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Mathematical Modeling of Nitrogen Removal from the

Vacuum Tank Degasser
Shan Yu, Jyrki Miettinen, Lei Shao, and Seppo Louhenkilpi

The removal of nitrogen from an industrial vacuum tank degasser depends on a series of
operational parameters, steel composition, and contents of surface‐active elements in liquid
steel, e.g., oxygen and sulfur. The effect of some specific elements on nitrogen removal in
the vacuum degasser has been (well) examined. Still, it is quite challenging to assess the
overall effect of the whole steel composition on the process. The focus of the present work
was to predict nitrogen removal from the vacuum degasser specially taking into account the
multi‐component effect of steel composition. An integrated computational fluid dynamics
(CFD) model for simulating nitrogen (and hydrogen) removal in industrial vacuum tank
degassers was therefore developed based on theories and methods that are relatively
separate in the literature. In order to include the multi‐component effect, the model is
coupled with an in‐house thermodynamics code that can be used to determine the activity
coefficient of nitrogen, oxygen, or sulfur as a function of steel composition and temperature.
The code was verified by comparing the calculated activity coefficients against experimental
measurements from various sources. Efforts were also put into developing an on‐line use
concept to control the nitrogen removal. The gas plume, flow field, and evolutions of
nitrogen and hydrogen during vacuum treatment were predicted and the on‐line concept was
demonstrated by presenting two operating diagrams. The results showed that the final
nitrogen content decreases with an increase in the chemical reaction rate constant and a
decrease in the initial nitrogen content. By contrary, the final nitrogen content increases
with a decrease in the chemical reaction rate constant and an increase in the initial
nitrogen content. Finally, the operating diagrams were validated by industrial data and
observations.

1. Introduction products.[1,2] Today, strict control of nitrogen content in

The dissolved nitrogen in liquid steel is either a harmful
impurity or a desired alloying addition. Nitrogen can exist
in steel as free nitrogen (solid solution) or in the form of
compounds. The mechanical and corrosion properties of
(stainless) steels can be effectively improved if nitrogen
remains in solid solution or precipitates as very fine and
coherent nitrides. However, if aluminum (Al), vanadium
(V), or niobium (Nb) nitride is formed at the grain
boundaries, the hot ductility of steel will be strongly
reduced, possibly leading to transverse cracking in
continuous casting and thus impairing the quality of steel
[
] S. Yu, J. Miettinen, L. Shao, S. Louhenkilpi
Research Group of Metallurgy, Department of Materials Science and
Engineering, Aalto University, Vuorimiehentie 2, FI-02150 Espoo,
Finland
Email: seppo.louhenkilpi@aalto.fi
DOI: 10.1002/srin.201400093
steels is required in most of the steelmaking companies to
meet the ever-increasing demand of high steel cleanli-
ness.[2] It is known that there exist many sources for
nitrogen pick-up throughout the steelmaking process.
However, for nitrogen removal, degassing treatment of
molten steel in a vacuum tank is commonly applied.
The behavior of nitrogen in molten steel under various
conditions has been studied by many investigators in the
past years.[1–6] In a gas-stirred vacuum tank, nitrogen
removal rate is mainly determined by three steps: mass
transfer of nitrogen from bulk steel to the interface of gas
and steel; chemical reaction of nitrogen removal at the
interface and mass transfer of nitrogen gas from the
interface to gas phase that is usually believed to be fast, i.e.,
not a controlling step of the overall process.[7–9] Since the
surface-active elements such as oxygen (O) and sulfur (S)
block the interfacial reaction sites and consequently slow
down the reaction rate, the overall nitrogen removal can be
controlled by chemical reaction if O and/or S content is
high, or by the mass transfer rate in liquid steel in the case

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of lower O and/or S content. The removal can even be 2. Model Description
determined by chemical reaction together with mass
transfer as a mix-controlled process if O and/or S content A vacuum tank degasser (VTD) with a capacity of 105-ton
is intermediate.[10–12] It should be noted that based on the liquid steel from Ruukki in Finland is studied here. The
experiments by Ito et al.,[13] the effect of oxygen on main dimensions and the structure of the ladle are given in
nitrogen transfer rate decreases as the temperature of Figure 1. As can be seen, two porous plugs where argon gas
liquid steel increases. The authors qualitatively explained is injected are located at the ladle bottom. The gas flow rate
this finding by introducing a surface fraction of oxygen for each plug is set approximately equal. Figure 2 depicts
gathering at the interface: A high temperature gives rise to the variations of operating parameters for the industrial
a lower oxygen fraction at the interface, thus leading to a VTD during a typical degassing process. The gas flow rate is
higher effective reaction area between the gas and liquid. kept in a low level at the beginning when the operating
Similarly, the resistance of the surface-active element pressure is reduced to prevent slag foaming. After that, the
sulfur to the denitrogenation declines as the temperature flow rate is increased gradually to the target level (100–
goes up.[14] Some related experiments on a laboratory scale 200 NL min1) as a deep vacuum pressure (usually below
have been conducted using a constant amount of surface- 1 mbar) is achieved within 5 min. This deep vacuum period
active elements and the results showed that the denitroge- usually lasts about 20 min and is the main focus of this
nation can be described as a second-order reaction.[8,15,16] work. After the deep vacuum treatment, the operating
The effect of some alloying elements on nitrogen removal pressure is restored to the ambient (i.e., environment)
behavior has also been examined[17–20,22–24] and the results pressure and the gas injection is terminated.
revealed that the elements such as titanium (Ti), zirconium The target product under the aforementioned con-
(Zr), vanadium (V), manganese (Mn), and chromium (Cr), ditions is medium carbon steel, where carbon content
which have stronger affinity with nitrogen than iron, would ranges between 0.1 and 0.35%. The liquid steel supplied to
enhance the nitrogen dissociation rate (the reaction rate for the VTD is fully deoxidized and the oxygen content is
the reverse reaction of nitrogen desorption), whereas the typically lower than 6 ppm, indicating that decarburization
elements such as aluminum (Al), silicon (Si), boron (B), can barely happen during degassing. Therefore, decarbu-
(copper) Cu, wolfram (W), and tin (Sn) having stronger rization is neglected in the model. The steel composition
repulsive force against nitrogen would retard the dissocia- before vacuum treatment is listed in Table 1.
tion rate.
Even though the effect of some specific elements on
nitrogen removal in the vacuum degasser has been
clarified, it is quite challenging to assess the overall effect
of all steel components on the process, which is referred to
as the multi-component effect in this work. The focus of
the present study was to predict nitrogen removal from the
vacuum degasser specially taking into account the multi-
component effect of steel composition. An integrated
computational fluid dynamics (CFD) model for simulating
nitrogen (and hydrogen) removal in industrial vacuum
tank degassers was therefore developed. The model is
based on a CFD routine using Euler–Euler approach, which
is coupled with an in-house thermodynamics code as
well as other thermodynamic and kinetic modules.
The in-house code was built on the basis of a large-scale
thermodynamics databank and can be used to calculate
the activity coefficient of nitrogen, oxygen, or sulfur as a
function of steel composition and temperature. As the
platform, a commercial CFD package (ANSYS FLUENT
14.0) was employed and augmented by a variety of user
defined functions.[25] Efforts behind the current study were
also put into developing an on-line use concept to control
the nitrogen removal since CFD calculations are often
time-consuming and cannot be at the present time
accepted for on-line use. The concept is generally based
on extensive (off-line) CFD simulations by using the
developed model and two prediction diagrams that cover
the range of operating parameters in an industrial vacuum
tank degasser are plotted. Figure 1. Schematic structure of the ladle used in the work.

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3. Hydrogen and nitrogen are removed by the stirring gas

Figure 2. Evolutions of gas flow rate and operating pressure during
degassing.
2.1. Simplifications and Assumptions
In the developed model, both dehydrogenation and
denitrogenation are considered. The degassing process
principally consists of three steps: hydrogen or nitrogen
mass transfer from the bulk liquid to the gas–steel
interface, degassing reaction at the interface, and mass
transfer of the (hydrogen or nitrogen) gas from the reaction
sites to the gas phase (i.e., bubbles), which is believed to be
fast. The process involves many complicated physico-
chemical phenomena such as multiphase flow, species
transport, and chemical reaction. The following simplifi-
cations and assumptions are therefore applied in order to
develop a numerical model to describe the process and to
reduce the computational demand:
1. Only argon gas and liquid steel are taken into account
when calculating the multiphase flow, slag phase is not
included in the flow calculations.
2. The model is isothermal. The temperature of the liquid
steel varies within about 50 K (i.e., 1898–1843 K) during
the whole vacuum treatment in the plant. The effect of
temperature variation is neglected and 1873 K is used in
the model when needed.
(bubbles) and through the open-eye that is located at
the bath surface. The bath surface in the VTD is
assumed to be flat and the area of the open-eye is
adjusted in the corresponding computational cells
according to the plant observations.
4. The overall dehydrogenation rate is limited by the mass
transfer of hydrogen in liquid steel since the interfacial
reaction is assumed to be fast. However, the overall
denitrogenation rate is determined by the mass transfer
of nitrogen in liquid steel and the interfacial reaction.
This is because in the case of nitrogen, the surface-
active elements such as oxygen (O) and sulfur (S) block
the interfacial reaction sites and consequently retard
the reaction rate.
5. Fully hydrated lime Ca(OH)2 is taken as the main
hydrogen source in the bath surface of non-open-eye
region that represents the slag covered area. In
this study, 250 kg lime is added in the ladle furnace
before vacuum degassing and 2 wt%[26] hydrogen of
the total hydrogen amount in Ca(OH)2 is assumed
as the hydrogen source entering the steel in the
simulations.
6. The liquid steel studied here is fully deoxidized,
suggesting that decarburization can barely happen.
The oxygen content in liquid steel is constant and is
set 6 ppm (cf. Table 1). The variations of activity
coefficients due to the change in steel composition
during vacuum treatment are neglected. The activity
coefficients are calculated based on the initial
composition with an in-house activity coefficient
code, which is briefly introduced in the following
text.
7. Sulfur and oxygen are regarded as surface-active
elements. The effect of other elements is taken into
account by using the activity coefficient sub-model.
2.2. Multiphase Flow
The gas–liquid multiphase flow in the VTD is solved with a
CFD routine based on the Euler–Euler approach. A one-
group interfacial area concentration (IAC) model, which

Al C Cr H Mn N Nb

Min. 0.015 0.1 0.033 0.0004a) 0.6 0.003 0

a)
Max. 0.127 0.35 1.78 0.0004 1.4 0.0073 0.081

Ni O P S Si Ti V

Min. 0.03 0.0002 0.006 0.0016 0.09 0.002 0.005

Max. 0.66 0.0006 0.017 0.0154 0.5 0.126 0.198
a)
Stands for the average content in liquid steel.

Table 1. Variations in the liquid steel composition before degassing operation, in wt%.

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considers bubble coalescence induced by random colli-
sion, bubble coalescence induced by wake-entrainment,
and bubble breakup induced by turbulent impact, is
employed to compute the interfacial area density
between the liquid steel and gas bubbles. The standard
k–e model is extended by applying different source
terms in its conservation equations to include the
bubbly effect on turbulent characteristics in the gas-
stirred system, such as drag, wake shedding and bubble
wobbling. With the extended k–e model, the predicted
turbulent quantities showed better agreement with
the ones from physical experiments carried out by
Sheng and Irons[27] than the standard one. The reader is
referred to ref.[21] for more detailed model description
and validation.
2.3. Species Transport
Both hydrogen and nitrogen dissolved in liquid steel
(hereinafter denoted as [H] and [N], respectively) can convert
into gaseous form according to the following reaction,
2 ½X ¼ X2 ð1aÞ
where X denotes hydrogen or nitrogen.
The above reaction is controlled by the Sievert’s law and
a transformed expression of the law is[1,28,29]
K X pffiffiffiffiffiffiffiffi
Y X; e ¼ 104:5 P X2 ð1bÞ
fX
where YX,e, KX, PX2 , and fX are the equilibrium mass fraction
in liquid steel, equilibrium constant (%/atm1/2), partial
pressure (Pa), and activity coefficient. For a certain
element (H or N), the equilibrium constant at 1873 K
can be calculated from
log K H ¼ 2:572; log K N ¼ 1:340 ð1cÞ
The general species transport equation, which is used to
compute the transient distribution of hydrogen or nitrogen, is
@ the liquid phase based on the WLE formalism.[30] In this
uq Þ ¼ rðaq ~
ðaq rq Y i;q Þ þ rðaq rq Y i;q~ F i;q Þ þ S i;q ð2aÞ
@t
where the subscript “i” denotes [X] (or X2) in phase “q,” which
means the liquid steel or gas, r is the phase density (kg m3),
aq, Yi,q, and ~
F i;q are the phase volume fraction, mass fraction
and diffusive flux (kg m2 s1) in each phase, respectively. The
source term Si,q (kg m3 s1) for each phase (denoted by the
subscript “steel” or “gas”) has the following relation resulting
from mass conservation
S ½X; steel ¼ S X2 ; gas ð2bÞ
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2.3.1. Dehydrogenation
For hydrogen, since the dehydrogenation rate is assumed
to be limited by mass transfer in liquid steel, the source
term in Equation (2b) is calculated from
S ½H; steel ¼ k½H arsteel ðY ½H;e  Y ½H; steel Þ ð3Þ
where k[H], a, and Y[H], are the mass transfer coefficient of
[H] (m s1), IAC (1/m) calculated by the IAC model
and local [H] concentration in the computational cell,
respectively.
2.3.2. Denitrogenation
For nitrogen, the denitrogenation rate is determined by the
mass transfer of [N] and chemical reaction at the interface.
The source term in Equation (2b) is therefore related to the
mass transfer rate of [N], Jm, and the chemical reaction
removal rate, Jr, which are expressed by[8]
Asteelgas k½N rsteel  
Jm ¼ Y ½N;in  Y ½N;steel ð4aÞ
MN
100Asteelgas k N rsteel 2
Jr ¼ ðY ½N;e  Y 2½N;in Þ ð4bÞ
MN
0:15f 2N
kN ¼ ð4cÞ
ð1 þ 16100 f O YO þ 6340 f S YS Þ2
where Asteel–gas, MN, Y[N],in, and kN are the interfacial area
between steel and gas (m2), mole mass of nitrogen
(kg mol1), [N] content at the interface, and apparent
chemical reaction rate constant (m s1 %), respectively. fO,
fS, YO, and YS are the activity coefficients and contents of
oxygen and sulfur in liquid steel, respectively.
It must be noted here that the mass transfer coefficient
of hydrogen or nitrogen mentioned above, i.e., k[H] or
k[N], is calculated using an eddy-cell model described in
ref.[21].
2.3.3. In-House Activity Coefficient Sub-Model
The activity coefficient mentioned above has been
commonly computed using the assessed activity data of
study, however, it is calculated from the liquid phase
substitutional solution data of the IAD database,[31] which
provides thermodynamic data for iron based alloys with
solutes Al, C, Cr, H, Mn, N, Nb, Ni, O, P, S, Si, Ti, and V.
As the substitutional formalism applies mole fractions
and expresses solute activities in regard to the Raoultian
standard state (pure component) and the WLE formalism
applies mass fractions and expresses solute activities
in regard to the 1 wt% standard state, the former data
must be converted to the latter to obtain the activity
coefficient. This is realized with formula based on the
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theory of thermodynamic standard states, as reviewed by non-slip condition is applied for the liquid, while the slip
Miettinen:[32] condition is imposed for the gas at the walls. The partial
pressure of gas production in the argon bubbles is
  simplified as
mLX MX
fX ¼ exp ð5Þ
RT M Fe g 1L
X Y X;e
nX2
PX2 ;bubble ¼ Pbubble ð7aÞ
nN2 þ nH2 þ nAr
where R is the gas constant (8.3145 J K1 mol1), MX is the
molar weight (g mol1), and MFe is the molar weight of iron
(55.85 g mol1). mLX is the chemical potential andg 1L where Pbubble and n are the total pressure in the bubbles
X is the
activity coefficient of component X in its infinite dilution and mole fraction, respectively. The partial pressure of
(solute mole fractions close to zero). Both terms are produced gas above the bath surface is estimated based on
calculated with the substitutional solution model and data. the transient mole fraction of each gas species coming out
from the bath and the vacuum pressure (Pvacuum)
2.3.4. Desulfurization
During vacuum treatment, sulfur is removed by the slag nX2
PX2 ;surface ¼ Pvacuum ð7bÞ
layer on the top of the liquid bath. The desulfurization rate nN2 þ nH2 þ nAr
can be determined by mass transfer of sulfur in the slag
phase, which however is not explicitly considered in the
present model. To include the effect of the surface-active
element, an analytical formula is applied:
3. Results and Discussion
ðjtÞ
½%S ¼ ð½%S0  ½%Se Þe þ ½%Se ð6aÞ
3.1. Activity Coefficients of Hydrogen and Nitrogen in
Liquid Steel
where [%S], [%S]0, and t are the sulfur content in steel (%),
the initial sulfur content in steel (%), and time (s), Figure 3 and 4 show the calculated activity coefficients of
respectively. j is a coefficient determined by the mass hydrogen and nitrogen in liquid steel containing various
transfer of sulfur in slag phase. [%S]e is the equilibrium solutes (“Z”) at different temperatures of 1540 8C (1813 K)
content, which is calculated by and 1600 8C (1873 K). It can be seen that in the Fe–H–X
system (cf. Figure 3), an increase in the content of Ti, V, Nb,
ð%SÞ0 þ ½%S0 msteel =mslag Cr, or Mn can lower the activity coefficient of hydrogen
½%Se ¼ ð6bÞ
LS þ msteel =mslag and thus leading to a reduced removal rate. On the
contrary, increasing the content of B, C, O, Si, N, Al, P, or S
where m, (%S)0, and LS are the mass amount (kg), initial
sulfur content in slag (%), and sulfur distribution ratio,
respectively.
The sulfur distribution ratio can be calculated based on
the slag composition by using the Temkin’s complete ionic
solution model and a value of 130 is obtained as listed in
Table 2, where the other variables used in Equation (6a)
and (6b) are also given.

2.4. Boundary Treatment

The surface of the liquid bath is treated as flat and only gas
can escape through it, which is carried out by adding a set
of sink terms into the conservation equations of gas phase
in each control volume adjacent to the surface.[33] The

j msteel [kg] mslag [kg] Ls [–] (%S)0 [%]

0.0025 105 000 1800 130 0

Figure 3. Calculated activity coefficient of hydrogen in liquid Fe–
Table 2. Values related to desulfurization model. H–Z alloys at 1540 8C (dotted lines) and 1600 8C (solid lines).

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can effectively lead to an increase in the activity
coefficient, indicating a promoted removal rate. It is also
found that the effect of Mo, Cu, Ni, or Mn is marginal. For
the Fe–N–X system (cf. Figure 4), Ti, V, Nb, Cr, or Mn has
similar effect on nitrogen activity coefficient and the
coefficient rises with increasing the content of B, C, P, Si, S,
Ni, or Cu. Those findings correspond well with previously
reported ones[17–20] except for the effect of Al. It must be
stressed that O and S are surface-active elements and even
if S increases the activity coefficient of nitrogen and thus
enhancing its removal rate, the total effect is negative.
Moreover, it is observed that under the current conditions
the effect of temperature appears to be minor (cf. the
dotted and solid lines in the figures). This only implies that
temperature can slightly affect the activity coefficient of
hydrogen or nitrogen in the system. The overall removal
rate could still greatly depend on temperature if the latent
heats of some elements and surface activity elements of
oxygen and sulfur are considered in the system.
Figure 4. Calculated activity coefficient of nitrogen in liquid Fe–N–
Z alloys at 1540 8C (dotted lines) and 1600 8C (solid lines).
3.2. Validation of the Activity Coefficients

The calculated results are further validated with measure-

ments from various sources. As listed in Table 3 and 4, the

Solute, Hydrogen-solute interaction parameter, eZH

Z
Calculated Measurements Refs.

Al þ0.015 þ0.0092; þ0.0116; þ0.0130; þ0.0150 [44]; [46]; [38]; [43]

B þ0.067 þ0.035; þ0.050; þ0.080 [45]; [38]; [46]
C þ0.060 þ0.052; þ0.053; þ0.060; þ0.072 [36]; [44]; [38]; [40]
Cr 0.0023 0.0020; 0.0022; 0.0023 [45]; [38,43,44]; [39,46]
Cu þ0.0005 0.0004; þ0.0005; þ0.0025 [46]; [38]; [41]
Mn 0.0020 0.0014; 0.0020; 0.0033 [38]; [35]; [44]
Mo þ0.0012 0.0130; þ0.0009; þ0.0014; þ0.0022; þ0.0029; þ0.0048 [36]; [43]; [41]; [40]; [39]; [44]
N þ0.027 þ0.027 [48]
Nb 0.0045 0.0023; 0.0033; 0.0040; 0.0068; 0.0160 [38]; [41]; [45]; [42]; [46]
Ni 0.0009 0.0000; 0.0008; 0.0016; 0.0020; 0.0023; 0.0024 [38,46]; [40]; [37,41];
[39]; [45]; [43]
O þ0.046 þ0.050 [47]
P þ0.0115 þ0.0110; þ0.0150 [38]; [37,41]
S þ0.012 þ0.000; þ0.008; þ0.017 [46]; [38]; [44]
Si þ0.031 þ0.020; þ0.022; þ0.027; þ0.029; þ0.031; þ0.033; þ0.038 [45]; [40]; [43]; [46];
[37,41]; [44]; [36]
Ti 0.019 0.013; 0.019 [45]; [41]
V 0.0072 0.0066; 0.0074; 0.0080 [41]; [38]; [43]

Table 3. Comparisons between calculated hydrogen-solute interaction parameters and measurements from various sources.

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Solute, Nitrogen-solute interaction parameter, eZN

Z
Calculated Measurements Refs.

Al 0.021 þ0.0100; 0.0106; 0.0230; 0.0280; 0.0580 [85]; [49]; [83]; [65]; [78]
B þ0.075 þ0.061; þ0.094; þ0.130 [67]; [66]; [74]
C þ0.014 þ0.125; þ0.130; þ0.135; þ0.147; þ0.250 [55]; [85]; [58]; [87]; [60]
Cr 0.050 0.045; 0.046; 0.047; 0.052; 0.060 [56,60]; [80,88]; [71,86]; [72]; [89]
Cu þ0.009 þ0.009 [60]
Mn 0.018 0.013; 0.018; 0.020; 0.023; 0.024 [62]; [51]; [54,60,86]; [61]; [52]
Mo 0.012 0.011; 0.013 [81]; [53];
Nb 0.065 0.061; 0.067; 0.070 [68]; [60]; [79]
Ni 0.0134 0.0100; 0.0110 [60,76]; [56,85];
O 0.160 0.120; 0.160; 0.185 [69]; [59]; [75]
P þ0.055 þ0.051; þ0.059 [50]; [73];
S þ0.013 þ0.007; þ0.013 [70]; [55];
Si þ0.051 þ0.047; þ0.048; þ0.057; þ0.060; þ0.070 [60]; [58]; [84]; [85]; [63]
Ti 0.37 0.18; 0.45; 0.53; 0.60 [64]; [77]; [68]; [82]
V 0.108 0.100; 0.105; 0.110 [60]; [53]; [57]

Table 4. Comparisons between calculated nitrogen-solute interaction parameters and measearments from various sources.

calculated activity coefficients are converted into hydro-
gen- and nitrogen-solute interaction parameters (eZX ) to
make them comparable with the measurements.
logðf ZX Þ
eZX ¼
%Z
It is concluded that the calculations are in good
agreement with the measurements in literature because
all calculated values lie within the scatter bands of the
measured ones, as shown in the tables. The only exception
is parameter eNiN (cf. Table 4) for which the activity
coefficient code predicts a slightly more negative value.
3.3. CFD Results
The CFD model has been tested with a set of examples and
it has proven to be capable of capturing the main features
of multiphase flows in the VTDs and of predicting final [H]
or [N] content by comparisons with some industrial
data.[21,22,34] In this paper, the convergence criteria of all
simulations are 103 for mass, momentum, and turbulence
equations and 106 for species equations. A base case is
firstly simulated to demonstrate the integrated model. As
for the base case, gas flow rate, vacuum pressure, and
degassing duration are respectively given 130 NL min1,
0.66 mbar, and 1100 s, corresponding to typical operating
parameters in the plant. The contents of various elements
in liquid steel are given average values based on the data
listed in Table 1.
ð8Þ Figure 5 depicts the gas volume fraction and liquid
velocity field of the base case. As can be seen, two plumes
are formed as a result of gas injections from the plugs at
the bottom. The rising liquid is directed toward the ladle
sidewall as it gradually approaches the middle height of
the liquid bath and finally, it flows radially outwards in
the vicinity of the free surface and then goes downwards
adjacent to the sidewall creating a recirculation flow.
Furthermore, the evolutions of nitrogen and hydrogen
contents in liquid steel during deep vacuum treatment are
shown in Figure 6, where the contents of nitrogen and
hydrogen gradually decrease as the operation proceeds
and the low content zones appear in the vicinity of the
plume.
3.4. Operating Diagrams for Online Use
In order to provide the VTD managers and operators some
fast information in real-time, an operating diagram that
relates nitrogen removal ratio, final [N] content with initial
[N] content, and the chemical reaction rate constant

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Figure 5. Contours of (a) iso-surface of gas volume fraction (10%), (b) gas volume fraction at the center section of plume 2, and (c) velocity
field of liquid steel at the center section of plume 2 for the base case.

Figure 6. Transient distributions of (a) nitrogen and (b) hydrogen in liquid steel during deep vacuum treatment for the base case.

depending on the steel composition is required. In
principle, the diagram can be produced on the basis of
extensive numerical experiments with various key param-
eters. Figure 7 describes the flow chart of producing such
diagram developed by the present authors. The in-house
code is used to calculate the activity coefficients of N, O,
and S under different conditions and the chemical reaction
rate constant (cf. Equation 4c) is averaged over the
degassing duration.
Figure 8 depicts the operating diagram under a fixed
gas flow rate of 130 NL min1 per each plug. All the
simulations behind the calculated diagram are performed
for 1100 s corresponding to the deep vacuum period of
the degassing process (cf. Figure 2). The liquid steel

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Figure 7. Flow chart of producing operating diagrams.
Figure 8. Contour of final [N] content versus initial [N] content and
average chemical reaction rate constant under a gas flow rate of
130 NL min1 per each plug, the nitrogen removal ratio is also
marked with dashed lines.
composition is varied in each simulation in order to cover
the whole range of the steel composition given in Table 1.
As depicted in the figure, a decrease in the initial [N]
content can lead to a reduced final [N] content. By
contrary, the final [N] content increases with an increase in
the initial [N] content and a decrease in the (average)
chemical reaction rate constant, i.e., the bottom-right
corner of the diagram. This is because a high chemical
reaction rate constant can improve the denitrogenation
condition in the gas–liquid system and vice versa. The
nitrogen removal ratio, which is defined as the removed
nitrogen in liquid steel relative to the initial one, is also
marked with dashed lines in the diagram. It is observed
that the removal ratio rises as the chemical reaction rate
constant and initial [N] content increase.
474 steel research int. 86 (2015) No. 5
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Figure 9. Contour of final [N] content versus initial [N] content and
average chemical reaction rate constant under a gas flow rate of
180 NL min1 per each plug, the nitrogen removal ratio is also
marked with dashed lines.
The operating diagram under a flow rate of 180 NL
min1 per each plug is plotted in Figure 9, where similar
correlations between the final [N] content, chemical
reaction rate constant, and initial [N] content can be
concluded. However, each (dashed) line of removal ratio in
the figure is found to move downwards, indicating a higher
removal ratio can be achieved with a more intense gas
injection and thus a bigger gas–liquid IAC.
The operating diagrams produced above are verified
with industrial measurements from the plant. The
comparisons of measured and predicted final [N] contents
under different gas flow rates are depicted in Figure 10,
where the predicted contents are drawn from the operating
diagrams with corresponding initial [N] content, gas
flow rate, and calculated average chemical reaction rate
constant based on the steel composition. Generally, good
agreement can be observed in both Figure 10a and b,
which suggests that the operating diagrams presented in
this report would be an informative and accurate tool for
on-line analysis of nitrogen removal in tank degassing
units. It should be pointed out that even though those
diagrams were produced for a specific industrial VTD, the
concept behind the diagrams (cf. Figure 7) is very general.
4. Conclusions
Nitrogen removal from an industrial vacuum tank degasser
has been investigated using an integrated CFD model that
considers both denitrogenation and dehydrogenation
corresponding to the real degassing process. Focus was
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www.steel-research.de
Figure 10. Comparisons of measured and predicted final [N] contents under different gas flow rates.
put on predicting nitrogen removal specially taking into
account the multi-component effect of steel composition.
For that purpose, a CFD routine of Euler–Euler approach
was coupled with an in-house activity coefficient code
as well as other thermodynamic and kinetic modules.
The in-house code was built on the basis of a large-scale
thermodynamic databank and can be used to calculate
the activity coefficient of nitrogen, oxygen, or sulfur as a
function of steel composition and temperature. In addi-
tion, an analytical formula of desulfurization has been
applied in the model in order to include the effect of
surface-active element sulfur during vacuum treatment.
The gas plume, flow field, and evolutions of nitrogen
and hydrogen during vacuum treatment were predicted. A
new concept of estimating nitrogen removal from the
vacuum degasser has been proposed and demonstrated
by producing two operating diagrams (corresponding to
gas flow rates of 130 and 180 NL min1, respectively). The
diagrams, which relate nitrogen removal ratio, final [N]
content with initial [N] content, and the chemical reaction
rate constant depending on the steel composition, showed
that the final nitrogen content decreases with an increase
in the (average) chemical reaction rate constant and a
decrease in the initial nitrogen content in liquid steel. By
contrary, the final nitrogen content increases with a
decrease in the chemical reaction rate constant and an
increase in the initial nitrogen content. It was also found
that a higher nitrogen removal ratio can be achieved with a
more intense gas injection, which provides a bigger gas–
liquid IAC. The in-house code has been thoroughly verified
by comparing the calculated activity coefficients against
experimental measurements from various literature sour-
ces. The CFD model as well as the diagrams were validated
by a set of industrial data and observations. The operating
diagram based on the proposed flow chart therefore
appear to be an informative and accurate tool for on-line
analysis of nitrogen removal in tank degassing units
ß 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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since CFD calculations are often time-consuming and
cannot be at the present time accepted for on-line use.
Still, there are a number of issues, which need further
considerations. The next goal is to extend the operating
diagram by including the sulfur distribution ratio, which
is of considerable importance to the effectiveness of
secondary metallurgy. More operating diagrams will be
studied and determined to cover a wider range of
operating parameters in the plant. Future work will also
be focused on improving and extending the CFD model,
e.g., considering the top layer of slag and temperature
variations during degassing.
Acknowledgments
The present study was funded by the Finnish Funding
Agency for Technology and Innovation (TEKES). The
research was carried out as part of the Finnish Metals and
Engineering Competence Cluster (FIMECC)’s ELEMET
program. The financial support is kindly acknowledged.
The authors also would like to thank H. Kytönen from Aalto
University and S. Ollila from Ruukki Metals Oy for their
generous help in the course of this work. P. Oksman from
Aalto University is highly acknowledged for language
corrections and suggestions to the manuscript.
Received: March 14, 2014;
Published online: October 14, 2014
Keywords: vacuum tank degasser; activity coefficient;
nitrogen; chemical reaction rate; CFD model
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