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Desulfurization of Molten Steel in RH-Degasser


by Powder Blowing to Produce Silicon Steel
Operational Results Maanshan ISCO
Conference Paper June 2015

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3 authors, including:
Christian Schrade

Zulfiadi Zulhan

Tenova

Bandung Institute of Technology

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Desulfurization of Molten Steel in RH-Degasser by Powder Blowing to Produce


Silicon Steel Operational Results Maanshan ISCO
C. Schrade, H. Nicolai, Tenova Metals Deutschland
Z. Zulhan, Metallurgical Engineering, Institut Teknologi Bandung, Indonesia

Contact data

C. Schrade, Tenova Metals Deutschland GmbH, Am Lichtbogen 29, 45141, Essen, Germany, Phone +49 201 1891
723, Fax: +49 201 1891 470, Email : christian.schrade@tenova.com

Summary

In ULC (ultra low carbon) - electric steel grade which is well known as NGO (non-grain oriented) silicon steel grade, the
presence of sulfur may increase magnetic hysteresis loss and suppress the grain growth. Therefore, the sulfur content
in this steel grade should be kept less than 0.005% or even less than 0.002%. Steel desulfurization during RH
treatment by the addition of Ca-based fluxes through a powder injection lance as well as through an alloying vacuum
hopper system was investigated by researchers in the 1990s. However due to the reduction of the RH vacuum vessel
refractory service life, particularly in snorkel and bottom part of RH vessel, this technique was not a common practice in
the steel industry. However, for non-grain oriented (NGO) silicon steel grades, which have the carbon and sulfur
content requirements of less than 30 ppm and 20 ppm, respectively, deep desulfurization is accomplished directly after
decarburization and alloying addition during the RH vacuum treatment. To calculate the sulfur content during and after
powder blowing of the RH vacuum process, a kinetic model of desulfurization, introduced previously by other
researchers, was improved and tested. The model is integrated in the Level 2 RH Process Automation system.
Industrial and practical results from plant operation of the 300t RH Plant of Maanshan ISCO, China are highlighted and
compared with the theoretical considerations.

Key Words

RH plant, desulfurization, powder blowing, silicon steel

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Introduction
The presence of sulfur in the steel has a strong
impact on the steel quality. The efforts to remove and
control sulfur content in steel products are started at
the ironmaking stage, hot metal pretreatment,
primary steelmaking and ladle metallurgy by top slag
reaction as well as by powder injection.
Desulfurization under a vacuum environment by
means of vacuum tank degassing (VTD) was
considered to be more effective due to intense mixing
and contact between molten steel and slag.
Desulfurization of molten steel under vacuum during
the RH-treatment was introduced by Okada et al [1],
in order to reduce sulfur content from 30 ppm to less
than 5 ppm by powder blowing of a CaO-CaF2 flux.
Knoop and Tiekink [2] reported test results of
desulfurization performance during RH treatment by
the addition of lime and pre-molten calcium-aluminate
flux via the vacuum hopper system with a sulfur
reduction from 50 ppm to approximately 30 ppm.
The installation of a powder injection lance on a RH
plant for dephosphorization and decarburization to
produce ULC steel grade was reported by Poucke et
al [3]. Iron oxide was blown for the purpose of
decarburization and lime is blown to reduce the
phosphor content of the liquid steel. In addition, the
lance was also used for desulfurization trials by
blowing of CaO-CaF2 or CaO-Al2O3 fluxes [4]. It was
observed that utilization of a CaO-CaF2 flux boosts
dramatically the wear of RH vessel refractories.
Consequently, it was decided to use pre-molten CaOAl2O3 fluxes for further desulfurization trials.
Since these trials, desulfurization during RH
treatment could not be established as a common
practice in the steel production process, mainly due
to the heavy wear of RH snorkel and inner vessel
refractories. However, regarding the production of nongrain oriented (NGO) silicon steel grades containing
ultra-low carbon and ultra-low sulfur levels there are
only few alternatives.
Due to contrary metallurgical mechanisms for
decarburization and desulfurization, it is not a good
practice to kill the steel by aluminum addition directly
after BOF / EAF tapping in order to provide a
reductive condition for desulfurization. Subsequently
oxygen injection during RH treatment must follow in
order to change the condition from reducing to
oxidizing for decarburization purposes. Instead, the
mechanism to produce NGO steel grade will be vice
versa: Desulfurization of the liquid steel will be
performed after decarburization and alloying addition
of the RH vacuum treatment.

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Kinetic Model of Desulfurization by Powder


Blowing
The desulfurization reaction by powder blowing
during the RH vacuum treatment is considered to be
controlled by mass transfer of sulfur in molten steel to
the surface of flux particle. The sulfur content in
molten steel during powder injection and the final
sulfur content are predicted by following equations
[5]:
S S S

Sf = So

(1)

(2)

The kinetic rate constant (ks) in equation 1 is


determined based on the equation proposed by Wei
et al. [6]:
ks =

(3)

Where Lsm = Ls s / f
Figure 1 shows the theoretical calculation of the
sulfur content during powder blowing, with an initial
sulfur content of 60 ppm. The final sulfur content is
dependent on the amount of powder blown. However,
a sulfur content of less than 20 ppm is difficult to
achieve starting from an initial level of 60 ppm. Based
on the model calculations, final sulfur content of less
than 20 ppm can only be achieved when the initial
level is less than 40 ppm, illustrated in Figure 2 and
3, respectively.

Figure 1: Calculation of sulfur content during powder


blowing for initial sulfur content of 60 ppm (300 ton
steel, blowing rate: 100 kg/min, LS: 250)
In order to perform these values the addition of flux of
5.0 kg/ton (Figure 2) is required by powder blowing.
On the other hand, around 3.3 kg/ton flux are

required to remove sulfur from 30 ppm to less than


20 ppm as shown in Figure 3.

Figure 2: Calculation of sulfur content during powder


blowing for initial sulfur content of 40 ppm (300 ton
steel, blowing rate: 100 kg/min, LS: 250)

Figure 3: Calculation of sulfur content during powder


blowing for initial sulfur content of 30 ppm (300 ton
steel, blowing rate: 100 kg/min, LS: 250)

Figure 4: Calculation of sulfur content during powder


blowing for various initial sulfur contents (300 ton
steel, blowing rate: 100 kg/min, LS: 250, Flux 5.0
kg/ton)

Figure 5: Calculation of sulfur content during powder


blowing for various blowing rate (300 ton steel, LS:
250, Flux 5.0 kg/ton)

The effect of the flux blowing rate on the final sulfur


content is shown in Figure 5. Lower sulfur content
can be achieved by reducing the flux blowing rate;
however, a longer treatment time is required resulting
in higher temperature losses and a higher operating
cost. Typical powder blowing rates range from 100
150 kg/minute.
The sulfur distribution ratio (Ls) of the flux, which
depends on the sulfide capacity of fluxes, plays an
important role in determining the final sulfur content
(Figure 6). A high Ls value provides a good condition
of blown flux to remove sulfur from molten steel so
that low final sulfur content can be achieved by
having high Ls values of flux.

Figure 6: Calculation of sulfur content during powder


blowing for various sulfur distribution ratio, Ls (300
ton steel, blowing rate: 100 kg/min, Flux 5.0 kg/ton)

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Theoretically, burned lime has high sulfide capacity,


however the melting point of lime is high (approx...
2600 C for pure CaO), therefore lime cannot be
melted during the desulfurization process. Solid
particles of lime can limit the reaction rate so that
lime diameters of less than 0.2 mm are required
enlarging the surface area for the reaction. The
desulfurization reaction can be increased by addition
of CaF2 or Al2O3 in the form of pre-molten additions.
As mentioned before the usage of CaO-CaF2 fluxes
promote high refractory wear of snorkel and lower
part of the RH vessel. For that reason, perfused / preis
recommended
as
molten
CaO-Al2O3
desulfurization agent to be blown through lance into
the RH vessel.

Operational Results at Maanshan ISCO


The 300 t Duplex RH Plant was installed and
commissioned by Tenova in 2014, Figure 7. The
plant is equipped with a multifunctional top lance with
the following functions:
Burner function for refractory heating
Blowing of metallurgical oxygen for process
purposes
Blowing of oxygen between treatments for
skull removal
Powder blowing for deep desulfurization

The designed powder blowing rate amounts to 50


150 kg/min. During powder blowing a lance distance
of 2 - 3 m to the metal bath is to be secured. Powder
is supplied by a pneumatic conveying system. Two
bins are provided for mixing of CaO powder and
Al2O3 powder. The RH plant layout in Figure 8 shows
the position of the powder bins, the multifunctional
lance and the alloy bins.

Figure 8: Layout for powder blowing system on RH


plant
The process route to produce NGO silicon steel is
BOF RH CCM. The RH production process of
NGO steel gradesas shown in Figure 9, contains the
following steps:

Decarburization from 450 ppm to less than


15 ppm
Deoxidation by aluminum addition
Alloy addition of FeSi and FeMn
Desulfurization by powder blowing from 60
ppm to less than 30 ppm
Final alloying and homogenization

All process steps are pre-calculated and updated by


recalculation by the Level 2 Process Model. Focusing
on the desulfurization process the Level 2 Process
Model determines:
The amount of powder to be blown
depending on initial and final sulfur level
The blowing and, consequently
The required blowing time

Figure 9: Process step on RH plant for NGO silicon


steel production
Figure 7: 300 t Twin RH Plant at Maanshan ISCO

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Five heats were observed and analyzed during the


commissioning period of the Maanshan RH plant.

The fluxes used for commissioning consisted of CaO


and Al2O3 with a mixing ratio of 60%:40%. The
calculated flux consumption was in the range of 3 5
kg/ton of steel. The fluxes were blown at a vacuum
pressure of less than 100 mbar. A sulfur removal
efficiency of more than 55% could be achieved by
blowing flux amounts of 5 kg/ton. Figure 10 shows
the calculation values of the sulfur content as a
function of time compared to the real analyzed data.
Figure 11 shows the results of the real analyzed data
in comparison of the Level 2 Process Model
calculation results giving a good correlation.

Conclusion
The production of NGO silicon steel grades, having
the requirement of ultra low carbon and ultra low
sulfur levels, deep decarburization as well as deep
desulfurization can be performed by the RH process.
A kinetic desulfurization model was developed in
order predict the sulfur contents during the process.
Five heat data for NGO steel production were
analyzed for fine tuning of the introduced/proposed
kinetic desulfurization model. It shows that the
proposed kinetic model can be used to predict sulfur
content during powder blowing as well as the final
sulfur content in the molten steel. This kinetic model
was implemented in Level 2 RH Process automation
system.

Abbreviations

Figure 10: Sulfur content during powder blowing,


calculated vs analyzed data

dp
k
Ls
Q
S
Se
Sf
So
St
t
Wf
Ws
f
s

diameter of powder particle [m]


desulfurization constant rate [1/second]
sulfur distribution ratio
steel circulation rate [kg/s]
sulfur content at time t [%]
sulfur content at equilibrium [%]
final sulfur content [%]
initial sulfur content [%]
sulfur content at time t [%]
time [second]
amount of blown flux [kg]
steel weight [ton]
flux density [kg/m3]
steel density [kg/m3]

References

Figure 11: Correlation of sulfur content, calculated vs


plant data
For the analysis of these heats, a flux sulfur
distribution ratio (Ls) of 250 was used in the
calculation of the Level 2 Process Model. A higher
sulfur distribution ratio might be attained by using
pre-molten CaO-Al2O3 instead of the CaO-Al2O3
mixing. Consequently, higher sulfur removal
efficiency can be expected

[1] Okada, Y.; Fukagawa, S.; Ieda, K.; Maya, K.;


Ikemiya, H.; Shinme, K.: Development of RH-Powder
Top Blowing Process; La Revue de Metallurgie
CIT, 1994, Juin, P. 923-930
[2] Van der Knopp, W.; Tiekink, W.: Desulfurization
during RH Treatment at Hoogovens Staal; La Revue
de Metallurgie CIT, 1996, Avril, P. 533-540
[3] Van Poucke, N. L.; Peeters, F. H.: Improvement of
Dephosphorization and Decarburization by Injection
of Metallurgical Powders in the RH; La Revue de
Metallurgie CIT, 2000, Avril, P. 527-534
[4] Van Poucke, N.: Use of the MESID Lance in the
th
RH-Degasser at the Sidmar Steel Plant; 4 European
Oxygen Steelmaking Conference (EOSC), Austria,
2003
[5] Zulhan, Z.; Patriona, Y.A.; Schrade, C.:
Desulfurization of Molten Steel in RH-Degasser by
Powder Blowing to Produce Non Grain Oriented
(NGO) Silicon Steel; SEAISI Quarterly Journal, 2013,
No. 4, P. 32-36
[6] Wei, J.-H.; Zhu, S. J.; Yu, N.-W.: Kinetic Model of
Desulfurization by Powder Injection and Blowing in
RH Refining of Molten Steel; Ironmaking and
Steelmaking, 2000, No.2, P.129-137

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