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A, and therefore an overall rate constant b, has been are both based on the same theory as previously mentioned,
used, which is defined as follows i.e. first order reaction at low surfactant concentration
and second order at high concentrations. This may be
krA
b~ (2) described as follows
M {1
kCR
The equilibrium content of element X can be calculated if ww ½%Neq z½%Ni
using Sievert’s law km (7)
KX first order reaction
%½X ~ ðpX2 Þ1=2 (3)
fX {1
kCR
where KX is shown for each element in Table 1. Hence, if vv ½%Neq z½%Ni
km (8)
equation (3) for the elements hydrogen and nitrogen can
be written as follows second order reaction
where kCR is the chemical reaction coefficient, km is the
ðpX2 Þ1=2 {DGx0
%½X ~ exp (4) mass transfer coefficient, [%N]iis the interfacial concen-
fX RT tration, [%N]eq is the nitrogen concentration in the steel
where pX2 is the partial pressure of element X in the gas melt in equilibrium with nitrogen gas.
phase, fX is the activity coefficient for element X, R is the
gas constant and T is the temperature in Kelvin. Also, in Experimental
order to simplify the calculation it was assumed that the The trials were performed at Uddeholms AB’s steel
partial pressure of element X was equal to the total plant in Hagfors, Sweden. More specifically, the
pressure in each case. sampling was concentrated on the vacuum degassing
The necessary equations for each element, hydrogen, part of the ladle treatment process.
nitrogen and sulphur are shown in Table 1. For
calculation of activity coefficients by using Wagner’s Process description
equation, the required interaction parameter eiH was The steel plant at Uddeholm AB in Hagfors is scrap
taken from a compilation by Engh.5 In addition, the based and the steel scrap is melted in an electric arc
standard Gibbs free energy values in Table 1 were taken furnace with a nominal capacity of 65 tons. After
from Hayes.6 Hence, by solving equation (1) for each melting and refining, the steel melt is tapped in a ladle
element, hydrogen, nitrogen, sulphur, the following and transferred to the heating station. Here, the furnace
expression was obtained slag is removed and the steel is deoxidised by aluminium
and alloyed. Thereafter, y740 kg of synthetic slag
%Xt {%Xeq formers are added in order to protect the steel melt
{ln ~bH t (5)
%X0 {%Xeq from the atmosphere and to assist the sulphur refining
where %Xt, %X0 and %Xeq are the element contents in operation during the vacuum degassing period. The steel
and slag are heated by graphite electrodes, which lead to
the steel at time t5t, t50 and at equilibrium respec-
melting of the synthetic slag. During the heating period
tively. Also, X equals H, S or N.
in the ladle furnace, the molten steel is homogenised
However, in the case of nitrogen it may be wise to
using induction stirring. Then, the ladle is moved to the
consider the second order reaction as well. For example,
degassing station, where a vacuum lid is placed on top of
Cho and Rao7 state that for high sulphur contents the
the ladle. Argon is purged through two porous plugs for
nitrogen desorption is a second order reaction. It has
stirring of the steel melt and to promote the conditions
also been suggested by Harada and Janke8 that with
for removal of hydrogen and nitrogen from the steel.
both high sulphur and oxygen contents in the steel, both
The ladle is also stirred with induction during the
first and second order reactions will take place.
degassing period in order to improve the fluid flow
Therefore, they suggest that the nitrogen removal may characteristics in the steel. Before sending the ladle to
be written as follows uphill casting, the molten steel endures a short time of
d½%N k’rA induction stirring in order to promote inclusion removal
~{ (½%N2 {½%N2eq ) (6) to the top slag. A schematic view of the process route
dt M
can be seen in Fig. 1.
where k9 is the second order mass transfer coefficient.
According to Deo and Boom,9 the two models pre- Sampling procedure
dicting mass transfer control (first order) and chemical The studied steel grade was an H13 steel, which had
reaction control (second order) may both be used. They the composition of 0?39C–1?0Si–0?4Mn–5?3Cr–1?3Mo–
Table 1 Thermodynamic relationships used in calculations of hydrogen, nitrogen and sulphur removal
Sample (steel) Al/wt-% H/ppm N/wt-% S/wt-% Otot/ppm Temp./uC Al/wt-% H/ppm N/wt-% S/wt-% Otot/ppm Temp./uC
BV(3) 0.10 6.8 N/A 0.0024 95 1671 0.05 8.5 0.02 0.0049 N/A 1669
V3 0.06 3.7 N/A 0.0019 10 1645 0.036 4.6 0.014 0.0044 21 1635
BV(6) N/A 8.7 0.017 0.0011 21 1650 0.07 8.0 0.021 0.0025 144 1635
V6 N/A 3.2 0.009 0.0008 10 1617 0.06 3.5 0.013 0.0018 21 1601
BV(9) 0.07 N/A 0.016 0.0015 36 1663 0.07 7.2 0.021 0.001 67 1636
V9 0.037 N/A N/A 0.001 9 1620 0.05 2.3 0.011 0.0008 12 1602
BV(15) 0.09 8.9 0.019 0.0022 77 1651 0.039 8.2 0.021 0.009 19 N/A
V15 0.05 2.4 0.010 0.0015 15 1603 0.012 2.5 0.013 0.0058 43 1629
BV(22) 0.06 8.7 0.017 0.0011 16 1653 0.08 8.2 0.019 0.002 31 1634
V22 0.03 2.5 0.008 0.0005 23 1589 0.03 1.3 0.009 0.0009 11 1591
3 Kinetics of hydrogen removal using first order reaction 4 Relative decrease in hydrogen content as function of
model vacuum degassing time
aluminium and nitrogen contents are missing due to also been stated by Bannenberg et al.11 that the de-
poor sample quality. From Table 3 it can be seen that hydrogenation time can be of y10 min during normal
the sulphur content in the slag increases during vacuum practice while reaching a value of 1?5 ppm. Therefore,
degassing. More specifically, the content varied between the current results support those of Bannenberg et al.11
0?1 and 0?38% after vacuum treatment. The average slag Sulphur removal
composition before vacuum treatment was 44?8CaO–
14?0MgO–30?6Al2O3–10?6SiO2. Furthermore, the aver- The equilibrium sulphur concentration in molten steel
age slag composition after vacuum degassing was can be calculated if the sulphide capacity of the slag, the
oxygen activity, activity coefficient of sulphur in the steel
41?4CaO–13?9MgO–31?5Al2O3–9?8SiO2.
melt and temperature are known. In addition, it is
The composition changes of the steel and the slag
necessary to know the weights of slag and steel to carry
show great consistency. Therefore, the values in Tables 2
out the calculations.
and 3 were deemed to be so reliable so that they can be
The equilibrium sulphur distribution LS between slag
used in the calculations for hydrogen, sulphur and
and metal can be expressed by the following equation
nitrogen below.
ð%SÞslag
Hydrogen removal log LS ~log
½%Smetal
Equation (5) was plotted using the hydrogen data in
Table 2 and the estimated equilibrium hydrogen con- 935
~{ z1:375zlog CS zlog fS {log aO (9)
tents calculated using equation (4), with values from T
Table 1. The results are shown in Fig. 3. It can be seen where (%S)slag and [%S]metal are the sulphur contents in
that the overall rate constant for hydrogen is more or the slag and metal phases respectively. Furthermore, CS
less constant during the first 8–10 min of degassing. is the sulphide capacity of the slag phase, fS is the
According to previous work3 the dehydrogenation activity coefficient of sulphur in the metal phase and aO
process is very rapid and that the time of completion is the oxygen activity in the steel melt.
of dehydrogenation process is 5–10 min. In the present work, a model developed at KTH,4
Figure 4 illustrates the relative decrease in the hydro- ThermoSlag, was used for calculations of the sulphide
gen content as a function of the vacuum treatment time. capacity. In addition, Wagner’s equation was applied for
As is seen, almost 70% of the initial hydrogen has estimation of the activity coefficient of sulphur. The
been removed during the first 10 min. Thereafter, there oxygen activity in the steel bath aO was calculated by
is only a slight of the hydrogen content with the vacuum assuming that the dissolved aluminium and oxygen in
treatment time. The required limit of hydrogen content the steel bath and alumina in the top slag were in
in the final product is reached well within the opera- equilibrium. The alumina activity in the slag phase was
tional time frame of 30 min of vacuum degassing. It has calculated by the IRSID slag model.12,13 In the present
Sample (slag) CaO MgO Al2O3 SiO2 S in slag CaO MgO Al2O3 SiO2 S in slag
BV(3) 48.4 12.7 30.0 8.9 0.17 39.2 14.7 28.3 17.7 0.094
V3 47.6 12.7 31.1 8.6 0.12 38.2 15.3 29.5 17.0 0.14
BV(6) 43.8 13.3 35.1 7.9 0.078 41.4 16.4 27.5 14.7 0.25
V6 42.1 14.6 36.4 6.8 0.1 40.4 16.1 28.4 15.0 0.38
BV(9) 46.7 12.3 30.1 10.9 0.16 46.7 14.1 29.0 10.2 0.11
V9 45.1 14.3 29.8 10.8 0.11 46.0 13.9 30.0 10.0 0.17
BV(15) 44.5 14.3 31.4 9.8 0.16 47.7 14.0 32.0 6.3 0.1
V15 45.8 13.9 29.3 11.0 0.097 46.2 13.8 32.2 7.8 0.094
BV(22) 43.8 13.3 35.1 7.9 0.078 45.9 14.8 27.6 11.7 0.056
V22 40.7 14.8 38.3 6.1 0.12 43.2 15.1 31.1 10.6 0.14
7 Kinetics of sulphur removal using first order reaction model: data are presented for following different slag amounts:
740, 1000 and 1400 kg
8 Kinetics of nitrogen removal using first and second order reaction models
the same for different heats, the slag amount does not degassing the nitrogen refining was more or less
affect the desulphurisation kinetics: 0?0505 (740 kg), negligible.
0?0506 (1000 kg) and 0?0423 (1500 kg). It should be Oxygen and sulphur have a strong influence on the
pointed out that normally the slag amount varies kinetics of nitrogen removal. According to Refs. 15 and
between 700 and 1000 kg. Hence, the case with 16 the nitrogen removal is described by a first order
1500 kg represents an extreme case scenario. Note that reaction when the oxygen and sulphur contents are
if the slag amount should be larger during normal ,80 ppm. Since the studied steel grade is an aluminium
practice the results should, of course, be revised. killed steel grade, the oxygen activity is quite low during
vacuum degassing. More specifically, less than 461024
Nitrogen removal if the standard state is assumed to be a 1% hypotheti-
In order to calculate the removal of nitrogen from the cal solution according to Beskow.17 This corresponds
steel bulk, equation (1) can be used. This is similar to to a maximum theoretical dissolved oxygen content of
what was discussed in the case of hydrogen removal. y40 ppm. The sulphur content in the present trials was
Here, the equilibrium content of nitrogen in the steel also quite low. In addition, the initial sulphur content
melt %Neq was calculated using equation (4) and the was generally well ,0?0025%, which corresponds to a
corresponding information given in Table 2 for nitro- sulphur activity of 0?0028 (assuming that the standard
gen. In order to simplify the calculation it was assumed state is a 1% hypothetical solution). Therefore, the
that the partial pressure of nitrogen was equal to the nitrogen removal can be described with a first order
total pressure in each case, which is the same procedure reaction for the present steel grade, which is also in
as that was used for the hydrogen case. The necessary reasonable agreement with the results in Fig. 8. It
equations are shown in Table 1. Also, when calculating should be mentioned that in the evaluation of Fig. 8,
the activity coefficients by using Wagner’s equation, the one of the points deviated and has been removed (series
required interaction parameters eiN were taken from a 2, sample taken at 15 min) due to an unrealistically high
compilation by Engh.5 Moreover, the standard Gibbs sulphur content.
free energy was taken from Hayes.6 For these specific plant conditions it was shown that it
Equation (5) was plotted using the nitrogen data in was possible to use a first order to calculate the nitrogen
Table 2 together with the estimated equilibrium nitrogen content. However, it is very important to keep in mind
contents from equation (4). Figure 8 shows the nitrogen that whenever another steel composition is considered in
removal kinetics as a function of vacuum treatment
time. A first order equation was used to calculate the
nitrogen removal to confirm that the nitrogen removal
was only depending on the transport of nitrogen in the
bulk. In addition, data using a second order equation
are also presented in the figure. However, as can be seen
a second order rate (equation (6)) gave no observed
improvement. In addition, the resulting R2 values from
the straight line calculated from the measured values
where almost the same for the first and second order
equations, as seen in Fig. 8.
Figure 9 illustrates the relative decrease in nitrogen
during vacuum degassing. About 50% of the initial
nitrogen was removed during the first 10 min for the
studied steel grade. These results are similar as those
for the case of hydrogen refining shown in Fig. 4. 9 Relative decrease in nitrogen content as function of
Moreover, it is clear that after 10 min of vacuum vacuum degassing time
the future, it might be necessary to use a second order to calculate the removal of sulphur, hydrogen and
reaction model to calculate the removal of nitrogen from nitrogen. For sulphur and hydrogen only first order
steel. This is due to that elements such as oxygen and reaction models were considered. However, for nitrogen
sulphur content have a large influence on the reaction both first order and second order kinetic models were
kinetics. studied. The specific conclusions from the study may be
summarised as follows.
Concluding remarks
1. Hydrogen and nitrogen removal kinetics can be
Figure 7 indicates that the slag weight does not affect described with first order reactions for the present steel
the removal rate of sulphur. However, as seen the R2 grade, as long as the sulphur content is ,0?003%.
values are 0?39 (740 kg), 0?53 (1000 kg) and 0?70 2. After 10 min of vacuum degassing the hydrogen
(1400 kg). These values are not so high, which may and nitrogen removal is more or less finished for the
imply that a first order reaction is not applicable for the steel grade studied.
sulphur removal. 3. It is not possible to apply a first order reaction to
Experimental studies have been carried out by Battle calculate the removal of sulphur. Instead, the sulphur
and Pehlke18 to determine the removal rate of nitrogen content for the studied steel grade seems to follow the
at high oxygen and sulphur contents. For those cases, equilibrium sulphur content at all stages during the
the oxygen and sulphur levels were said to affect the degassing
removal rate. However, in the present case the steel
contains low levels of oxygen (9–43 ppm) and sulphur
(0?0005–0?0058%) after vacuum degassing, as seen in References
Table 2. In general, low levels of oxygen and sulphur are 1. D. Janke: Stahl Eisen, 1987, 107, (19), 867–874.
found to influence the nitrogen removal in different 2. K. Steneholm, M. Andersson and P. Jönsson: Steel Res. Int., 2006,
ways as discussed by different authors.16,18,19 However, 77, (6), 392–400.
in this study the levels are well below the information 3. M. Hallberg: ‘Process models for sulfur, hydrogen and inclusion
refining’, PhD thesis, KTH, Stockholm, Sweden, 2004.
found in previous research, so no direct comparison can 4. M. M. Nzotta, D. Sichen and S. Seetharaman: Metall. Trans. B,
be made. Note that the levels of total oxygen measured 1999, 30B, 909–920.
for the studied heats are presented in previous work.2 5. T. A. Engh: ‘Principles of metal refining’; 1992, Oxford, Oxford
Many studies imply that a mixed model may be used University Press.
6. P. Hayes: ‘Process principles in minerals and materials production’;
to calculate the removal of nitrogen.15,20 However, as
1993, Brisbane, Hayes Publishing.
seen in Fig. 8 the data in this study show that a first 7. W. D. Cho and Y. K. Rao: Ironmak. Steelmak., 1995, 22, (3), 239–
order calculation approach is valid. 245.
Normally, at this studied steel plant, the steel endures 8. T. Harada and D. Janke: Steel Res., 1989, 60, (8), 337–342.
a vacuum treatment and thereafter a floatation time. 9. B. Deo and R. Boom: ‘Fundamentals of steelmaking metallurgy’;
1993, London, Prentice Hall International.
Hence, with the knowledge obtained in this study, the 10. www.provac.se
vacuum treatment time may be optimised with respect to 11. N. Bannenberg, H. Lachmund and B. Prothmann: Steelmak. Conf.,
hydrogen, sulphur and nitrogen leaving the process 1994, 77, 135–143.
optimisation concerning inclusion characteristics to the 12. H. Gaye and J. Welfringer: Proc. 2nd Int. Symp. on ‘Molten slags
floatation period. As previous work has shown,2 the and fluxes’, 357–375; 1984, Warrendale, PA, Metallurgical Society
AIME.
levels of impurity elements are below the requirements at 13. H. Gaye, P. V. Riboud and J. Welfringer: Proc. 3rd Conf. on
a shorter time of vacuum treatment than what is ‘Molten slags and fluxes’, 259–262; 1988, Glasgow, The Institute of
required to meet the demands on the inclusion content. Metals.
This indicates that the following process step (the final 14. www.thermocalc.com
stirring) may be an important step to obtain an inclusion 15. W. P. Wu, K. W. Lange and D. Janke: Ironmak. Steelmak., 1995,
22, (4), 295–302.
control for these specific steel grades. 16. W. P. Wu, K. W. Lange and D. Janke: Ironmak. Steelmak., 1995,
22, (4), 303–309.
Conclusions 17. K. Beskow: ‘Formation and chemical development of non-metallic
inclusions in ladle treatment of steel’, PhD thesis, KTH,
In the present study the removal of hydrogen, nitrogen Stockholm, Sweden, 2003.
and sulphur during vacuum degassing of a tool steel 18. T. P. Battle and R. D. Pehlke: Ironmak. Steelmak., 1986, 13, (4),
grade (H13) in an ASEA-SKF ladle furnace was studied. 176–189.
19. R. Yamanaka, K. Ogawa, H. Iritani and S. Koyama: ISIJ Int.,
Slag and steel samples were collected before and after 1992, 32, (1), 136–141.
vacuum treatment for 10 heats. Thereafter, the deter- 20. N. Bannenberg, B. Bergmann and H. Gaye: Steel Res., 1992, 63,
mined chemical compositions of steel and slag were used (10), 431–437.