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JOURNAL OF IRON AND STEEL RESEARCH, INTERNATIONAL. 20129 19(5) : 23-28

Mathematical Model of RH Blow Argon Mode Affecting :

Decarburization Rate in Ultra-Low Carbon Steel Refining
LI Chong-wei' , CHENG Guo-guang' , WANG Xin-hua' , ZHU Guo-sen3, CUI Ai-min3
(1. Beijing Beiye Functional Materials Corporation, Beijing 100192, China; 2. School of Metallurgical and
Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, China; 3. Shougang
Qian'an Iron and Steel Co Ltd, Qian'an 064400, Hebei, China)

Abstract: A mathematical model in present study has been established to investigate the effect of Rheinstahl Heraeus
( R H ) blow argon mode on the decarburization rate in ultra-low carbon steel refining based on the R H equipment of
Shougang Qian'an Iron and Steel Co Ltd (SQISCO). The calculated results show that the increase of argon flowrate
promotes the carbon elimination from argon gas bubble surface, molten steel free surface in vacuum as well as splash
droplet surface, while reduces that from the interior of liquid steel. It has been found the critical turning point of
flowrate ascension is at the 5'h minute and the optimum blow argon flowrate in later stage is 2 100 L/min in accord-
ance with the 2 stages argon blow mode, which have been confirmed in the commercial production in SQISCO.
Key words: RH ; vacuum; mathematical model; argon flowrate: decarburization

Efficient refining of I F steel requires the carbon argon mode put forward by this paper has been con-
concentration less than 0. 003% and refining time firmed reasonable to acquire extra-low carbon con-
less than 15 min. The decarburization reaction in centration in relatively shorter time.
RH generally occurs in following four locations: free
1 Establishment of Mathematical Model for
surface of liquid steel in vacuum chamber, argon gas
bubble surface, interior of liquid steel in vacuum"]
RH Decarburization
and splash droplet surfaceCz1.Argon injected from a 1.1 Thermodynamics of decarburization reaction
up-snorkel in RH as the power source of liquid steel The decarburization reaction in the reaction site
circulation, its flowrate directly affects the circula- can be represented by the following equation.
tion behaviour of molten steel and the decarburiza- CCl+COl =CO(g) (1)
tion reaction. Because of the difference of the decar- In this reaction, the equilibrium constant K is
burization mechanism along with the proceeding of
RH refining process, the practical production cannot
adopt only a constant blow argon flowrate during
K- Pco*
acao
-
expressed as followingc3].
'Co*
WCCl
= 10'1 160/T+Z.003)
q01
(2)
whole decarburization period. But there is little de-
tailed statements reported on how to determine the 1 . 2 Establishment of RH natural decarburization
best mode of blow argon flowrate so far. The pur- mathematical mode
pose of the present study is to establish a mathematical The RH natural decarburization mathematical
model of blow argon mode to investigate the mechanism model was established on the basis of the 4 decar-
affecting the decarburization rate of ultra-low carbon burization sites: interior of liquid steel, argon gas
steel refining and optimize the argon blow regime, based bubble surface, free surface and splash droplet sur-
on the commercial production data of Shougang Qian'an faceC4].The diagrammatic sketch of RH decarburazi-
Iron and Steel GILtd (SQISCO). The optimum blow tion sites is shown in Fig. 1.

Foundation Item: Item Sponsored by National Key Technology Research and Development Program in 11"' FiveYear Plan of China
(2006BAE03A13)
Biogr8phy:LI Chong-wei(l982-), Male, Doctor; E-mail: lichongwei-l23@yahoo. com. cn; Received Date: March 28, 2011
 24 Journal of Iron and Steel Research, International
bubblesurface I 1innersites I
n I
I where, ni, is the number of moles of Ar; nko is the
Fig. 1 Diagrammatic sketch of RH decarburazition sites
The following assumptions are made.
1 ) For each calculation circulation of the model,
the carbon and oxygen content in the ladle and vacuum
are constant respectively ;
2) The decarburization reaction proceeds in the
vacuum vessel only;
3) The carbon and oxygen concentration at the
gas-metal interface is in equilibrium with the partial
pressure of CO in the gas phase;
4) The rate of decarburization is controlled by
the mass transfer of carbon.
The mass balance of carbon and oxygen in the ves-
sel under these conditions is represented by Eqn. ( 3 )
to Eqn. (7).
W(dw[clL/dt) =Q(w[cl, -wcclL 1 (3)
W(dwcolL/dt) =Q(w[olV -w[o], ) (4)
W(dw[clV/dt)=Q(w[clL-W[C], )-(CAcI,+
CAcIin +CAcIface CACIspt ) (5)
CAcI =CACIA~ CAcIin 4- CAcl~me C A c l s p ~ (6)
M O
W(dw[olv /dt> =Q(ut[ol, - ~ [ o ] ), --(dAr+
MC
din + +
dface dspl ) (7)
where, Mc , Mo are the molecular mass of carbon
and oxygen, kg/mol; [ACIA, , [ACIin, [ACIf.,, ,
[Ac].,l are the carbon removing quantity on argon
gas bubble surface, in internal liquid steel, on free
surface and splash droplet surface respectively, t/min;
and Subscript L, V is ladle and vacuum chamber.
1.3 Decarburization mathematical model of argon
gas bubble surface
In Ref. [5] : reaction sites are in thermodynam-
ics balance; the rate determining step of the C-0 re-
action is controlled by the mass transfer of carbon.
Thus, the decarburization rate of reaction on argon
gas bubble surface can be expressed as follows:
VOl. 19
where, Ab is surface area; pm is the density of melt;
kbis liquid phase mass transfer coefficient of carbon!
and ZU[~I,is equilibrium carbon content on gas-liquid
surface which is estimated using the following equation.
P C 0 . b is the partial pressure of CO gas in the bubble
and is calculated using the following equation.
(10)
moles of CO gas in the bubble; n&, is calculated by
summing the reaction quantity with the rising bub-
ble; and Pbubble is the pressure of the bubble and is
represented by its relationship with bubble size using
the following equation.
Pbubble =p n o x
[ 2.J
-3
(11)
where, Pnois hydrostatic pressure at the nozzle posi-
tion; dbis the bubble diameter; and d b . 0 is the initial di-
ameter of argon gas bubble and assumed to be 0.006 m.
In the Higbie’s model, the mass transfer coeffi-
cient for a rising bubble in a liquid can be expressed
as the following.
(12)
where, Dc is the diffusion coefficient of dissolved carbon
in the melt (3.0 X m2/s) ; and t. is the contact time
which is estimated using the following equation.
d
t =b
Uslip
(13)
where uslipis the relative velocity of bubble.
From the above mentioned, the decarburization
quantity of Ar bubble surface in unit time can be ex-
pressed as follows:
(14)
On the basis of above established mathematical
model, the changes of overall decarburization rate
with blow argon modes could be calculated and dis-
cussed. A lot of commercial carbon samples were
taken once every minute in SQISCO with different
blow argon modes designed while the other condi-
tions such as initial steel compositions of carbon and
oxygen and pressure drop curve were controlled sim-
ilar. The process of I F steel production in SQISCO
is: “KR-+BOF+RH+CC”. Its main parameters of
RH are shown in Table 1.
Issue 5 Mathematical Model of RH Blow Argon Mode Affecting: Decarburization Rate 25

Table 1 Main parametem of RH equipment in Qian’an Iron and Steel

Total melt Diameter of vacuum Diameter of Length of Flowrate of blowing
Parameters
in ladle/t vessel/mm snorkel/mm snorkel/mm argon gas/(L min-’)
Numerical value 210 2 138 650 1075 800- 2 000

the following formula Eqn. (21)c63and Eqn. (22)c’1 :

2 Parameters Determination in Model
E= nRT/VdV=QRT/6OX22.4 ln(Po/Pv)
In the RH process, Ar gas injected at the up- V1

snorkel wall causes strong fluid flow. The melt cir- (21)
culates from the ladle to the vacuum vessel through E=g$,,,--pA,) X l o 3 V, a (1-(I) (22)
the snorkels. Due to the existence of viscosity be- where, (I is the gas volume relative ratio in total gas-
tween the bubble and steel liquid, there exists a rel- liquid two phase region; and Vi is the total volume
ative velocity to the steel liquid for Ar bubbles. As- of gas-liquid two phase region.
suming the bubbles shape is always spherical, the In Eqn. (21) and Eqn. ( 2 2 ) , the volume of gas-
relative velocity of bubble uslipcan be expressed as liquid two phase region could be expressed as the
the following formulaC6’: following:

(15)
where, u is surface tension of molten steel, 1. 8 N/m;
um,ltisviscosity of steel, 0. 005 7 kg/rns; pAris density
of Ar gas, kg/m3 9 and b is the constant (-30).
In the previous studyc7], the continuity equa-
tion of Ar bubble radius variation in the floatation
process is:
(16)
The circulation of liquid steel is expressed as
the following formulaC8’:
Q=11. 404/3G1/3
The velocity of liquid steel:
u= Q (18)
60Xplx?
The up-floating time of bubble:
H
t=-
u +uslip
where, Pv is pressure of the vacuum vessel9 and H
is height of the melt.
By the ideal gas equation of state, the number
of Ar bubble in liquid steel could be written as the
following formula :
(23)
It could be observed that Vi , the volume of gas-
liquid two phase area as indicated in Fig. 2 , has di-
rect relation with the pressure in vacuum and the
blow argon flowrate, which influences the internal
decarburization behavior of liquid steel. When the
pressure in vacuum keeps constant, the gas volume
of gas-liquid two phase tends to be larger with the
increase of blow argon flowrate. A coefficient 7 is in-
troduced to describe the influence of blowing argon
flowrate on internal decarburization of liquid steel.
7 is defined as:
Vi
1=1-- VI (24)
(17)
where VI is volume of liquid steel in vacuum.
It could be deduced from above Eqn. (24) that
the upgrading of blow argon flowrate, which makes
the volume of gas-liquid two phase <Vj>increasing,
results in the reduction of the internal decarburization
(19)
I h

So, the surface area A band volume value Gmof

Ar bubble in liquid steel at any time can be calculat-
ed using the mathematical methods. Fig. 2 Diagram of infloence of g~wliqoidtwo phase
The driving energy of rising gas is expressed as volume on internal decarblvization
 26 Journal of Iron and Steel Research, International
reaction coefficient ( v ) , that is unfavorable to inter-
nal decarburization.
3 Calculated Results
The blowing argon of R H refining process not
only has some extent of decarburization ability itself
but also can lead to the change of carbon removing
quantity at other decarburization reaction sites. The
calculated results about the effect of different blow
argon modes on the overall carbon concentration
based on the above model are to be discussed in de-
tails in the following to make clear the decarburiza-
tion mechanism.
3 . 1 Critical ascension turning point of argon blow
flowrate
Generally a argon blow mode in R H is com-
posed of 2 stages in whole decarburizing process
with respect for the difference of reaction mecha-
nism along with the refining proceeding, which is
taken a lower argon blow flowrate firstly from the
start of vacuum refining, then is turned into a
stronger one until the end of decarburing. So it is
very important for decarburization with high effi-
ciency to decide the turning point of argon blow
flowrate from the first lower to the latter strong.
This critical turning point is defined as Tc in this
paper and the optimum Tc is got from the model cal-
culated results and has to be proven reasonable in
commercial practice.
The argon blow flowrate, which takes Heat
No. 08102179 in SQISCO as example, is 1200 L/min in
the former stage and 2100 L/min in the latter re-
spectively, the Tc is settled as first, 3'h, 5'h, 7'h,
gth minute from the start of vacuum treatment to in-
vestigates the carbon concentration changes compar-
atively. It is shown in Fig. 3 that the decarburization
rate is the fastest and the endpoint of carbon content
0 1 3 6 7 9 11 1316
Timdmin
Fig. 3 Influence of blow argon modes on
carbon concentration
VOl. 1 9
is the lowest as Tc is designed 5'h minute. On the
other hand, Tc, that is settled earlier than 5'h or
later than this moment makes the decarburization
rate slower and result in the increase of endpoint
carbon content unfavorably in the same way. In
conclusion that the optimum Tc was the fifth minute
through the model calculation for R H in SQISCO.
3.2 Effect of argon blow flowrate on carbon elimi-
nation quantitiy at decarburization reaction sites
Fig. 4 describes the internal decarburizing quan-
tity changes as a function of time in the 5 different
modes. It is clear from this Fig. 4 that the internal
carbon removing quantity is increased with the ex-
tension of T c , which is higher 35 X l o p 6 when 7°C as
gth minute than that as first minute. This result sug-
gests that the Tc settled should not be too early.
5
.I I I /
Fig. 4 Internal decarborization quantity of 5
different modes changes with time
Fig. 5 and Fig. 6 describes the carbon removing
quantity at argon gas bubble, vacuum free surface
and splash droplet changes with time in the above
same 5 modes. The quantity of carbon taken off at
those sites is increased with the ascension of blow argon
0 1 3 6 7 9 1 1 1 3 1 6
Time/min
Fig. 5 Argon gas bubble carbon removing
quantity changes with time
Issue 5 Mathematical Model of R H Blow Argon Mode Affecting: Decarburization Rate 27

"I I -Intemaldecarbrizationrate I
-
I \ -.- Other sites decarburhationrate I

$cJ I
-.-.-.
0 8 1 , I

1 3 5 7 9 11 1 3 1 5
Timdmin
Fig. 6 Surface and splash droplet carbon removing
quantity changes with time
flowrate, earlier. For instance, the carbon remo-
ving quantities from argon gas bubble surfaces in
Fig. 5 and from free surfaces and splash droplets in
Fig. 6 reach the maximum. It is demonstrated that
earlier asention of blow argon flowrate is favorable
to the decarburization.
3.3 Determination of critical turning point ( T c ) of
argon blow flowrate
Through the above analysis it is clear that the
influence of blow argon flow on overall decarburiza-
tion eiists plus and minus 2 circumstances. Under
the same initial conditions, the earlier ascension of
argon flowrate promotes the decarburization on the
argon gas bubble surface, free surface and splash
droplet surface while it reduces that in interior of
liquid steel. Because the influence is contradictory
to each other, there exists a critical ascension turn-
ing point of blow argon flowrate to make sure the
decarbonization efficiency highest during overall de-
carburing process.
In order to find out the critical turning point ac-
curately, Fig. 7 shows the changes of decarburiza-
tion rate in the steel interior and at other sites with
time according to the initial conditions of Heat
No. 08102179. Tc could be determined from the in-
tersecting point of both lines of internal decarburization
and other sites decarburization in Fig. 7. Hence, it is
reasonable that the flowrate of argon blow should be
kept lower prior to Tc in Fig. 7 and then raised rap-
idly until the end of decarburization. In other words
the ascension of blow argon flowrate before the Tc
suggested in Fig. 7 is unnecessary, but the immedi-
ate increase of blow flowrate after that time can im-
prove the whole decarburization rate effectively.
0 2 4 6 8 10 12 14 16
Fig. 7 Changes of internal decarburization rate and other
sites decarburization rate with time
3.4 Flowrate of argon blow at later stage
The argon blow flowrate at later stage (after
Tc) is another important key factor for R H decar-
burization after the determination of critical turning
point Tc , although the flowrate in the former peri-
od (before T c ) is not changed so much in general
from the consideration of steel circulating well at
early stage. T h e five later flowrate blow argon
modes were settled as 1500, 1800, 2 100, 2 400,
2 700 L/min respectively and their initial conditions
were similar with the Heat No. 08102179 which its
initial flowrate was 1200 L/min before T c as 5 th mi-
nute. The carbon concentration changes calculated
from the model with time is shown in Fig. 8. It is
demonstrated from this Fig. 8 that the decarburiza-
tion rate in blow flowrate modes as 1500, 1800 L/
min is obviously lower than that in other modes and
the final carbon concentration are also higher than
that in other modes. When blow flowrate is in-
creased to 2 100, 2 400 and 2700 L/min, the change
of carbon content curves are little. Hence the opti-
mal later blow argon flowrate could be concluded as
2100 L/min.
0 1 3 5 7 0 11 1316
Timelmin
Fig. 8 Influence of flowrate on carbon concentration in
5 different modes
 28 * Journal of Iron and Steel Research. International
3.5 Validation of commercial date to model
Both of the representative heats (No. 082012179
and No. 08303643) were selected to check the con-
sistency between the model calculated results and
commercial ones. The initial carbon concentration of
those two heats were 230 X , 260 X and the
other initial conditions including vacuum pumping
curves were very similar, only different parameters
were the blowing argon flowrate modes. The chan-
ges of carbon concentration and blow argon flow-
rates in refining process are drawn in Fig. 9.
Timebin
Fig. 9 Changes of carbon concentration and blow
argon flow of chosen heats with time
The carbon concentration changing curves of
the both heats are nearly same until 5& minute. After
then, the blow argon flowrates of No. 08303643 and
No. 08102179 were to ascend at 5* and gth respectively.
Obviously the decarburization rate of No. 08303643
was significantly faster than that of No. 08102179
correspondingly.
So according to the actual condition of
Shougang Qian'an Iron and Steel Co Ltd, the criti-
cal turning point of blow argon blow rate Tc should
be the 5th minute and after that the blow argon flow-
rate should be ascended to 2100 from 1200 L/min
as soon as possible to ensure high efficient decar-
burization.
4 Conclusions
1) There is an obvious relationship between de-
carburization rates and argon blow modes. The in-
crease of argon flowrate reduces decarburizing rate in
VOl. 19
the interior of liquid steel, especially in early refi-
ning stage, while promotes the carbon elimination
from argon gas bubble surface, molten steel free
surface in vacuum as well as splash droplet surface.
2) The critical ascension turning point (Tc)of
argon blow flowrate is the key parameter for obtai-
ning a higher decarburizing efficiency, which could
be determined from the intersecting point of lines of
internal decarburization rate and other three sites
decarburization rate in accordance with the decar-
burization mathematical model.
3) It is shown from the present calculating model
that the argon blow flowrate at later stage (after
T c ) has much influence on the decaburization rate.
Generally, the higher the flowrate of argon blow is,
the faster the decarburization rate becomes. Howev-
er over bigger flowrate is unnecessary due to a fur-
ther raising of decarburizing rate being very limited.
4) It has been found the critical ascension turn-
ing point of argon blow flowrate is at the 5th minute
and the optimum blow argon flowrate in later stage
is 2100 L/min in SQISCO , which have been con-
firmed in the commercial production.
References:
Masamitsu T, Hiroshi M, Tadashi S. Mechanism of Decar-
burization in R H Degasser [J]. ISU International. 1995, 35
(12): 1452 (in Japanese).
YU Neng-wen. Mathematical and Physical Modeling of Multi-
function R H Refining Process [D]. Shanghai: Shanghai Uni-
versity, 2001 (in Chinese).
The Japan Society for the Promotion of Science. Steelmaking
Data Sourcebook [MI. New York: GBSP Publishers, 1984.
LI Chong-wei, CHENG Gucquang, W m G Xin-hua, et al. The
Establishment of RH Natural Decarburization Mathematical Model
and the Study of Mechanism of Decarburization [J]. Journal of the
Chinese Rare Earth Society, 2010(3): 112 (in Chinese).
Levich V G. Physicochemical Hydrodynamics [MI. Engle
wood Cliffs: PrenticeHall Inc. 1962.
Harashima K , Mizoguchi S, Kajioka H. Kinetics of Decaburi-
zation of Low Carbon Liquid Iron under Reduced Pressures
[J]. Tetsu-tcrHagane, 1988, 74: 449.
Park Y G , Do0 W C, Yi K W , et al. Numerical Calculation of
Circulation Flow Rate in the Degassing Rheinstahl-Heraeus
Process [J]. ISIJ International, 2000, 40: 749.
Wallis G B, Mcgraw-Hill. OneDirnensional Twcrphase Flow
[MI. New York: [s. n. 3, 1969.