach is used to evaluate the input parameters to achieve an
equilibrium fluid slag. For example consider the following parameters:
Carryover slag: The amount of slag carryover from the furnace is easier to control because
these slags have a lower FeO content and therefore have higher viscosities. The amount of
slag carryover for high-C heats are usually less than for low-C heats.
Alloy additions: Good alloy recoveries are standard for high-C steel due to the lower oxygen
content during tap and the limited amount of furnace slag carryover. The addition of alloys
with low Al levels is very important, as Al pickup can occur under these circumstances, which
may lead to casting problems if the metal stream is not shrouded.
Flux additions: The flux addition at tap should be balanced by sufficient additions of suitable
fluidizers. It is important to realize that considerably less fluidizers are generated when highC steel is tapped than when low-C steel is tapped. Less furnace slag is carried over to the
ladle, improved alloy yields generate less SiO2, and the amount of SiO2 entering into the slag
from steel deoxidation is considerably less due to the lower O content in the steel during tap.
Ignoring the parameters above and adding a "standard" 80/20 lime/spar flux mix, can form
very stiff slags at the ladle furnace; which upon arcing create excessive dust and result in poor
thermal efficiency. It is not uncommon to find slags that are so "hard" that arc-flare damage
occurs in the slag line, especially on the stir-plug side. These lime over-saturated slags have
poor desulfurizing properties, because the amount of liquid that can desulfurize is limited even
though the liquid portion of the slag has a high sulfide capacity. Unfortunately, one of the
misconceptions on sulfur removal (especially the Si killed grades) is that the addition of more
lime to a slag will improve desulfurization. The addition of lime to a slag that can dissolve
more lime is beneficial, but the addition of lime to the slags mentioned above only increases
the refractoriness of the slags and actually decreases desulfurization.
3. SAMPLING PROBLEMS WITH NON-EQUILIBRIUM SLAGS:
Slag samples are usually taken with a steel rod in the vicinity of the stir area of the ladle. If
the slag has a high fluidity, such a sample would be fairly representative of the slag in the
ladle. However, when the fluidity of the slag is low, so that slags are stiff or crusty, a rod slag
sample in the stir area might give a very misleading result. Such a sample would give an
indication of the liquid composition of the slag but would not be representative of the total
slag composition in the ladle. A more representative slag sample would be a cup sample of the
crusty slag in the middle of the ladle. The results in Table III represent the differences
between a calculated ( mass-balance) and analyzed slag composition for a specific high-C steel
heat.
Table III. Differences between the calculated and analyzed slag
compositions.
% MgO
% CaO
% Al2O3
% SiO2
% CaF2
% FeO +
% MnO
Calculated
(Slag A)
3
70
2
12
12
<1
Analyzed
(Slag B)
9
53
4
21
13
<1
The calculated slag analysis confirm what was seen in practice. Very stiff slags that contain
excess lime. The large discrepancy between the calculated slag and the analyzed slags is due
to poor sampling of the slag in the stir area of the ladle. Without a metallurgically predictive
slag model, the engineering/operating solution to this problem was a major addition of
fluorspar which assured the achievement of metallurgical goals at the expense of the
refractories. The problem is compounded by adding too much lime, then adding too much
spar to compensate. In a LF operation, this consumes more time and energy. A more detailed
treatment of slag rheology follows because of its major application in such situations.
4. DESULFURIZATION PRINCIPLES AND SLAG RHEOLOGY
Most steelmaking slags are composed of a mixture of liquid and solids. The balance between
the liquid and solid fractions of a slag has a large impact on the rheology of the slag, and is a
function of slag composition and temperature. The composition of the slag is influenced by all
the contributions from the steelmaking process (EAF slags, fluxes). A key requirement in the
design of optimum slags is that these slags are fluid at processing temperatures. A common
mistake that is made in mass-balance calculations (such as sulfide capacity and sulfur
distribution) is the assumption that the slags are completely liquid at steelmaking
temperatures. In many cases the slags could be over-saturated with CaO and/or MgO so that
worse than calculated sulfur removal is observed. This is illustrated in the following example:
Consider the following two slags at 1600C (2912F):
% SiO2
% CaO
% MgO
Phases present
Slag A
38
45
17
Slag B
35
50
10
It is the lime dissolved in the liquid fraction of the slag that is removing sulfur from the steel
and not the lime as determined by the chemical analysis of the "total" slag. The undissolved
lime in the slag does not remove sulfur [14]. The composition of the liquid fraction of slag B
is very similar to the composition of slag A. The addition of more lime than the slag can
dissolve (slag A to slag B), will only result in a decrease in the amount of liquid in the slag
that can desulfurize (liquid composition stayed constant) and an increase in the viscosity of the
slag. The errors that can be made by not considering the solid/liquid ratio of a slag are
illustrated in Table IV.
Table IV. Example of possible errors in the calculation of final metal sulfur content
Considering the total
slag chemistry (Slag A)
Si (wt%)
0.035
0.035
0.035
WM (tons)
100
100
100
WS (lb.)
2000
2000
(2000*0.43) = 860
0.698
0.717
0.698
20
20
20
log CS
-3.01
-2.74
-3.01
LS
36.71
67.62
36.71
SF (wt%)
0.025
0.021
0.030
Correct
Wrong!!
Correct
[% O] (ppm)
Calculated
result
The application of the "reduced" slag model is a very useful tool to evaluate and design
desulfurization slags for C-Steel and stainless steel production since it calculates to a 100%
fluid slag. The model provides information on the solid-liquid phase equilibrium relationships
for multi-component slags as a function of temperature and composition which is critical for
the engineering of slags to achieve desulfurization goals. The choice of fluidizers (SiO2,
Al2O3 and/or CaF2) in the design of these slags is very important because the solubility of CaO
and MgO is strongly dependent on the type of fluidizer used. The slags listed in Table V were
generated with the reduced slag model and the effect of fluidizer on the solubility of CaO
and MgO is clearly illustrated. All the slags in Table V have a high fluidity and are just
saturated with respect to CaO and MgO and are therefor also compatible with magnesia and
dolomite refractories. From Table V it can be inferred that Al2O3 and CaF2 are much
stronger fluidizers than SiO2 for increasing the solubility of CaO in the slag. The effect of
Al2O3 on the solubility of CaO and MgO is illustrated in Figure 3. These slags are also just
saturated with respect to CaO and MgO and therefore contain the maximum amount of CaO
and MgO that can be dissolved at 1600C (2912F).
Table V. Compositions of slags that are just CaO and MgO saturated at 1600C
(=optical basicity, Cs = sulfide capacity, and Sf=final sulfur)
% CaO
% MgO
% Al2O3
% SiO2
% CaF2
-Log Cs
Sf*
Slag 1
45
17
38
Slag 2
52
10
17
21
0.696
3.04
0.035
0.744
2.35
0.017
Slag 3
54
13
22
11
0.766
2.04
0.010
Slag 4
58
8
23
9
3
0.788
1.72
0.005
CaO
MgO
17
1600C
57
56
16
55
15
54
53
52
14
13
51
12
11
50
49
10
48
47
46
45
58
18
44
0
10
15
20
25
30
35
Using the reduced slag model a infinite number of slags can be designed with various
sulfide capacities, using various combinations of fluidizing agents, to obtain specific
metallurgical goals.
4.1. Slags for resulfurized steel grades
To generate fluid slags of decreased thermodynamic sulfide capacity (while maintaining
basicity for basic refractory compatibility) requires substitution of MgO for CaO. These slags
will have lower CaO/SiO2 ratios which will increase the solubility of MgO in the slag. The
MgO saturation values as a function of CaO/SiO2 ratios are shown in Figure 4. All these slags
are 100% fluid at steelmaking temperatures and compatible with magnesia slag line
refractories.
45
1700C
1600C
40
35
30
25
20
15
0.4
0.6
0.8
1.0
1.2
1.4
% CaO/% SiO2
Figure 4. MgO saturation requirements of CaO-MgO-SiO2 slags at 1600C (2912F)
The use of more than about 3% of Al2O3 and CaF2 as fluidizers should be avoided as these
components will increase the solubility of lime in the slag and hence desulfurization. An
alternate approach is to manipulate slag rheology in order to minimize sulfur removal (where
it is desired to first desulfurize and then precisely resulfurize). By adding excess CaO and
MgO to the slag (often as calcined dolomite), the fluidity of the slags can be decreased so that
the effective amount of liquid that can desulfurize is diminished. In either of these
circumstances the slag model allows the prediction of resulfurization efficiency.
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