Process metallurgy

Dedicated to Professor Dr.-Ing. Dieter NeuschOtz on the occasion ofhis 65th birthday

Thermodynamic and kinetic aspects of the desulphurisation reaction in secondary

metallurgy
Helmut Lachmund, Yongkun Xie and Klaus Harste

The desulphurisation of liquid steels with a refining ladle top slag is one of the most important processes of secondary metallurgy. But the
process control is even now based on empirical rules. Deviations from the sulphur contents aimed at can often be observed in practice.
An improvement of the process control supported by knowledge of the thermodynamics and kinetics of the desulphurisation reaction is of
great importance, especially for the production of steels with very low sulphur contents.
To investigate the removal of sulphur, operational trials were carried out in 185 t steel ladles. In the trials the stirring gas flow rate, the
pressure on the bath surface and the steel composition were varied as process parameters. The obtained results show that ladle slags
saturated with lime have a high sulphide capacity. The desulphurisation rate of steel melts increases if the specific stirring energy is
enhanced by increasing the gas flow rate or reducing the pressure on the bath surface. In the case of production of AI/Si-killed steel
melts, a desulphurisation degree above 90 % can be obtained by a vacuum treatment within 10 minutes.

Thermodynamische und kinetische Betrachtungen der Stahlentschwefelung bei der sekundarmetallurgischen Behandlung. 1m
Bereich der Sekundarrnetallurqie ist die Entschwefelung von Stahlschmelzen mit einer reaktiven Pfannenschlacke einer der wichtigsten
metallurgischen Vorgange. Die ProzeBkontrolle basiert jedoch meistens auf empirischen Ansatzen. Abweichungen vom erwOnschten
Schwefelzielgehalt sind in der Praxis keine Seltenheit. Eine Verbesserung der ProzeBkontrolle, die im wesentlichen durch Kenntnisse der
Thermodynamik und Kinetik der Stahlentschwefelung unterstOtzt wird, ist fOr die Erzeugung von Stahlen mit niedrigsten Schwefelgehalten
von groBer Bedeutung.
Zur Untersuchung des Schwefelabbaus wurden Betriebsversuche in 185-t-Stahlpfannen durchgefOhrt, wobei die GasspOlrate, der Druck
an der Badoberflache sowie die Stahlzusammensetzung als ProzeBparameter variiert wurden. Die Versuchsergebnisse zeigen, daB
kalkgesattigte Schlacken eine sehr groBe Schwefelaufnahmekapazitat besitzen und die Entschwefelungsgeschwindigkeit zunimmt, wenn
die spezifische SpOlenergie durch eine ErMhung des Gasdurchsatzes oder eine Verringerung des Drucks an der Badoberflache gestei-
gert wird. Bei Erzeugung AI/Si-beruhigter Stahlschmelzen kann ein Entschwefelungsgrad Ober 90 % durch eine 10-minutige Vakuumbe-
handlung erreicht werden.

For most of the steel grades sulphur is an undesirable
element since a lot of material defects can be caused by
inadmissible sulphur contents. Hence there is a general
need to reduce the sulphur content in liquid steel as far as
possible.
In the steel plant of Aktiengesellschaft der Dillinger
Huttenwerke around 180000 t of steel per month are pro-
duced. The product range extends from high-strength
steels for structural and mechanical engineering up to
special steels for line-pipe, boiler construction and off-
shore sectors. According to specifications the sulphur
content of such steels should be very low, usually less than
10 ppm. In order to reduce the sulphur content, special
process techniques have to be used. In this paper the nec-
essary conditions for a successful desulphurisation of steel
melts during secondary metallurgy are described. In addi-
tion, results obtained from operational trials concerning the
steel desulphurisation are presented.
Metallurgical fundamentals
In modem steel shops the primary steelmaking aggre-
gates, namely converters or electric arc furnaces, are used
just for refining hot metal and scrap. All other metallurgi-
cal objectives, such as alloying, homogenisation, purging
and temperature adjustment, are performed by secondary
metallurgy in ladle or ladle furnace with a top slag.
The task of the ladle top slag is many-sided. It protects
the liquid steel against oxidising atmosphere on the one
hand and carries out metallurgic work on the other hand.
Therefore, the ladle slag should have suitable physical and
chemical properties which are characterised mainly by a
low melting temperature, a low oxygen potential as well as
a high sulphur capacity.
The formation of the ladle top slag takes place already
during tapping. It usually consists of:
slag carried over from the converter or electric arc
furnace,
deoxidation products,
wear of the ladle lining,
residual ladle slag of the previous heat,
slag forming agents added.
In ladles lined with dolomite or magnesite bricks, the
major components of initial ladle slag are CaO, Ah03,
Si02, FeO, MnO and MgO. During the ladle treatment of
AI-killed steels the following reactions between metal and
slag can simultaneously occur:

Dr.-Ing. Helmut Lachmund, manager; Dr.-Ing. Yongkun Xie, research (CaO)+[S]+ .%[AI]= X (A1203 )+(CaS) , (I)
and development steelmaking, AG der Dillinger Hiittenwerke, Dillingen;
Dr.-Ing. Klaus Harste, general manager for production and quality
control, Saarstahl AG, Volklingen, Germany.
(FeO) + .%[AI] = X(AI 203 ) + [Fe], (2)

452 steel research 72 (2001) No. 11 + 12

 Process metallurgy

(MnO) + ,7j[Al] In order to relate the sulphide capacity to the sulphur

distribution between slag and metal at equilibrium, the
partial pressures P0 2 and Ps 2 in equation (5) should be
replaced by the activities of oxygen and sulphur in liquid
steel according to:
Because of these reactions the FeO-, MnO- and Si02-
contents in slag as well as the S- and Al-contents in liquid
steel decrease. Depending on the aluminium content in
liquid steel, iron oxides and manganese oxides can be
almost completely reduced, whereas the reduction of sili-
con oxides is limited due to thermodynamic reasons. The
final ladle slag consists mainly of CaO, Ab03 and Si02
with a small amount of MgO. Under the consideration that a[s] = j[S] [%S], the fol-
The ability of a slag to absorb sulphur from a metallic lowing expression for the sulphur distribution ratio is ob-
phase is often expressed by its sulphide capacity Cs, a tained:
measurable quantity which is defined in [1] by:
(%S) _ C J[S] K 6
- -- s·_·- (8)
[%S] a[O] K7
Cs = (%8)) Po, (5)
Ps2 where a[o] and j[S] are the activity of oxygen and the ac-
tivity coefficient of sulphur in liquid steel. The equilibrium
where P0 2 and Ps2 are the partial pressures of oxygen constants K6 and K7 are functions of temperature [5; 6]:
and sulphur gases present in vicinity of the slag phase. For
isobaric and isothermal conditions the sulphur capacity 5832
logK6 =--+0.356, (9)
varies only with the slag composition and can be experi- T
mentally determined. The achievable data on the sulphur
capacities of many binary, ternary and multi-component 6535
slag systems were published in [2; 3]. The measured re- logK7 =---0.964. (10)
sults show that the sulphur capacity of a slag increases
T
with rising temperature and concentration of basic oxides. From equation (8) it can clearly be seen that the sulphur
Figure 1 shows, as an example, the iso-sulphide capacity distribution ratio depends on the oxygen activity in liquid
for the CaO-Ab03-Si02-MgO system at 1600 °C [4]. At a steel. With decreasing oxygen activity the value of
constant MgO-content, the value of Cs increases consid- (%S)/[%S] increases, so that the steel desulphurisation
erably with an increase in the CaO-content. Consequently, becomes more effective.
high-basic slags should be used for steel desulphurisation. The oxygen activity of Al-killed steel melts is actually
determined by the aluminium content. According to reac-
tion (1), a so-called desulphurisation potential EP is intro-
duced in [7; 8]:
I -3.90
• -3.39
(11)

where K 1 is a modified equilibrium constant. Somewhat

similar to the sulphide capacity Cs, the desulphurisation
potential is also a function of the slag composition. To
characterise the slag behaviour a lime saturation index,
which is defined by the proportion of the actual CaO-
content to the CaO-content for lime saturated slags, was
used in the mentioned works. Figure 2 shows the change
of the lime saturation index with the slag composition. The
curve with a value of one represents lime saturated slags.
Slags with a lime saturation index less or more than one
I..._ _ -"'T'"-_....;=-to--~a-.,...-"'T'"-"'T'"~~
are under- or over-saturated with lime, respectively. Its
90 80 70 60 50 40 30 20 10 0
influence on the desulphurisation potential is shown in
.. %CaO
figure 3. The highest desulphurisation potential is achiev-
able by use of lime saturated slags. An under-saturation of
Figure 1. lao-sulphide capacity lines (logIOCs) for CaO-AI203-SiOy
MgO system with 10 % MgO at 1600 °C according to [4] (figures in
lime in the ladle slag leads to a decrease in the desulphuri-
% refer to mass contents) sation potential due to thermodynamic reasons. The over-

steel research 72 (2001) No. 11 + 12 453

Process metallurgy

'?
0 25 Performance of plant trials
x • with lime addition :::R
0
Q. o without lime addition
2.0
C')
0
w 20 In the steel plant of Aktiengesellschaft der Dillinger
ci
«"...
Cll
+'
c Hiittenwerke, the production of quality steels is essentially
15 1.5
15a- .E
M
succeeded by secondary metallurgy in a steel ladle. A gas
c b stirring station and three vacuum tank degassers can be
0 1.0
+' 10 x used for the ladle treatment under atmospheric pressure
Cll
If)
'§ en
:::R
and under vacuum. The steel ladle with a capacity of 185 t
.c 5 0.5 e.... is lined with dolomite bricks in the lower part and magne-
a-
"5 ~
If)
QJ
:::R
~
site bricks in the slag zone. Figure 5 shows a schematic
0 0 0 illustration of the steel ladle. Three porous plugs are ec-
1.2 1.1 1.0 0.9 0.8 0.7 0.6 0.5
centrically arranged in the ladle bottom. Argon gas can be
Lime saturation index fed into the steel melt via the bottom plugs and/or the
Figure 2. Lime saturation index of ladle slags according to [8] submerged gas blowing lance. At the vacuum tank de-
gassers the gas flow rates for each bottom plug can be
saturation of lime leads to heterogeneous slags which re- separately controlled, whereas at the gas stirring station a
sults in a decrease in the desulphurisation potential due to general value is used to control the total gas flow rate
kinetic reasons. Therefore, an optimisation of the slag through the three bottom plugs.
composition is required to ensure a good removal of sul- In the case of production of Al-killed steels, lime and
phur from steel melts. aluminium will be added into the ladle during converter
The sulphide capacity as well as the desulphurisation tapping. The addition of manganese, silicon and other
potential describe the maximal ability of slags to absorb
sulphur at equilibrium state. In practice, the ladle treatment Specific stirring energy, Wit
time must be adapted to the production schedule of a steel 3 15 30 150 300
plant. A rapid refining process in the ladle is desirable. J!!
Since the chemical reactions themselves run quickly at ~

M 10
0
steelmaking temperatures, the extraction rate is controlled
by the mass transfer within the metal and slag phases. In ~ 5
2
this case an intensive bath stirring with the help of gas ~
injection leads to an acceleration of the refining process. It c
0
+=>
has been confirmed by experimental studies that the desul- m
phurisation rate increases considerably if the gas stirring '§
.c
rate exceeds a critical value [9... I I], as shown in figure 4. a-
"5 0.5
This phenomenon may be caused by an emulsification of
If)
QJ .---.I-~
0
slag droplets into the metal phase. In literature there are a
great number of reports on the slag emulsification. How- 0.005 0.01 0.05 0.1 0.5
ever, the experimental investigations were mostly carried Specific gas flow rate Q, m 3(S.T.P.)/(t·min)
out on model systems [12... 16]. Slag emulsification and its
effect on the refining process in steel ladles under opera- Figure 4. Influence of the gas stirring flow rate on the desulphuri-
tional conditions have been not well studied yet. sation rate according to [10]

....
SiO;
blowing lance

I
"~3
....
s: N~(1).1
.Ql
QJ
s: --Q 'f----
I Ol
c
ii=
sampling hole
I
100 L.. o
__ n _
~~~~~~~~-~-..).

o 20 40 60 80 100
1111I1
~I.'~
II nl II
~Il.~ _
n
~Il.~
111I

% A1 203' ----. porous N2 N3 N1

Figure 3. Desulphurisation potential as a function of the lime plugs:
saturation index according to [8] (figures in % refer to mass con- Figure 5. Schematic illustration of the steel ladle used at Dillinger
tents) HOttenwerke

454 steel research 72 (2001) No. 11 + 12

 Process metallurgy

alloying agents depends on the steel quality to be pro- 0.2 1.0

[Mnl
duced. After tapping the ladle is directly transported to the
::.'
0 2
gas stirring station where argon gas is injected simultane- -g~ ....c
ously through the bottom plugs and the gas blowing lance co ....
c 2
60> 0.1 0.5 c0
to homogenise bath temperature and chemical composi- «-
tion. Thereafter the steel ladle is transferred to a tank de- ~8 y
c
~~
gasser for further secondary metal1urgical treatment, such ~~ e.
as vacuum treatment and adjustment of the bath tempera-
ture and the steel composition. 0 0
To investigate the metal-slag reactions during the ladle
treatment, plant trials were carried out under various op- 6 30 ::.'
0 2
erational conditions. The objective of the trials was fo- -0::.'2
CO
-0
.... C
co _- C Q)
cused on the investigation of steel desulphurisation and C co- c
slag emulsification. Therefore the steel composition, the ~S 4 20 ,..!..,o
:25
~O
NO
Q,..!..,
stirring gas flow rate and the pressure on bath surface were -
I~
I (/) '"
~Q) ~O
varied as process parameters. During the gas stirring proc- (/)u.. 2 10 N
~
~~

~~~Uo
ess, steel and slag samples were taken from the ladle to
determine the change of their composition, depending on
treatment time. 2 4 6 8 10
Gas stirring time. min
Results Figure 6. Change of steel and slag composition of an AI/Si-killed
melt with gas stirring time
Desulphurisation by gas stirring treatment under at-
mospheric pressure. The trials were carried out at the gas
After about 4 minutes there are no remarkable changes in
stirring station as well as at the tank degassers, where dif-
their concentrations. In contrast, silicon oxide is stable and
ferent gas flow control units are instal1ed. Heats used for
cannot be reduced during the gas stirring treatment under
the trials can be principal1y divided into two groups,
atmospheric pressure even if a relatively high Si02-content
namely Al/Si-killed heavy plate grades with Si-contents
is present in the ladle slag.
greater than 0.1 % and sheet grades with Si-contents less
From the change of sulphur content in liquid steel a
than 0.02 %. At this point it should be noted that for the
desulphurisation degree is calculated by:
production of sheet grades the liquid steel is deoxidized by
aluminium only. No Si-containing alloying agents are
[%S]·IDI._[O/OS] 100 °
added to the ladle. Table 1 shows the operational condi- - I(
(12)
1]s - [%S]ini' Yo
tions for the trails performed under atmospheric pressure.
At the beginning of the gas stirring treatment, the steel
where [%S]ini is the sulphur content in liquid steel at the
melts had temperatures of about 1650 DC and the AI-
contents were in the range from 0.04 to 0.07 % for both beginning of the gas stirring treatment. The value of 11S
quality groups - Al/Si-killed heavy plate grades and Si-free characterizes the efficiency of steel desulphurisation,
sheet grades. The ladle slag was normally saturated with therefore, it can be used for comparing the results obtained
lime, its amount was in the order of about 15 kg/t steel. from trials under various operational conditions.
Figure 6 shows a typical change in the steel and slag The achievable desulphurisation degrees by a gas stir-
composition of an Al/Si-kil1ed heat during the gas stirring ring treatment under atmospheric pressure are presented in
treatment under atmospheric pressure. The gas flow rate figure 7 as a function of gas flow rate. Three or four heats
used for this test was 1.8 m 3(S.T.P)/min via the blowing
lance and 0.8 m 3(S.T.P)/min via the bottom plugs, respec- 100
tively. From this figure it can be seen that the AI- and S- • AI/Si-kilied heats
::.'
0 2 • Si-free heats
contents of liquid steel are reduced continuously, the Mn- 80
<Ii
content increases, the Si-content firstly decreases and then ~
OJ
keeps almost constant. This is in good agreement with the Q)
-0 60
variation of the slag composition. Under the mentioned c
0
+l
operational conditions iron and manganese oxides can be co
(/)

quickly reduced by aluminium dissolved in liquid steel. .§ 40

.L:
Q.
'3
(/)
Q)
20
Table 1. Conditions for trials performed under atmospheric pres- 0
sure
Equipment steel melt gas injection gas flow rate, m\S.T.P)/min
1 2 3
gas stirring Si-free and lance: 1.8
lance + plugs Total gas flow rate, m3(S.T. p. )/min
station Al/Si-killed plugs: < 0.8
Figure 7. Achievable desulphurisation degree by a gas stirring
tank degasser Al/Si-killed bottom plugs < 3· 0.6 treatment for 10 min under atmospheric pressure

steel research 72 (2001) No. 11 + 12 455

Process metallurgy
80,...---------------....,
-e> without argon protection
'#. _with argon protection
ai
~ 60
OJ
Q)
"U
c:
o 40
~
'ss:
% 20
III
Q)
o III
2 4 6 8 10
Gas stirring time, min
Figure 8. Change of the desulphurisation degree with time by a
gas stirring treatment under atmospheric pressure with and without
argon protection
were used for each of the investigated gas flow rates. From
the figure it is obvious that under the experimental condi-
tions the achievable desulphurisation degree is directly
proportional to the gas flow rate. In addition, the desul-
phurisation of Al/Si-killed heats is much better than that of
Si-free heats although the bath temperature and the alu-
minium content for both kinds of steel grades are almost
the same. A comparison of the slag composition indicates
that a relatively high concentration of iron and manganese
oxides can be found in the ladle slag of Si-free heats after
the gas stirring treatment. This is equivalent to an insuffi-
cient slag reduction. The reason for a worse slag reduction,
and so for a lower desulphurisation of Si-free heats is not
well-known yet. According to the information in [17], the
desulphurisation rate goes down with decreasing silicon
content of steel melts since the interfacial tension between
steel and slag is enhanced by reduced silicon contents.
In practice the gas stirring treatment of steel grades
without prescription of vacuum treatment takes place un-
der atmosphere. In this case a contact of steel melt with air
is not impossible. As a result, a reoxidation of liquid steel
may occur. Its influence on the steel desulphurisation was
also investigated by plant trials. The trials were performed
with AI/Si-killed steel melts at the tank degasser. To re-
move air, the tank degasser together with the steel ladle
was firstly evacuated down to 4 mbar and then flushed
with argon. As the inner pressure of the system returned to
I bar, the gas stirring process started by argon injection via
the bottom plugs. During the gas stirring process the tank
degasser was kept closed, a penetration of air into the steel
ladle could be avoided. Figure 8 shows, for instance, the
achievable desulphurisation degree obtained from trials at
a total gas flow rate of 1.35 m3(S.T.P.)/min with and with-
out argon protection. It can be seen that the argon protec-
tion, respectively the environmental atmosphere has no
significant influence on the steel desulphurisation. This
phenomenon was confirmed by trials at other gas flow
rates.
DesuIphurisation by gas stirring treatment under
vacuum. Within the scope of secondary metallurgy, vari-
456
100
~ evacuafions-]·~------deepvacuum------~~
..
;:g
0
80
Q)'
~
OJ
Q)
"U 60
c:
0
~ 40
'§
s:
0..
'S
Q)
20
0
0
0 5 10
Vacuum treatment time, min
Figure 9. Achievable desulphurisation degree by a vacuum treat-
ment of AI/Si-killed steel melts at a total gas flow rate of 0.75
m3(S.T.P.)/min
ous processes for the treatment of steel melts under vac-
uum have been developed and successfully used in prac-
tice, such as the VD, VOD and RH process. Apart from
their special application characters, a simultaneous elimi-
nation of hydrogen, nitrogen and sulphur is possible in
case of a vacuum treatment. Today these processes are
indispensable in the mass production of quality steels.
In the steel plant of Aktiengesellschaft der Dillinger
Hiittenwerke the vacuum treatment is performed by three
tank degassers or VD units. Presently more than 98 % of
heats are produced by a vacuum treatment with the pur-
pose of a rapid dissolution of alloying agents, an accelera-
tion of metal-slag reactions as well as a better removal of
dissolved gases. The vacuum treatment normally takes 10
minutes under pressures less than 4 mbar. During the vac-
uum treatment argon gas with a flow rate of about 3 . 0.25
m 3(S.T.P.)/min is continuously injected into steel melt via
the bottom plugs. In addition to gas stirring, an adjustment
of steel composition and an optimisation of ladle slag re-
garding its lime saturation index takes place.
Figure 9 shows the measured time dependence of the
desulphurisation degree for vacuum-treated Al/Si-killed
steel melts. In comparison to the curves in figure 8 it can
be seen that the desulphurisation of steel melts under re-
duced pressure is more efficient than under atmospheric
pressure. A great part of the sulphur can be removed al-
ready during the evacuation of the tank degasser, which
takes about 4 minutes. In the following treatment time
under deep vacuum the sulphur content will be further
reduced. A final desulphurisation degree of about 90 % is
achieved at the end of the vacuum treatment.
Similar trials were carried out with reduced argon flow
rates of3 . 0.1 and 3 . 0.2 m 3(S.T.P)/min. The variation of
the desulphurisation degree with time is comparable to that
shown in figure 9, but at a somewhat lower rate.
As mentioned above, the gas stirring treatment under
atmospheric pressure is less effective on the desulphurisa-
tion of Si-free steel melts. Usually, steels with Si-contents
smaller than 0.02 % will be produced without vacuum
treatment because of the risk of a silicon pick-up [8]. To
reduce the sulphur content of such steels special trails were
steel research 72 (2001) No. 11 + 12
 Process metallurgy

100 slag emulsification on the steel desulphurisation, determi-

~
0 nations of the sulphur content in non-metallic inclusions
w- 80
~
OJ
w used. After tapping the steel melt was treated by a simulta-
"U 60
C neous argon injection via the gas blowing lance and the
0
t~
.§
40
s:
a. 20
"5
<1l
W
0 iodine/methanol solution for 17 hours. The undissolved
o substances or remainders were filtered off. Their composi-
at after 5 min before reaching after 3 min after 5 min
tapping gas stirring vacuum 4 mbar vacuum vacuum
Figure 10. Change of the achievable desuiphurisation degree of
Si-free steel melts in different operational steps
performed. In these trials Si-free steel melts were firstly
treated by a gas stirring process of 5 minutes under atmos-
pheric pressure, where a total argon flow rate of 2.6
m3(S.T.P.)/min via the blowing lance and the bottom plugs
was used. Afterwards a short time vacuum treatment was
performed at a total argon flow rate of 0.75
m3(S.T.P.)/min. The achievable desulphurisation degree in
various process steps is presented in figure 10. An average
17S value of only about 10 % could be obtained by the gas
stirring treatment under atmospheric pressure. The scatter
of the 17S value became smaller as the ladle was trans-
ported from the gas stirring unit to the tank degasser. A
considerable increase in the desulphurisation degree took
place only during the treatment under reduced pressure. In
regard to the sulphur content at tapping, an accumulated
desulphurisation degree of about 80 % is obtained by use
of this operational procedure. From the trials it can be
concluded that the insufficient sulphur removal for Si-free
steel melts under atmospheric pressure is mainly caused by
a lower mass transfer rather than by a change in the slag
composition.
Sulphur content in non-metallic inclusions. In the tri-
als mentioned above, the progress of steel desulphurisation
was estimated by means of the chemical analysis of steel
samples. In order to get information about the influence of
4.------;::========:::::;1 ... S-content in slag
were made. For this test an Al/Si-killed steel melt was
bottom plugs under atmospheric pressure. Steel and slag
samples were taken from the ladle during the gas stirring
process. The steel samples were firstly analysed by con-
ventional methods and then separately dissolved in an
tion was determined with the help of an X-ray fluorescence
analyser. The remainders consist mainly of oxides and
sulphides, so they can be considered as non-metallic inclu-
sions in liquid steel.
As shown in figure 11, the change of the sulphur content
in inclusions with time is quite different from that for ladle
slag. Whereas the sulphur content in ladle slag continu-
ously increases, the sulphur content in inclusions decreases
with stirring time. The difference between both values
becomes gradually smaller. A comparable sulphur content
in inclusions and ladle slag is observed after several min-
utes, this is clearly shown by the ratio of %Sinclusion to
%Sslag. The relatively large value of %Sinclusion/%Ssiag in
the early stage of the gas stirring process indicates a posi-
tive influence of the slag emulsification on the steel desul-
phurisation. Emulsified slag droplets act as an interme-
dium for the sulphur transport in such a way that they
adsorb sulphur during their residence time in the steel melt
and take it to the ladle slag when they are separated from
the steel melt. This process is repeated during the whole
gas stirring period since new slag droplets can be continu-
ously generated.
Discussion
Relationship between desulphurisation rate and stir-
ring energy. The performed trials have shown that the
steel desulphurisation under vacuum runs much faster than
under atmospheric pressure. To be able to compare the
desulphurisation rate under different pressures, a suitable
basis should be used. For gas stirring systems the specific
stirring energy is a characteristic value with respect to the
stirring intensity. According to [5] the specific stirring
energy can be calculated by:

y S-content in inclusions
~
0 3 • %SinclU5ion / %S51a9 c = RoT·Q m -ln ( 1+ p m .g.h) . (13)
+-'
c T¥,11 . VN Psurface
.$ :'0.
0
c
(J

5
s:
2
..... ~

~
._-;a;
. . _-------+---
y
y
6 Taking 185 t steel ladles with a bath depth of about 3.1
m into account, the specific stirring energy under deep
a.
vacuum, psurface S 4 mbar, is five times as large as that
"5
en • under atmospheric pressure if the other parameters such as
•
bath temperature and gas flow rate are unchanged. Conse-
quently, a faster steel desulphurisation is obtained by a
O-l---.....--,..-....... ...,----r---.--r-..--1
vacuum treatment.
o 2 4 6 8 10
Since the achievable pressure during the vacuum treat-
Gas stirring time, min
Figure 11. Variation of the sulphur content in non-metallic inclu- ment depends on the operational state of the vacuum sta-
sions and ladle slag tion, it varies mostly in the range between 2 and 4 mbar,

steel research 72 (2001) No. 11 + 12 457

Process metallurgy

1.00
.... c
0.75
~
ell
..Q
T"" 0.20
~ 0.50
::J
Ul
Ul
0.25 .2l
~ ~ 0.15
0...
0
2.0
c
1.5
.ef
~ Io, 1.0 I'C 40 Wit .. 300W/t ~
3: i-=
0
q::: u)
0.5
~ c0
E ....... 100 200 300 400
o
0.020 r----------------, Specific stirring energy, WIt
Figure 13. Relationship between the desulphurisation rate and the
0.015
specific stirring energy obtained by trials with AI/Si-killed steel
0.010 melts in a 185-t ladle

0.005
O-l-----...,.--
o 5 10 15 20
Treatment time, min
Figure 12. Steel desulphurisation during vacuum treatment with a
constant stirring energy
which leads to a remarkable change in the stirring energy.
For a better assessment of the influence of pressure, trials
with constant stirring energy instead of constant gas flow
rate were also carried out. For these trails a computation
program was connected to level 2 of the vacuum station.
With the help of this program the necessary gas flow rate
for a desired specific stirring energy can be automatically
adjusted to the on-line measured pressure. Figure 12 ex-
hibits the results of such a test. The procedure of the test
can be shortly described as follows. A measurement of the
bath temperature and bath depth, a pre-adjustment of the
steel analysis as well as a correction of the ladle slag com-
position concerning its lime saturation index were firstly
made before the vacuum treatment started. The automatic
adaptation of the argon flow rate began as the pressure on
the bath surface fell down to about 200 mbar. A specific
stirring energy of 40 Wit was used in the first stage of the
vacuum treatment, and 300 Wit in the second stage. Dur-
ing the vacuum treatment steel samples were taken from
the ladle at intervals of about 3 minutes. From the figure it
can be seen that the desulphurisation rate increased rapidly
if the specific stirring energy was increased. The change of
the sulphur content with time for each individual gas stir-
Figure 13 presents the relationship between the desul-
...,._---.
phurisation rate and the specific stirring energy, which is
25 30
estimated in the present work by all trials with Al/Si-killed
steel melts under vacuum as well as under atmospheric
pressure. The desulphurisation rate increases linearly with
the specific stirring energy. A break point, something like
the curve in figure 4, is not observed. In addition, there is
no difference between the k values for gas stirring treat-
ment under vacuum and under atmospheric pressure if a
comparable specific stirring energy is used for both cases.
A comparison of the desulphurisation rate estimated in
the present work and in the reports [10] and [II] is shown
in figure 14. The deviation of the data obtained from the
various investigations is large. This may be attributed to
the different operating conditions such as the reactor ge-
ometry, the gas blowing technology, the amount and com-
position of ladle slag. For instance, the permanent specific
interface between metal and slag in smaller ladles is sig-
nificantly larger than in big ladles. Therefore, a relatively
high desulphurisation rate is expected for smaller ladles in
the range of lower specific stirring energy. This effect can
be clearly seen from figure 14.
Influence of slag amount. It has to be pointed out that,
in addition to the stirring energy, the slag amount also has
c - Trials in present work. 185 t ladle
~ 1.00 - - Trials in a 2.5 t converter after [10]
T""

~-
- Trials in a 6 t ladle after [11]
,/
ring stage obeys an exponential function, namely:
~c
,/
.Q 0.10
.. ..-/
[%S] = [%S]ini . e-kt (14)
m
.§
where the coefficient k describes the desulphurisation rate. s:
0..
By combining equations (12) and (14), one obtains: ijj
~ 0.01
(15)
10 100 1000
With knowledge of the k value it is possible to predict the Specific stirring energy, WIt
necessary gas stirring time for a targeted desulphurisation Figure 14. Comparison of the desulphurisation rate estimated by
degree. trials in different works

458 steel research 72 (2001) No. 11 + 12

 Process metallurgy

100 phurisation rate and the specific stirring energy has

:oR
0 been found;
ai 80 in the case of gas stirring treatment under atmosphere,
~
Ol
Q)
the influence of argon protection on the steel desul-
"U
c 60 phurisation is negligible;
0
-.p
(ll
slag droplets emulsified in liquid steel act as an inter-
(/)
'C 40 medium for the sulphur transfer from steel melt to ladle
::::l
.c
a. slag and have a positive influence on the sulphur re-
"5 moval.
(/)
Q)
20
0

0 Acknowledgement
10 20
Specific ladle slag amount, kglt
Figure 15. Achievable desulphurisation degree as a function of the
specific slag amount
a decisive influence on the achievable desulphurisation
degree. The following equation can be obtained from a
mass balance:
l Vo!. 2, Academic Press, London, 1974.
TIs = wm
[%S] ·\00% . (16)
I+~·-­
Ws (%S)
A graphic expression of this equation is shown in figure
15. The achievable desulphurisation degree increases with
raising the slag amount. As known from figure 3, a sulphur
distribution ratio (%S)/[%S] larger than 1000 is realisable
for steel melts with AI-contents of about 0.03 % and by
use of lime-saturated ladle slags. In this case a specific slag
amount of approximately 10 kg/t steel is required to ensure
a desulphurisation degree above 90 %.
Conclusions
To improve secondary metallurgy in steel making with
respect to desulphurisation, operational trials were carried
out in 185 t ladles. The main results obtained from the
trails can be summarised as follows:
a high desulphurisation degree of above 90 % is
achievable by use of lime-saturated ladle slags;
the desulphurisation rate is mainly determined by the
specific stirring energy, rather than by the specific gas
flow rate at standard temperature and pressure. A faster
sulphur removal under vacuum is caused by a strong
gas expansion. A linear relationship between the desul-
30
The present paper is based on the Research Project No.
7210-PR/080, supported by the European Coal and Steel
Community. This is gratefully acknowledged.
(A 0 I 718; received: 18. August 200 I)
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