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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

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

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
Q. o without lime addition
w 20 In the steel plant of Aktiengesellschaft der Dillinger
c Hiittenwerke, the production of quality steels is essentially
15 1.5
15a- .E
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
'§ en
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-
"5 ~
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
steelmaking temperatures, the extraction rate is controlled
by the mass transfer within the metal and slag phases. In ~ 5
this case an intensive bath stirring with the help of gas ~
injection leads to an acceleration of the refining process. It c
has been confirmed by experimental studies that the desul- m
phurisation rate increases considerably if the gas stirring '§
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
QJ .---.I-~
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]

blowing lance

s: N~(1).1
s: --Q 'f----
I Ol
sampling hole
100 L.. o
__ n _

o 20 40 60 80 100
II nl II
~Il.~ _

% 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

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
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
.... 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
stirring gas flow rate and the pressure on bath surface were -
I (/) '"
~Q) ~O
varied as process parameters. During the gas stirring proc- (/)u.. 2 10 N

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(
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
content increases, the Si-content firstly decreases and then ~
keeps almost constant. This is in good agreement with the Q)
-0 60
variation of the slag composition. Under the mentioned c
operational conditions iron and manganese oxides can be co

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

Table 1. Conditions for trials performed under atmospheric pres- 0
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,...---------------...., 100
~ evacuafions-]·~------deepvacuum------~~
-e> without argon protection
'#. _with argon protection ;:g
ai 80
~ 60 Q)'
"U Q)
c: "U 60
o 40 c:

'ss: ~ 40

% 20

2 4 6 8 10 0
0 5 10
Gas stirring time, min
Vacuum treatment time, min
Figure 8. Change of the desulphurisation degree with time by a Figure 9. Achievable desulphurisation degree by a vacuum treat-
gas stirring treatment under atmospheric pressure with and without ment of AI/Si-killed steel melts at a total gas flow rate of 0.75
argon protection m3(S.T.P.)/min

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

456 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
were made. For this test an Al/Si-killed steel melt was
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
bottom plugs under atmospheric pressure. Steel and slag

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

..... ~

. . _-------+---
6 Taking 185 t steel ladles with a bath depth of about 3.1
m into account, the specific stirring energy under deep
vacuum, psurface S 4 mbar, is five times as large as that
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

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

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

- Trials in a 6 t ladle after [11]
ring stage obeys an exponential function, namely:
.Q 0.10
.. ..-/
[%S] = [%S]ini . e-kt (14)

where the coefficient k describes the desulphurisation rate. s:
By combining equations (12) and (14), one obtains: ijj
~ 0.01
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

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

0 Acknowledgement
10 20 30
Specific ladle slag amount, kglt The present paper is based on the Research Project No.
Figure 15. Achievable desulphurisation degree as a function of the 7210-PR/080, supported by the European Coal and Steel
specific slag amount Community. This is gratefully acknowledged.
(A 0 I 718; received: 18. August 200 I)
a decisive influence on the achievable desulphurisation
degree. The following equation can be obtained from a References
mass balance:
[I] Richardson, F. D.: Physical Chemistry of Melts in Metallurgy.
l Vo!. 2, Academic Press, London, 1974.
TIs = wm
[%S] ·\00% . (16) [2] Verein Deutscher Eisenhiittenleute [ed.:] Slag Atlas, 2nd edn.,
I+~·-­ Verlag Stahleisen GmbH, DUsseldorf, 1995.
Ws (%S) [3] Turkdogan, E. T.: Physicochemical properties of molten slags and
glasses, The Metals Society, London, 1983.
A graphic expression of this equation is shown in figure [4] Nzotta, M. M.; t». 5.; Seetharaman, 5.: ISH Intern. 38 (1998) No.
15. The achievable desulphurisation degree increases with II,p.1170/179.
[5] Oeters, F.: Metallurgie der Stahlherstellung, Springer-Verlag,
raising the slag amount. As known from figure 3, a sulphur
Verlag Stahleisen GmbH, DUsseldorf, 1989.
distribution ratio (%S)/[%S] larger than 1000 is realisable [6] The Japan Society for the Promotion of Science: Steelmaking Data
for steel melts with AI-contents of about 0.03 % and by Sourcebook, Gordon and Breach Science Publishers, Montreux,
use of lime-saturated ladle slags. In this case a specific slag 1988.
amount of approximately 10 kg/t steel is required to ensure [7] Bergmann, B.; Bannenberg. N.: stahl u. eisen III (1991) No. I, p.
a desulphurisation degree above 90 %.
[8] Bannenberg, N.; Lachmund, H; Prothmann, B.: Proc. 77th Steel-
making conf., March 22., 1994, Chicago/Illinois, p. 135/43.
Conclusions [9] Deng, J. X; Oeters, F.: steel res. 61 (1990) No. 10, p. 438/48.
. [IO]Asai, 5.; Kawachi, M; Muchi, 1.: Proc. Scaninject III, June 1983,
Part I, Article 12.
To improve secondary metallurgy in steel making with
[I I] Berg. B.; Carlsson, G.; Brdmming, M: Scand. Journ. Metallurg. 14
respect to desulphurisation, operational trials were carried (1985), p. 299/305.
out in 185 t ladles. The main results obtained from the [I 2] Pluschkell, w.; Redenz, B; Schiirmann, E.: Arch. Eisenhuttenwes,
trails can be summarised as follows: 52 (1981), p. 85/90.
a high desulphurisation degree of above 90 % is [13] Wie, T.; Oeters, F.: steel res. 63 (1992) No.2, p. 60/67.
achievable by use of lime-saturated ladle slags; [14]Lin, Z; Guthrie, R. I. L.: Metal!. Trans. 25B (1994), p. 855/64.
[15]/guchi, M; Sumida, Y; Okada, R.; Morita, Z-I.: ISH Intern. 34
the desulphurisation rate is mainly determined by the
(1994) No.2, p. 164170.
specific stirring energy, rather than by the specific gas [16]Drogemeier, P.; Neifer, M; Rodl, S.: steel res. 66 (1995) No.5, p.
flow rate at standard temperature and pressure. A faster 194/98.
sulphur removal under vacuum is caused by a strong [17] Wosch, E.A.T.; El-Geas.\y. A.HA.; El Gammal, T.: steel res. 71
gas expansion. A linear relationship between the desul- (2000) No. 1+2, p. 39/43.

steel research 72 (2001) No. 11 + 12 459

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