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Journal of Shanghai University (English Edition), 2002, 6(1): 1 - 2 3

Article ID: 1007-6417(2002)01-0001-23

Physical and Mathematical Modeling of the Argon-Oxygen Decarburization


Refining Process of Stainless Steel
WEI J i-He ( @ ~ @ )
School of Materials Science and Engineering, Shanghai University, Shanghai 200072, China
Abstract The available studies in the literature on physical and mathematical modeling of the argon-oxygen decarburization (AOD)
process of stainless steel have briefly been reviewed. The latest advances made by the author with his research group have been summarized. Water modeling was used to investigate the fluid flow and mixing characteristics in the bath of an 18 t AOD vessel, as well as
the "back-attack" action of gas jets and its effects on the erosion and wear of the refractory lining, with sufficiently full kinematic similarity. The non-rotating and rotating gas jets blown through two annular tuyeres, respectively of straight-tube and spiral-flat tube
type, were employed in the experiments. The geometric similarity ratio between the model and its prototype (including the straighttube type tuyeres) was 1:3. The influences of the gas flow rate, the angle included between the two tuyeres and other operating parameters, and the suitability of the spiral tuyere as a practical application, were examined. These latest studies have clearly and successfully brought to light the fluid flow and mixing characteristics in the bath and the overall features of the back-attack phenomena of
gas jets during the blowing, and haye offered a better understanding of the refining process. Besides, mathematical modeling for the
refining process of stainless steel was carried out and a new mathematical model of the process was proposed and developed. The model performs the rate calculations of the refining and the mass and heat balances of the system. Also, the effects of the operating factors, including adding the slag materials, crop ends, and scrap, and alloy agents; the non-isothermal conditions; the changes in the
amounts of metal and slag during the refining; and other factors were all considered. The model was used to deal with and analyze the
austenitic stainless steel making (including ultra-low carbon steel) and was tested on data of 32 heats obtained in producing 304 grade
steel in an 18 t AOD vessel. The changes in the bath composition and temperature during the refining process with time can be accurately predicted using this model. The model can provide some very useful information and a reliable basis for optimizing the process
practice of the refining of stainless steel and control of the process in real-time and online.
Key words stainless steel, argon-oxygen decarburization (AOD) process, fluid flow and mixing, back-attack phenomenon, non-rotating and rotating gas jets, decarburization, water modeling, mathematical modeling.
w o r l d ' s s t a i n l e s s s t e e l o u t p u t a r e p r o d u c e d using this

1 Introduction

process.

C o m p a r e d to the o t h e r r e f i n i n g p r o c e s s e s of s t a i n less s t e e l ,

In this r e f i n i n g p r o c e s s , s e v e r a l a n n u l a r t u b e t y p e

the a r g o n - o x y g e n d e c a r b u r i z a t i o n ( A O D )

t u y e r e s a r e u s u a l l y used to c a r r y o u t h o r i z o n t a l side

p r o c e s s has a n u m b e r of obvious a d v a n t a g e s . Since the

b l o w i n g and i n j e c t i o n . T h e m o t i o n of the fluids in t h e

first AOD v e s s e l was c o m p l e t e d and p u t into o p e r a t i o n

b a t h is v e r y v i o l e n t . T h i s can p r o m o t e and i n t e n s i f y

in 1968,

t h e h e a t and m a s s t r a n s f e r , and is v e r y a d v a n t a g e o u s

been

this s e c o n d a r y s t e e l m a k i n g t e c h n o l o g y has

applied

rapidly

in a c c e l e r a t i n g the r e f i n i n g r e a c t i o n s and i m p r o v i n g

It n o t o n l y has b e c o m e t h e

the h o m o g e n e i t y of b a t h c o m p o s i t i o n and t e m p e r a -

extensively

throughout the world.

and

developed

principal m e t h o d of p r o d u c i n g s t a i n l e s s s t e e l and o t h e r

t u r e . On the o t h e r h a n d , as an i m p o r t a n t a p p l i c a t i o n

high c h r o m i u m a l l o y s , but it can also be used to m a k e

of t h e s u b m e r g e d gas i n j e c t i o n t e c h n i q u e ,

a l m o s t all s t e e l s .

s e r i o u s s h o r t c o m i n g of the AOD p r o c e s s is the s h o r t

At

present,

over

75%

of the

the m o s t

life of the r e f r a c t o r y lining. An obvious f e a t u r e is the


Received Nov. 22, 2001
Project supported by the National Natural Science Foundation of
China (59474016)
WEI Ji-He, P h . D . , Prof., E-mail: jihew@eastday, com

n o n - u n i f o r m w e a r and e r o s i o n of the lining.

It is

c l o s e l y r e l a t e d to the g a s b l o w i n g c o n d i t i o n s and the


fluid m o t i o n p a t t e r n s in the b a t h . T h e " b a c k - a t t a c k "
a c t i o n of gas j e t s , w h i c h o c c u r s all in t h e m e t a l l u r g i c a l
processes with any submerged gas blowing,

is r e -

ferred to as an important factor in bringing about this


situation. Investigating and obtaining a clear understanding of fluid flow phenomena and mixing characteristics as well as back-attack action during the AOD
process, mathematically modeling this process will
contribute towards the improvement and optimization
of the installation design and blowing technology, and
computer control of the process in real-time and online.
The fluid flow and mixing in the AOD vessels with
different capacities have been investigated by some
researchers using water modeling [1-4]. These studies,
to different extents, provided some useful information
for understanding the practical process. In all previous studies of this type, however, a tube tuyere has
been used to model an annular tube tuyere, and multituyere blowing has been replaced with single tuyere
blowing [2-4]. Moreover, the gas blowing rates used
for the model units have not been adequately determined. Thus, kinematic similarity between the model
and its prototype has not been fully maintained.
To improve the state of the gas jet at the tuyere
outlet and the fluid flow pattern, and thus to suppress
and eliminate the "back-attack" action of gas jets and
alleviate the erosion to the lining, many studies have
been conducted, e. g- Ref. [5 - 19]. Some schemes,
e. 9 . , those that altered the circular pipe tuyere into
flattened types with different flatness values [~' 6.9]
and spiral types with different structures [7] , reduced
the width of the annular slit (the subtuyere) as was
possible[7, 91, have been evaluated. The results available now showed that raising the blowing pressure,
using the flat-, micro-hole assembling- or spiral-type
tuyere, reducing the width of the annular slit (the
subtuyere) of an annular tube tuyere and others may
all decrease the back-attack frequency, to different
extents. The state of a gas jet at the outlet of an annular tube tuyere could markedly be changed to a
forced rotating motion when the tuyere was altered to
one with a spiral structure (71 . Under a certain blowing
condition, the rotating motion of the jet could effectively decrease the mechanical erosion of the refractory lining by the fluid flow. However, the fluid flow
and mixing phenomena in an AOD bath with rotating
gas jets have not been studied. Moreover, there
would indeed be quite a few something in common for
the relevant back-attack behaviors of gas jets in differ-

Journal of Shanghai University

ent submerged gas blowing processes. As a result of


different gas blowing directions, however, the corresponding gas jets must have different behaviors and
features, and there will also be some differences between their back-attack action. Furthermore, all the
previous investigations also have not made stricter
calculations for the gas outlet parameters of the
tuyere; the sites taken for measuring the back-attack
pressure have mostly been positioned inside the
tuyere. Therefore, that cannot necessarily bring to
light the overall situation of the back-attack phenomenon.
With respect to mathematical modeling for the AOD
process, numerous models have been proposed and developed to attempt to accomplish optimization and
computer control of the process. Some of them are
based on mass and heat balances E22S3, and some of
them are in terms of the process kinetics [26-28J and the
thermodynamics with mass balance C291. A real-time
online control model for the refining process has also
been developed and applied E31. These studies, to different extents, also offered some useful information
for understanding and improving the process practice.
However, all these available models for the refining of
stainless steel have not reflected and described fully
the real situations of the process and, to a certain degree, have all this or that shortcomings. Using these
models, in fact, it is difficult to predict quantitatively
and accurately the changes in the chemical composition and temperature of the bath during the practical
process and the influence of the relevant factors, as
well as their interactions.
Therefore, it is still needed, and is of important
theoretical and practical meaning, to study further
and more deeply this process. Considering these situations, the AOD refining of stainless steel was investigated by the author with his research group in recent
years, taking the process in an 18 t vessel for example. The latest studies and advances made on physical
and mathematical modeling of the refining process are
summarized as follows.

Physical

Modeling

of

the

AOD

Process[31 - 3~3
2.1

Similarity conditions and determination of


gas blowing rate for model
In the AOD process, the gas is horizontally blown

Vol. 6 No. 1 Mar.2002

WEI J.H. Physical and Mathematical Modeling of the Argon-OxygenDecarburization ...

into the bath from the side wall near the bottom of the
vessel, through several tuyeres ( 4 6 ) . The motion of
the liquid outside the gas-liquid two-phase flow in this
system is gas driven. The motion of the liquid outside
the gas-liquid two-phase flow will be due to gas agitation and be independent of the turbulent and viscous
force characterized by the Reynolds number. The
buoyancy, inertial force and gravity will mainly govern the motion of the gas side blowing streams.
Therefore, the modified Froude number Fr" could also be chosen as a decisive dimensionless number for
this system:
2

u g ~ ppig ~gd
Fr" = p ~ pa
- p~ gd

(1)

where ug is the velocity of gas, m . s 1 ; [)~j;ind ,,~ are,


respectively, the density of the gas and the liquid, kg
m - a ; g is the acceleration due to gravity, m ' s - 2 ; d
is the characteristic dimension of the system, m. To
maintain the kinematic similarity of the fluids in the
prototype and its model, accordingly, their modified
Froude numbers need to be kept equal, besides maintaining their geometric similarity. Taking d to be the
tuyere diameter, the following relationship can be derived from ( Fr" ) ,, = ( Fr" ) p :

( PfIO) p ( ~glm ) 1/2 ( Prim ) 1/2 ( d., ) 5/2


Qm = Qp (p~o) ~ pip
pap
~

(2)

where subscripts m and p indicate respectively the


model and its prototype; Q is the volume flow rate of
gas at the standard state, Nm 3" h- 1 ; pg0 is the density
of the gas used at the standard state, kg" Nm-3; and
pg is the density of the gas at the tuyere outlet.
Obviously, for a given original and model system,
the gas densities at the tuyere outlets both for the
model and the vessel, Pgm and pgp, are the two key
parameters, and they are closely related to the gas
flow properties in a tuyere. In order to ensure that
the kinematic similarity between the model and its
prototype was as high as possible, the corresponding
values were determined on the basis of theoretical calculations of the parameters of the gas streams in the
tuyeres. During calculation it was assumed that the

gas streams in the tuyere used for the water modeling


would all be adiabatic friction flows. The corresponding flows in the tuyere used for practical refining were
treated as heating friction processes since they all
have a marked heating friction feature [36391. In addition, the gases would be heated by the molten steel
and expand after entering the bath. Correspondingly,
their densities would be reduced. An appropriate response would be to increase the gas blowing rates for
the model. This is true principally for the gas stream
of the main tuyere. The results of theoretical calculations and estimation of the heat transfer between the
gas jet and the liquid steel in the AOD vessel showed
that the outlet temperature of the subtuyere gas
stream would have reached or slightly exceeded the
average value of the gas in the bath.
Another factor that needs to be considered is CO
formation during refining. The average utilization ratio of 02 is about 40%-50% for the AOD refining of
austenitic stainless steel [47. This means that the gas
flow rate of the main tuyere for the model should be
further raised to simulate the practical effect. All of
these considerations would improve markedly the
kinematic similarity of fluid flows between the model
and its prototype.
For the blowing refining of austenitic stainless
steel in an AOD vessel of 18 t capacity, the gases used
for the main tuyere and subtuyere are, respectively,
mixed 02 : N2 gas (4 : 1 ) and N2 in the initial (first)
stage of the refining; and mixed 02: Ar gas ( 3 : 2 ) and
Ar in the second (middle) period of the refining. With
a geometric similarity ratio of the model to its prototype (including the straight tube tuyeres) of 1:3, and
with modeling of the various gases used for refining
with air, calculations for the initial and middle stages
of blowing were conducted under conditions of heating
friction flow of the gases in a practical tuyere. As far
as the values of Q,~ are concerned, the calculated results showed that the difference for the two blowing
stages was not too large. The calculated results for
the middle period of blowing (not including the effect
of CO formation on the value of Q,~) with some related parameters are presented in Table 1.

Journal of Shanghai University

Table 1

Gas blowing rates used for 18t AOD vessel and its model in middle blowing stage and values of related p a r a m e t e r s
18 t AOD vessel

Parameter

Main tuyere

Model (1:3)

Subtuyere

Main tuyere ( * )

1
Gas blowing rate ( Q ) , Nm3"h i
p~0, kg" Nm- 3
pg, kg'm 3

Subtuyere

500 x 2

100 x 2

7.91 x 2

11.32 x 2

3.625 x 2

1. 4392 +

1. 6343 +

1.1844 +

1.1844+

1.1844+

4.2430

1.2611

1.2882

1.2645

Liquid mass in bath ( M~), t

18.00

0.1132

pL, kg- m - 3

7370 #

1000 +

Liquid level height in bath ( H ) , m

1.10

0.37

Depth of tuyere ( H z ) , m

0.95

0.32

Gas inlet pressure ( P z ) , MPa

1. 3272

1. 3996

0. 1671

0.2142

Gas outlet pressure ( P z ) ,

0. 4996

0. 2746

0. 1031

0.1031

Gas inlet temperature (T1), K

323.0

323.0

298.00

298.00

Gas outlet temperature (T2), K

526.40

1052.10

285.21

290.00

Fr" calculated from gas blowing rate

848.44

735.00

848.42

735.00

Gas outlet velocity calculated from Fr" ( ug), m" s- l

416.52

605.50

160.76

128.60

Gas outlet velocity calculated theoretically ( u g ' ) , m" s - z

416.20

604.42

160.13

128.00

MPa

* 1 and 2 are, respectively, for the cases where heat expansion of main tuyere gas after entry into bath of AOD vessel was not and was considered.
+ Ref. [36-38]; ~: Ref. [41].

2.2

Experimental conditions
Manometer

~740

14

"1
o 10~ 10"~10' 10" o

meter~
AOD model
Valve~

-%,

| Annular
yerel
Cumpresse~ air,,~ with straight- I
. ~ ~
t~uner

tube or spiral- I
fiat main tuyerd

Pressure sensor
I"

~467

Dynamic resista-I
nee strain-mater ~

(YD-2ttype) [

1010
0

~'10

0' 10~Vl0

5:3:--/

T
PI
[ l,ight-beam
oscilloscope

I(SCl6Atype)

(a)
Fig. 1

(b)

Schematic diagram of model apparatus of 18-t AOD vessel used for w a t e r modeling e x p e r i m e n t (a) and
its tuyere position a r r a n g e m e n t ( b )

Fig. 1 (a) is a schematic diagram showing the dimensions of the model apparatus of an 18 t AOD vessel
that was used for the experiments. Seventeen tuyere
positions were fixed on its side wall, and the maximum angular separation of two tuyeres being 150 , as
shown in Fig. 1 (b). The inner tube of the tuyere

used for the model was made of brass; the outer tube
of the tuyere was a circular pipe made of red copper.
The structure and cross-section of the straight tube
tuyere are presented in Fig. 2(a) and (b), respectively.

Vol. 6 No. 1 Mar. 2002

WEI J. H. :

Physical and Mathematical Modeling of the Argon-Oxygen Decarburization ...

Iq

290

"~ ....................................................................................................

1.,

326

t --

-1

(a)

Dl=4

~_--4

D 2=8

Fig. 2

(b)
(c)
Structure (a) and cross-sections with dimensions of straight tube tuyere (b) and (main tuyere) spiral-flat tuyere (c)
used for the model of 18-t AOD vessel

An annular spiral-flat tuyere of inserting a spiral


flat into the central tube (the main tuyere) was employed to obtain a rotating gas jet. A cross-section
with dimensions of the spiral tuyere used is shown in
F i g . 2 ( c ) ; the relevant pitch was 4 6 . 5 7 mm. It has a
better gas blowing performance [3z' 33l
The mixing time in the bath ( r m ) , which was defined as r0.95, was measured by the electrical conductivity method. A saturated KC1 solution was added to
the liquid surface near the wall above the sector zone
between the two tuyeres. For each experimental point
at each operating mode, the measurement was repeated at least 5 - 6 times, and then an arithmetical mean
value of the results obtained was taken. Polystyrene
particles of 1 mm diameter and 0 . 9 7 g" cm-3 density
were used as a tracer; an S L V - 2 0 adjustable laser
generator with frequency scanning provided a laser
slit light source.
The back-attack frequency and intensity of a gas jet
were continuously detected and monitored using an

anti-water pressure sensor made specially. The site of


measuring the pressure was located at the over zone
just close to the tuyere outlet (Fig. l a ) . The refractory lining was modeled with boric acid cast-plate of
100 x 100 10 mm for the experiment of the refractory lining erosion and wear.
The influences of the gas blowing rate, the angular
separation of the two tuyeres and the type of tuyere
on the stirring and flow conditions, the mixing time,
the stability of the blowing process, the back-attack
action and the erosion and wear of the lining were examined. For comparison with the practical process and
the real tuyere used, the values of Qm for three other
cases were also determined. These were assumed to
correspond respectively to adiabatic friction flow of
the gas in the tuyere, to adiabatic friction flow of the
gas in the tuyere with gas heating expansion, and to
adiabatic friction flow of the gas in the tuyere with gas
heating expansion and the formation of CO. The operating modes used are shown in Table 2.

Journal of Shanghai University


Table 2

All operating modes examined


I

II

III

IV

1+3

1+3+4

2+3

Q.,l(formain tuyeres)

12.94

20.12

25.34

15.82

22.64

Q.~2(for subtuyeres)

3.97

6.026

6.026

6.53

6.53

Blowing pressure of main tuyere/subtuyere +

(gauge value), MPa

0.066/0.07

0.135/0.125

0.185/0.125

0.09/0.137

0.16/0.137

Assumed condition of gas stream in AOD tuyere ~'~


Total gas blowing rate for two tuyeres. Nm3"h -t

No.
Angle included between the two tuyeres, 0, ( " ' )

4+

5+

6+

20

40

60

80

100

115

130

150

1-adiabatic friction flow; 2- heating friction flow; 3-considering gas heating expansion; 4- considering formation of CO.
~ 0 corresponds to single tuyere blowing.
+ for rotating gas jet and study of back-attack action

Corresponding to the blowing pressures of A - E in


Table 2, the gas blowing rates of the spiral-flat type
tuyere were, respectively, the values of I - V. For
the erosion and wear experiments of the refractory
lining, the pressures used for the two types of tuyeres
were all taken to be the value of E. In this case, the
gas blowing rate of the main-tuyere of the straighttube type tuyere was relevantly 27.58 Nm~" h-1
2.3

The features of gas s t i r r i n g and liquid flow

in the bath
It can be seen from the experimental process that
the gas blown horizontally into the bath through an
annular tube type tuyere from the side wall near the
bottom of the vessel, was in the form of a jet and
formed a few very large bubbles near the tuyere outlet. Under the combined action of the inertial force
and the buoyancy, the gas jet gradually acquired an
upward motion after penetrating a certain distance along the horizontal direction in the bath liquid. At the
same time, the liquid around it was continuously
sucked in, a gas-liquid two-phase flow was formed,
and a great quantity of small bubbles was generated.
Also, the cross-sectional area of the two-phase stream
was gradually enlarged. At the liquid surface of the
bath, the gas inside the two-phase stream escaped into
the gaseous phase. Simultaneously, the kinetic energy of the liquid was changed into potential energy,
thus leading to the liquid surface level at the center of
the two-phase zone being higher than the surface level
around the zone. This part of the liquid had downward
motion owing to the force of gravity and flowed towards the peripheral wall of the vessel along the radial

direction. This brought about fluctuating motion of


the entire liquid surface of the bath and formed a stationary wave under the obstruction of the wall. Then,
this part of the liquid had downward motion along the
side wall. During this process, it was again drawn into the two-phase stream, forming vortexes and eddies
of varying sizes. In the process of gas escape, a considerable part of the gas was also drawn into the bath
by the falling liquid and again turned into small bubbles by interaction of the gas jet with the liquid
stream. These bubbles flowed with the liquid stream
and floated up and escaped again during circulatory
motion. From beginning to end, the liquid of the bath
underwent very active stirring and circulatory motion
during blowing. There was no obvious dead zone anywhere in the bath. An increase in the gas flow rate intensified the gas agitation, but did not alter these
kinds of features of the liquid flow in the bath. Correspondingly, the fluctuation and wave motion of the
bath surface were aggravated and its stability was reduced.
The influence of the angle included between the
two tuyeres on features of gas stirring and liquid flow
in the bath was very marked and may even govern the
stability of blowing refining, particularly with a larger
gas flow rate. When the angular separation between
the two tuyeres was below 40 , the two gas streams
intersected and merged, with their interaction increasing as they rose in the bath. This made the bath
liquid surface more dynamic. The smaller the angular
separation, the more serious this situation became.
When the angle included between the two tuyeres was
beyond 115 , the two gas streams eventually collided

Vol. 6 No. 1 Mar. 2002

WEI J. H. Physical and Mathematical Modeling of the Argon-Oxygen Decarburization ...

head on with increase in the angle. This also results


in lower stability of the bath liquid surface. With a gas
blowing rate corresponding to III in Table 2, at angular separations of 20 and ~ 1 3 0 there were violent
oscillation and splashing of the liquid at the bath surface. This not only makes the blowing process difficult to stabilize but also greatly intensifies erosion of
the refractory wall by the fluids. With all the gas
blowing rates used, at angular separations of 60 100 , the liquid surfaces of the bath remained relatively smooth and steady. As far as the stability of the
blowing process is concerned, it is inexpedient for the
angle included between the two tuyeres to be excessively large or small.
When a spiral annular tube tuyere was used, the
gas jet was obviously rotating near the tuyere outlet.
The discharge angle of the jet at the tuyere outlet did
not noticeably enlarge. Its rotating velocity decreased
considerably with distance from the tuyere outlet.
However, because of inertial force, the ascending
gas-liquid two-phase flow and the liquid around it continued the rotating motion as the velocity decreased.
The cross-sectional area of the two-phase flow was
slightly larger than when the straight-tube tuyere was
used. As gas flow rate was increased, the rotating
motion became more intense, and the size of the twophase flow region became larger. Many small bubbles
were formed near the tuyere outlet in the rotating
motion of the gas jet. Large bubbles, which frequently appear when a non-rotating jet is used, seldom occurred even at the highest gas flow rate. At a given
gas flow rate, the distance penetrated by the rotating
jet along the horizontal direction in the bath was
slightly less than that of a non-rotating jet. However,
the circulatory motion velocity of the liquid and the
related intensity of the vortexes and eddies were larger, resulting in the liquid surface of the bath being
more active in that the surface was more agitated.
The position (the included angle) of the two tuyeres also strongly affected the gas agitation and liquid
flow in the bath when rotating gas jets are used. The
effects of this parameter were more sensitive than
when non-rotating gas jet were used and were more
related to the stability of the blowing process, particularly at the higher gas flow rates. At the given gas
flow rates tested, the liquid on the bath surface was
relatively both active and steady when the angular

separation between the two spiral-flat tuyeres was


80; a stationary wave with a shorter wavelength was
on the surface. However, the blowing process was
fairly smooth and steady, with no violent splashing of
the liquid on the bath surface, even at the maximum
gas flow rate used (III in Table 2). When the angular
separations of 60 and 100 were used, oscillations and
fluctuations of large amplitude were often formed on
the bath surface accompanied by violent splashing.
With respect to the stability of the blowing process,
the usable range of the included angle between the
two tuyeres, when using the rotating gas jets, was
narrower than when using the non-rotating jets.
The different back-attack phenomena of the two
kinds of gas streams were clearly observed during the
experiments, and will be described later.

2 . 4 Mixing time in bath and effects of angular


separation between two tuyeres and gas flow rate
Figs. 3 and 4 show the results of the mixing time
measured experimentally in the AOD model bath with
non-rotating and rotating gas jets. Here, Fig. 3 presents the results of mixing time as a function of the
angle included between two tuyeres at the given gas
flow rates, and Fig. 4 shows the results of the mixing
time as a function of gas flow rate at the given angular
separations. It is very clear that the AOD process under the operative conditions with non-rotating and rotating gas jets has excellent mixing efficiency.
It can be seen from Fig. 3 that with non-rotating
gas jet, r,~ was shortest in the angular range of 60 100 (reducing to a minimum value at 80). Fig. 4 illustrates that, with a gas flow rate range corresponding to II, IV and V in Table 2, there was an interval
with the shortest mixing time. The changes in rm
with 0 and Qm all showed a parabolic feature.
The relationships between the mixing time in the
A0D bath, the angle included between the two tuyeres, and the given gas flow rates completely correspond to the stirring and flow conditions in the bath.
Qualitatively, at a given gas flow rate, an excessively
large or small angle included between the two tuyeres
will increase the energy consumption and reduce the
effective stirring power, thus leading to a decrease in
mixing efficiency. The author hopes to develop technology that will ensure both a shorter mixing time and
an active and stable bath. For the practical process,
the specific gas flow rate is not determined by the

Journal of Shanghai University

20

.-..~
O

8 _~

'O""i,
o

,-~

20
(

",,,~
.9

~ ,~O

lO
d

c
I

20 40 60 80 100 120 140 160


Angle between tuyeres ()

20

Gas flow rate (Nm3/h):


a-16.91
b-22.35 c-26.15
d-29.17
e-31.37
10
--

Spiral-fiat tuyere

o --

Straight-tube tuyere

Fig. 3

20 40 60 80 100 120 140 160


Angle between tuyeres()
Mixing times in the AOD model bath as a function of the included angle
between two tuyeres at the given gas flow rates using non-rotating and
rotating gas jets

Angle:60*

Angle:8ff

oi
..x

16
16
R
~" 14 " ~
E

12

"=

e~ l0
.9
.~ 8

26
Q(Nm3/h)

2*8 3(~ 32

Angle:100 o

......

....

..................

6
18 20

Fig.4

18 2~) 2*2 24

22 24 26
Q(NmVh)

28

* --

Spiral-flat tufyere

o --

Straight-tube tuyere

3*0 32

Mixing times in the AOD model bath as a function of gas flow rate at the
given included tuyere angles using non-rotating and rotating gas jets

Vol. 6 No. 1 Mar. 2002

WEI J. H. : Physical and Mathematical Modeling of the Argon-Oxygen Decarburization ...

mixing time but according to the actual requirement of


the refining reactions, its adjustability and flexibility
are not so good. T h e r e f o r e , the influence of the angular separation is more significant and may be taken as
a basis for selecting an efficient tuyere arrangement.
It was presumed that the situation with the gas flow
rate corresponding to V in Table 2 might perhaps be
closer to practice. At this gas blowing rate, the angular range of 60 - 100 offers more efficient tuyere position. Observations and experimental results all indicated that, in this case, not only the mixing effectiveness was better but also the blowing process was
smoother and steadier. This recommended range of
angular separation of the two straight-tube tuyeres is
larger than the value (54 ) obtained by Leach et
al. [13 from the results of water modeling for a 16 t
AOD vessel, which may probably be related to the use
of single tube type tuyeres in their experiments.
The mixing times in the bath with rotating gas jets
were similar to those for using the straight-tube tuyeres. In the optimal operating range of 60 - 100 for
the straight-tube tuyeres, the angular separation was
less sensitive for the two spiral-flat tuyeres. Comparatively, the mixing efficiency at 80 would be best. At
given angular separations between the tuyeres and gas
flow rates, the mixing times using the spiral-flat tuyeres were slightly shorter than that with the straighttube tuyeres. T h e r e f o r e , using the spiral-flat tuyeres
will result in a higher mixing efficiency. Considering
the overall effects on the stability of the blowing process (the surface effects) and the mixing efficiency in
the bath, the angular separation of 80 was the optimal position for the two spiral-flat tuyeres.
Taking comprehensively account of the effects of
the gas blowing rate and the angular separation for the
two tuyeres, the following relationships were obtained from the experimental data:
for non-rotating gas jets,

t'22 04 ( Qma ) - o.072( tq,~m2)-0.345(S/S0)-0.075


( 2 0 _ 8 0 o)

rm=

n
)0.042( Qm2) -o22o( S / S o )
30 17(,~.~1

0"484 ,

(80 - 150 o)
(3)

for rotating gas jets,

14.61(Qml)

-0.142(Qm2)-0.139( S / S o ) -0.21,

(60" - 80 )
rm = 29.67( Q,,1 ) -o.15o(Q,,2) -0.099( S/So)O.29,
(80 - 100 )
(4)

where S and So are, respectively, the area of the


sector section included between the axes of the two
tuyeres and the cross-sectional area of the bath, m z.
It can be seen that in the A0D process using two
tuyere blowing with annular straight-tube type
tuyere, the mixing time in the bath is not so simply
proportional to Q a ( a < 0) as in the case of gas blowing in a ladle using a single tube tuyere. The gas
stream of the subtuyere would be able to provide a
marked shielding effect to the gas stream of the main
tuyere F8] . With respect to mixing, suitable increase in
the gas blowing rate of the subtuyere would also be
advantageous
The relationships shown by Equation ( 4 )
slightly different from those when utilizing

are
the

straight-tube tuyeres. The exponents of Q,,a and Qm2


are both negative values. This would be concerned
with the range of the angular separation used. In addition, the non-rotating jets from the subtuyere also
has a physical shielding effect on the rotating gas jets
of the main tuyeres, but compared to that on a nonrotating jet, the action is evidently weakened owing
to the rotating motion of the main tuyere jet.

2.5

T h e gas stirring energy and its r e l a t i o n s h i p

w i t h m i x i n g time
Regarding the gas stirring energy in a gas agitation
ladle system, there are different calculation equations
in the literature The divergences of these equations
are basically due to different considerations for buoyancy power and expansion work during floating up of
the bubbles Actually, during floating up, every bubble undergoes the action of buoyancy, and its volume
gradually increases with decrease in the static pressure; the buoyancy suffered increases correspondingly. On the other hand, the bubble itself would also
do work to the liquid with its volume increasing. That
is to say, as a bubble floats upward, the real "buoyancy power" should include two parts, one owing to the
pure buoyancy and the other to expansion. The former would be caused purely by buoyancy and the latter would result from a decrease in static pressure;

10

Journal of Shanghai University

they would not be equal [42]. In addition, the temperature of the gas stream after entry into the bath, Tg,
must be lower than the molten steel temperature, because it is impossible that the heat transfer rate between the gas stream and the bath is high enough to
allow equilibrium to occur in gas blowing processes [4345]. Moreover, the theoretical calculations[36a9]
indicated that, under the experimental conditions, the
gas will discharge at subsonic velocity, the outlet
pressure being equal to the back pressure. However,
the stream can still have a considerable velocity (for
instance, see Table 1) and a substantial kinetic energy. Therefore, it is inappropriate to neglect the effect
of the kinetic energy of the stream, although the related agitation efficiency is low [46]. Furthermore,
isothermal expansion of the gas near the outlet does
not take place in a water modeling process.
Based upon the considerations above, the densities
of the gas agitation energy for the main tuyere and
subtuyere, era1 and e~2(W" t- 1) were respectively estimated using the following equation:
8m = b + 7]l~T + 712~k

"12) +

Tg

1 T2
7/2( ~ - ~ p g u g ) 2 }

46.82(eml) - '6 (era2) -0.320(S/So) -0.075,

(20 - 80 o)
rm = 43.91(eml)o.oaa(em2)_o.21o(S/So)O.4S4

(6)

'

(80 - 150 )

for rotating gas jets,


{23.15(e~1)

-0.113/

~ m 2 Jx - 0 ' 135/t S / S o )

(6o

-0.21

80 )

Vr~ = 44.04(eml)_o.12O(em2)_o.o98(S/So)O.29,
(80"

(7)

100")

These equations are in an identical form to Equations


(3) and (4).

O. 1031
plgH1
p~qH1
=
M?mT~{[21n(l+-~-o )-po+pLgHll+
r]l(1 -

"buoyancy power", and equivalent to the intensity of


induction agitation in a 50 t ASEA-SKF furnace as predicted by Nakanishi et a l . ~483 As pointed out by
Figueira and Szekely[3], the kinematic similarity of
the model to its prototype in their modeling experiment was very poor. Their results do not necessarily
reflect the practical situation. The relationships between the mixing time and the densities of gas stirring
energy, obtained from the experimental data and the
calculated results, were as follows:
for non-rotating gas jets,

2.6
(5)

where eb is the real "buoyancy power", eT is the expansion power of the gas at a constant pressure near
the tuyere outlet, ek is the kinetic energy, P0 is the
atmosphere pressure. The various Tg were estimated
according to the method described in Ref. [47]; 7/1
and r/2 were taken to be 0.06 and 0.02, respectively.
It is reasonable to believe that the above analysis and
Equation (5) are applicable both to a non-rotating gas
jet and to a rotating one. However, it is necessary to
determine the values of the related parameters for a
rotating gas jet, which were performed using a reasonable and reliable appropriation method E32'33] .
Not considering the energy loss as a result of the
interaction between the non-rotating streams of the
two straight-tube tuyeres, the total density of gas
stirring energy was appropriately 150 - 320 W" t-~,
and 155 - 330 W" t- 1 for the two rotating streams of
the two spiral-flat tuyeres. These values are much
higher than those ( 4 . 5 - 8 . 0 W ' t - ~ ) obtained by
Figueira and Szekely[3] in terms of two times of the

Dimensionless correlation of mixing time

The dimensional analysis indicated that, for mixing


in the bath during the AOD process with two tuyere
blowing using an annular tube tuyere, the following
equation is valid:
U~ll "Cm g2 rm

f(

dl

'

d2

-~,~)
=0
P~

Dgl U (11 Pg2 U g2 H

De De

' plgdl ' p~qd2 'De ' dl

'

d2 ' pl '

(8)

where the subscripts 1 and 2 denote, respectively,


the appropriate parameters of the main tuyere and
subtuyere, and De is the equivalent diameter of the
bath. Taken u = u g l [ Q ~ l / ( Q ~ l + Qm2)] + ug2[ Qm2/
(Q,~I + Qm2)] and all, d2, d to be respectively the
equivalent diameters of the main tuyere and subtuyere
and the total of the two tuyeres combined into one
(the effective cross-sectional areas are accordingly
equal), the corresponding dimensionless relationships
of the mixing time were obtained:
for non-rotating gas jets,

Vol.6 No. 1 Mar,2002


26212.01(Frl"
ur,,

WEI J.H. Physical and Mathematical Modeling of the Argon-Oxygen Decarburization ...

)0.390(Fr2-) - o 111( S ~So) - 0.075

(20 - 80 )

30588.92(Frl")o.451(Fr2")-.ST(S/So) .484 ,
(80 o - 150 )
(9)

for rotating gas jets,


-urm _

-~

t 30787"49(Frl")'337(Fr2")-'5(S/S)-21,(60
- 80 )
60950.07(Frl.)o.331(Fr2.)-o.o16(S/So)O.Z9,

11

of a non-rotating. As mentioned above, large bubbles


seldom occurred. Many small bubbles formed at the
place not being far from the tuyere outlet were simultaneously striking the side wall; the residual gas of
the jet was in swirling contracting backward and attacking the surface of the tuyere outlet and the side
wall around it. Obviously, the back-attack phenomena
of the two kinds of gas jets have respectively the different characteristics from that of a bottom-blowing
jet.
The back-attack phenomenon of a horizontal gas

( 8 0 - l o o o)

(10)
Equations ( 9 ) and (10) demonstrate clearly that
the gas jet from the main tuyere still has a governing
influence on the fluid flow and mixing in the bath, although the gas jet from the subtuyere has a physical
shielding effect on it. Comparatively, the rotating gas
jet of the main tuyere has a greater effect than the
non-rotating gas jet. It may be reasonably asserted
that the results obtained reflect fairly fully the flow
and mixing characteristics of the fluids in the prototype on account of the sufficiently high kinematic similarity of the model to its prototype under the experimental conditions. This has been confirmed in practice during the production of stainless steel in an 18 t
AOD vessel.

2.7
Back-attack phenomena of gas jets with
submerged horizontally blowing
The back-attack phenomena of the gas jets were
clearly observed during the experiments, no matter
what the straight-tube or spiral-flat type tuyere was
used. In the case of the straight-tube tuyere used,
large bubbles formed at the not too far position from
the tuyere outlet were striking backward the side wall
over the tuyere outlet under the oppression of the liquid in motion, and broken into small bubbles. At the
moment of large bubble detached, the gas jet was simultaneously contracting toward the tuyere outlet direction, attacking the front surface of the tuyere outlet and the side wall around it, thus causing one backattack. T h e n , the jet was stretching forward under
the action of the succeeding follow-up gas, and carrying within itself the next back-attack. This process
was repeatedly conducting in this way.
The back-attack phenomenon of a rotating gas jet
demonstrated its general features different from that

jet, in a broad sense, should include three parts. One


is the back-attack action of the residual bulk of the gas
jet at the tuyere outlet, which is the back-attack in a
narrow sense. The second is the counteraction of the
jet [141. The third is the striking action of the bubbles
detached from the jet bulk against the side wall under
the repression of the liquid in motion. In addition, the
back-attack action of a gas jet would be closely related
to the circulatory motion of the liquid in the bath.
This would be true at least with a horizontal gas jet.
In the case of bottom blowing, the appropriate backattack phenomenon is mainly composed of the former
two actions.

2.8
Back-attack frequencies and pressures of
gas jets with submerged horizontally blowing
The determined results on the back-attack frequencies of the rotating and non-rotating jets with the two
tuyere blowing through the annular tube tuyere at the
given gas blowing rates and blowing pressures are
shown in Tables 3 and 4, respectively. The back-attack frequencies of the rotating and non-rotating jets
all showed a raising tendency with an increase in gas
blowing rate or blowing pressure of the main tuyere.
The influences of the angle included between the two
tuyeres on the back-attack frequency for the two kinds
of gas jets were all not too large under the experimental conditions, only the situation at the small gas
blowing rates was seemingly exceptional. The data in
Table 3 also indicated that the back-attack frequency
of a rotating jet was slightly higher at a same gas outlet flow rate.
The difference of operating modes specified in Tables 3 and 4 is that there was a higher gas flow rate of
the main tuyere for the straight-tube type tuyere. Appropriately, the back-attack frequency of the rotating
gas jet was evidently decreased.

Journal of Shanghai University

12

Table 3 Determined results on back-attack frequencies of rotating and non-rotating gas jets with two tuyere blowing through annulartube tuyere at the given gas blowing rates and angle included between the two tuyeres (Hz)
12.94(main tuyeres)

15.82(main tuyeres)

20.12(main tuyeres)

22.64(main tuyeres)

25.34(main tuyeres)

4-

4-

3.97(subtuyeres)

6.53(subtuyeres)

6. 026(subtuyeres)

6.53(subtuyeres)

Gas blowing rate, Nma. h- 1

Angle included
between the two
tuyeres, O

60
80*
100

6. 026(subtuyeres)

Rotating
jet

Non-rotaring jet

Rotating
jet

Non-rotaring jet

Rotating
jet

Non-rotaring jet

Rotating
jet

Non-rotaring jet

Rotating
jet

Non-rotaring jet

(6)
(6)
(7)

(3)
(5)
(8)

(4)
(5)
(7)

(2)
(3)
(3)

(9)
(9)
(9)

(10)
(8)
(9)

(12)
(9)
(11)

(8)
(9)
(9)

(12)
(11)
(11)

(12)
(11)
(13)

Table 4 Determined results on back-attack frequencies of rotating and non-rotating gas jets with two tuyere blowing through annulartube tuyere at the given gas blowing pressures and angle included between the two tuyeres (Hz)
0.066(main tuyeres)

0.09(main tuyeres)

0. 135(main tuyeres)

0.16(main tuyeres)

0. 185(main tuyeres)

4-

0.07(subtuyeres)

0. 137(subtuyeres)

0.125(subtuyeres)

0.137(subtuyeres)

0. 125(subtuyeres)

Gas blowing pressure


(gauge value), MPa

Angle included
between the two
tuyeres, t9

60*
80
100

Rotating
jet

Non-rotaring jet

Rotating
jet

Non-rotaring jet

Rotating
jet

Non-rotaring jet

Rotating
jet

Non-rotaring jet

Rotating
jet

Non-rotaring jet

(6)
(6)
(7)

(8)
(9)
(8)

(4)
(5)
(7)

(6)
(9)
(9)

(9)
(9)
(9)

(12)
(13)
(13)

(12)
(9)
(11)

(15)
(14)
(15)

(12)
(11)
(11)

(17)
(17)
(17)

Table 5 Determined results on back-attack frequencies of rotating gas jet with single tuyere blowing through single tube tuyere at the
given gas blowing pressures (flow rates)
Blowing pressure (gauge value), MPa

0.066

0.09

0.135

0.16

0.185

Gas blowing rate, Nm3"h- 1

6.47

7.91

10.06

11.32

12.67

Back-attack frequency, Hz

10

13

13

15

It can also be clearly seen from the data in Tables 3


and 4 that relatively to the gas s t r e a m of the sub-

rate to that of the main t u y e r e , which is in a g r e e m e n t


with the results obtained by Cho et al. [131

tuyere, the gas stream from the main tuyere has a decisive influence on the back-attack phenomenon.
However, at a same gas blowing pressure, the back-

It should be pointed out that there would all be the


multiple action points when large bubbles and a group
of small bubbles strike the side wall during back-at-

attack frequency of the rotating gas jet with the single

tacking. As a result of this kind of characteristic for a

tuyere

tuyere

horizontal gas jet, its each back-attack, in fact, will

T h e r e was a

all involve the action of a group of bubbles including

similar pattern for the non-rotating jet. T h a t appears

the residual bulk of the jet. This was fully confirmed

to show that the gas stream of the subtuyere may alle-

by the obtained back-attack waves shown in Fig. 5. It

blowing

through

the

single

markedly increased ( T a b l e 4 and 5 ) .

tube

viate the back-attack phenomenon to a considerable

can be seen from Fig. 5 that there was correspond-

extent. The gas stream of the subtuyere also has an

ingly a group of positive and negative pulses for each

evident "shielding" effect on the back-attack action


besides the cooling and physical shielding effects to
the flow of main tuyere gas [31-33]. Additionally, this

back-attack, and the pulse numbers included in each


back-attack were roughly close to each other at the

effect is enhanced with an increase in its relative flow

given blowing parameters.

Vol. 6 No. 1 Mar. 2002

WEI J. H. :

Physical and Mathematical Modeling of the Argon-Oxygen Decarburization .

13

kPa

+1.0
'

0.0
kPa

+l.0

-1.0

0.0:
-1.0)

I0 " ~ - ~ l

I_0,s-!

one back-attack

onc back-attack
Non-rotatinggas jet

Rotating gas jet

(a) Blowing pressures of the main tuyere and subtuyere (gauge values) : 0.16 MPa and 0. 137 MPa, 0 = 80

+1.0

kPa i

kPa

00

+1.0
-1.0
0.0
I

-1,0 -

io.

z..i

! ~ O.Is ~ !

one back-attack

onc back-attack

Non-rotatinggas jet

Rotating gas jet

(b) Blowing pressures of the main tuyere and subtuyere (gauge values): 0. 066 MPa and 0.07 MPa, 0 = 80*
Fig.5

Back-attack waves of gas jets for a part of operating modes during the AOD water modeling blowing

2 . 9 Rate and appearance of erosion and wear


of refractory lining with horizontally side b l o w ing
The changes in the average rate of erosion and
wear for the boric acid plate with the angle included
between the two tuyeres during the water modeling of
the AOD process using the different types of tuyere
were obtained. In the case of the gas blowing process
with the straight-tube type tuyere, the average erosion and wear rates of the boric acid plates during the
treatment of 10 min were 0. 03015,

0. 02756,

0.

03219 g ' s - 1 , respectively for the angular separations


between the two tuyeres of 60 , 80 and 100 . The
erosion and wear rate of the lining was the lowest at
the angle included between the two tuyeres of 80 .

When the spiral-flat tuyere was used, the average


rates were essentially not related to the angular separation between the two t u y e r e s , corresPondingly,
were all 0. 01733 g" s-~. Comparing with that of the
straight-tube type t u y e r e , it decreased by 37% 46%.
After the t r e a t m e n t of 10 min, the boric acid plates
were markedly changed into thinner, especially at the
periphery tightly close to the tuyere outlet. A series
of concave pits and pocked marks were formed in a
rather large range near and over the tuyere outlet. It
is evident that for the boric acid plates, the erosion of
the liquid and the solution of the boric acid would
cause them changing more uniformly into thinner.
The formation of the concave pits and pocked marks

Journal o.f Shanghai University

14
would be the results of striking repeatedly by the bubbles with the back attacking of jet. Under the conditions of the rotating gas jets, relatively, the pits and
marks formed were fewer, shallower and more uniform, and their distribution area was smaller. There
were also some curved stripes. The kinds of appearance characteristics of the treated boric-acid plates
like that are completely corresponding to the observed
back-attack features of the gas jets, and reflect generally the actual situation about the damage of the refractory lining in the AOD process. In the practical
AOD process, the buoyancy stood by the bubbles
would be much larger, approximately over 7 times of
that for water modeling, and the zone formed the concave pits and pockmarks will be farther from the
tuyere outlet.

2.10 Using effectiveness and practical suitability of the annular (main tuyere) spiral-flat type
tuyere
The results of the water modeling experiments indicated that relatively to the annular straight-tube
tuyere, the annular spiral-flat type tuyere used is able
to become the gas stream of the main tuyere into being the rotating motion with a suitable intensity. That
can make the bath attain a better agitation, thus
reaching a better mixing efficiency. Furthermore, it
can decrease and even eliminate large bubbles, and
bring about a great number of small bubbles forming.
That will alleviate quite effectively the back-attack of
gas jet, decrease the non-uniformity and rate of the
erosion and wear of the refractory lining, thus improving the life of the refractory lining for the horizontal side blowing processes including the AOD process. Also, the utilization ratio of the oxygen gas and
the rates of the refining reactions will be enhanced
owing to marked increase in the reaction interface. It
should be said that this type of the tuyere possesses a
good latent using power and composite effectiveness
and well suites for industrial application.

3 Mathematical Modeling of the AOD


Refining Process of Stainless Steel [49- 51]
3.1

Analysis of the AOD process

It is well known that in AOD stainless steel making, the supplied oxygen is utilized to remove the car-

bon in the molten steel. The argon ( o r nitrogen)


blown simultaneously can decrease the partial pressure of the carbon monoxide and promote decarborization, thus achieving the effectiveness and objective of
removing carbon and reducing the loss of chromium.
However, the silicon and manganese dissolved in the
molten steel can also absorb the blown oxygen and restrict the oxidation reactions of carbon and chromium.
There exists throughout the competitive oxidation of
the carbon, chromium, silicon, manganese, and other
elements dissolved in the steel during the whole refining process.
Moreover, at high carbon concentrations, there
would be insufficient oxygen to oxidize the carbon
transferred to the reaction interface from the bulk of
the molten steel. This means that at high carbon concentrations, the rate of decarburization would be primarily related to the rate of oxygen blow. When the
carbon content in the steel is decreased to a certain
low level, the rate of decarburization may change to
being controlled by the mass transfer of carbon to the
reaction interface from the liquid bulk. Correspondingly, there is a critical point or a critical state in the
process like that in oxygen - converter steelmaking.
The oxygen gas entering the bath would also contact the iron atoms as a matrix of stainless steel and
form iron oxide, but most of the iron oxide formed
would, subsequently, quickly be reduced by the carbon, chromium, silicon, manganese and other elements in the molten steel. This means that the iron
oxide formed also would be an oxidant for them, and
would be mainly an intermediate product of the gas
blowing refining. In addition, their oxidation, to a
certain extent, would be related to the supplied oxygen rate even at low carbon concentration levels.
Furthermore, the bath always demonstrates an obvious non-isothermal characteristic during the refining
process, which can directly and strongly influence the
equilibrium and rates of the various refining reactions. Another feature of the AOD process is that the
bath is strongly agitated by the gas streams. This can
very effectively promote and intensify the heat and
mass transfer and is very advantageous in accelerating
the refining reactions and improving the homogeneity
of the bath composition and temperature, as pointed
out previously.

Vol. 6 No. 1 Mar.2002


3.2

Mathematical

WEI J. H. Physical and Mathematical Modeling of the Argon-OxygenDecarburization ...


1
[Fe] + ~-O2 = (FeO)

model of the process

Based on the previous analysis, a new mathematical model for the AOD refining process of stainless
steel has been proposed and developed, in which the
conditions and characteristics mentioned have all been
considered and noted.
3.2.1

Basic assumptions of the mathematical model

The initial assumptions of the new mathematical


model for the refining process were as follows:
1. The oxygen blown into the molten steel simultaneously oxidizes the carbon, chromium, silicon, and
manganese dissolved in the steel and the iron as a matrix; the iron oxide formed is also an oxidant for the
other elements and is essentially an intermediate
product of the refining process.
2. All the possible oxidation-reduction reactions
take place simultaneously and reach and establish a
combined equilibrium in competition at the liquid/bubble interfaces [41' 52- 56]
3. At high carbon contents, the oxidation rates of
elements are primarily related to the supplied oxygen
rate; at low carbon concentration levels, the rate of
decarburization is mainly determined by the mass
transfer of carbon in molten steel.
4. The unabsorbed oxygen blown into the liquid
steel will escape from the bath and form C02 with CO
in the exhaust gas, rather than dissolving and accumulating in the steel.
5. The bath composition and temperature are continually changing and are uniformly distributed at any
moment during the whole refining process.
6. The oxidation of elements in the steel other than
C, Cr, Si, and Mn is temporarily not taken into account; i. e . , the oxygen consumed by the other elements is ignored.
3.2.2

Refining reaction schemes

The oxidative reactions of the carbon, chromium,


silicon, and manganese dissolved in the molten steel
and the iron as a matrix of the steel by the blown oxygen can be written as

system can be produced from combinations of reaction


(11) through (14), respectively, with reaction (15):
[C] + (FeO) : {CO} + [ F e ] ,
A G c = AG~ + R T l n

a[] a(FeO)

(16)

a cr2o3
,AGcr = z~G[=r+ R T l n

(17)

a [Cr] a (FeO)
[Si] + 2(FeO) = (Si02) + 2 [ F e ] ,
a (sio2)
2
a[si] a (FeO)
[Mn] + (FeO) = (MnO) + [ F e ] ,

A G c = AG~i + R T l n

AGMn = AC~n+ R T l n

a(MnO)

(18)

(19)

a [Mn]a (~eO)
where a i - - t h e activity of i component; AGi and z3G7
- - t h e Gibbs free energy at the refining conditions and
the Gibbs free energy at the standard state for oxidation reaction of i element, respectively, J. g- 1 ; R - the gas constant, J" tool-1. K-1; T - - t h e bath temperature, K. These all belong among the possible reactions which occur in the system. Thermodynamically,
the reaction schemes presented by reactions ( 1 1 )
through (15) and reactions (16) through (19) can all
characterize the chemical-equilibrium feature of the
refining system but, kinetically, they are different,
the former being direct, and the latter being indirect.
3.2.3

Rate equations of the process

At high carbon contents, the average loss rates of


the carbon, chromium, silicon and manganese dissolved in the steel in the competitive oxidation are,
separately,
Wm dE%C] _ 2 ~ o
- 100Mc dt
22400 xc
Wm d [ % C r ] _ 2T/Qo
- 1.5 100Mc------~ d ~
22400 Xcr
Wm d [ % S i ] _ 2r]Qo
dt
22400 xsi

- 2 100Msi

3
2[Cr] + ~-02 = (Cr203)

(12)

- 100MMn

(14)

Pco

2[Cr] + 3(FeO) = (Cr203) + 3 [ F e ] ,

(11)

(13)

(15)

The following independent reaction equilibria in this

1
[C] + ~Oz = ICOI

[Si] + 02 = (SiOz)
1
[Mn] + ~-O2 = (MnO)

15

Wm d [ % M n ]
dt

2rlQo
- 22400XMn

(20)
(21)
(22)

(23)

At low carbon concentration levels, the average rate


of decarburization can be expressed as

16

Journal of Shanghai University

- Wmd[%C]-AreaPmkC([%C]-[%C]e)
dt

Wmdt ( d[ %Cr] Mcr2a

(24)

At this time, the following reaction can appropriately


be considered:
(Cr203) + 3[C] = 2[Cr] + 3ICOI

d[%C]
dt

:2 - ( - 8 1 - ~ )

(26)

where
81 = --

100McQo(1 - r]) + Q~.b


Wm
22400
F

AreaPmkc _ Pt
Wm
s2 =

ro Om C
Wm

[ %C3

)Qo<l-

dt

2Mcr +

d[ %Mn]
dt

The appropriate rising rate of the bath temperature is


dT_ /

dt

~/Mc@~d[%Cr] MMnod[%Mn] ~_
cp,~lk ~
~
+ MMn
dt

MsGd[%Si]

d[%C] + d[%Cr] +

Msi dt ) - Cp'm T ( dt
dt
df%Mn3 +d[%Si3 / 100
dt
--dt /-~-m{QOpoCp,o[(1 -r~)rgMco d[ %C]
Tg,ol + qloss + qs} + Cp.COTg Mc
dt

a[cr]
+ [ %C]
a CrxO3Kcr_c

(lOO

100

MMnO+ d %si]MsG / ] cp,~( T + d T ) + ( qlos~ +


MMn
d t 2Msi ]
q5)dt
(29)

(25)

Paying attention to the diluting role of the inert gas


(argon or nitrogen) and non-reacting oxygen, the following expression can be derived:

Ws

~6

(27)

+ Qs.

(28)

AHc d[%C] + AHcrd[ %Cr] + AHMnd[ %Mn]


dt
dt
dt
+ AHsid[ %
at Si]

)1/(lOOCp'm+lOOcp'sWs/Wm)
(30)

and Area--the total reaction interface, cm2; f c - - t h e


Henrian activity coefficient of carbon in molten steel;
kc--the mass transfer of carbon in molten steel, cm"
s - l ; Kcr.c--the equilibrium constant of [C]-(Cr203)
reaction; M~--the mole mass of i substance, g "
mole-l; Pt--the total dimensionless pressure in the
AOD vessel; Qo--the flow rate of oxygen, Ncma"
s - l ; Qsub--the total flow rate of inert gas, Ncma"
s- 1; xi--the distribution ratio of oxygen for / component in liquid steel; Wm--the mass of liquid steel, g;
[ % / ] - - t h e mass percent concentration of i solute in
molten steel, mass-% ; [% C]e--the equilibrium concentration of carbon in molten steel at reaction interface, mass-% ; rl--the utilization ratio of oxygen;
pm--the density of molten steel, g-cm -3
3.2.4

Heat balance of the system

QodtpoCp.o Tg,o +
Wm

QsubdtpsubCp,sub Tg,o +

d[ %C]AI..1
~ -~'aixC

W~cp,~T + 1 - ~ (

d[ %Cr] ~ ~,,.
d-i

M"/Cr --

d[ %Si]
d[ %Mn]Au
AHsi) dt = W m [ 1 +
dt
~--M.
dt
[d[%C]+d[%Cr]+d[%Mn]+d[%Si]/dt
I.
\ dt
]lOOJ
dt
dt
dt
Cp,m( T + d T ) + Qo(1 - 7])dtpo%,oTg + Q~ub"
W m

dtp~.bCp.~.bTg + ~

vessel, J" s-i; q2--the heat loss by conduction from


the lower of the vessel, J's-1;

q3--the heat loss by

conduction from the upper of the vessel, J's-1; q4-the heat loss by conduction from top of the vessel, J"
s- 1 ; q5--the heat loss absorbed by refractory lining of
the vessel during bath rising temperature,
qu--the uncertain heat loss of the system,

J" s-l;
J" s-l;

Tg, Tgo--the temperature of gas and its initial value,


K; cp, i--the specific heat of i substance at constant

The heat balance equation is


Wmcp,mT +

where qloss = q1+ q2+ q3 + q4 + qu; the refractory


lining with the shell was referred to approximately as
a multi-layer plate; ql, q2, q3 and q4 were, respectively, determined in terms of the one-dimensional
transient heat-conduction problems; q5 was taken to
be Wlcp,j AT and qu = (ql + c/2 + q3 + q4) x15%;
ql--the heat loss by conduction from bottom of the

d [ % C ] ) d t Mco

dt

M----cCp,co Tg

pressure, J" g- i. K- i ; Wl--the mass of refractory lining, g; Ws--the mass of slag, g; AHi--the oxidation
enthalpy of i element,

J" g-l; p~--the density of i

substance, g" cm -3
The parameters of the model were discussed and
more reasonably determined. Particularly, the Gibbs
free energies for the oxidative reactions of the elements dissolved in the molten steel were used to calculate the distribution ratios of the oxygen blown into
the bath among the elements.

Vol. 6 No. 1 Mar. 2002

WEI J. H. Physical and Mathematical Modeling of the Argon-Oxygen Decarburization...

3 . 3 Application of the mathematical model to


industrial practice
T h e new model has been applied to the industrial
practice of the austenitic stainless steel making (in-

17

of the model are fully confirmed.


Since the concentrations of Cr, Si, and Mn at the
ends of blowing periods were not determined in production,

the evaluations for the deviations of their

cluding ultra-low carbon steel) and tested on data of

values predicted by the model cannot be directly giv-

32 heats obtained in producing 304 grade steel in an

en. H o w e v e r , the Cr content in the steel after the

18 t AOD vessel, to examine its reasonability and reli-

pre-deoxidization indirectly predicted by this model

ability.
3.3.1

( 1 7 . 8 7 m a s s - % ) also agreed again excellently with


Deviations of results predicted by the mathe-

the determined value ( 1 7 . 7 4 mass- % ). This verifies

matical model from determined values

further the reasonability and reliability of the model.

As far as the carbon concentrations and bath temperatures at the ends of blowing periods are concerned, the predicted results by the model were in ex-

3.3.2
Competitive oxidation of elements and distribution ratios of blown oxygen among elements

cellent a g r e e m e n t with the determined values.

For

ous elements in the AOD refining process of stainless

period I of blowing, the maximum absolute deviations

steel, like that in any multi-component reaction sys-

T h e r e must exist the competitive oxidation of vari-

were 0. 0083 mass-% and 1 5 . 8 4 K, and the relative

tem. The blown oxygen has different distribution ra-

mean deviations are 1 . 8 1 %

tios among elements, and the ratios will dynamically

and 0 . 4 2 % , respective-

ly. For periods II and III of blowing, the maximum

change with the refining conditions, particularly the

absolute deviations are 0. 0014 mass-% and 7 . 5 9 K,

composition and t e m p e r a t u r e of the bath. T h e Gibbs

0.0000 mass-% and 0 . 7 1 K, and the relative mean

free energies of various oxidation reactions were first

deviations are 1 . 2 1 %

and 0.

employed to try to determine the values of this param-

0 3 5 % , respectively. The model can accurately pre-

e t e r for the elements by the author. The distribution

dict the carbon contents and bath t e m p e r a t u r e s at the

ratios of blown oxygen among C, Cr, Si, and Mn dis-

ends of blowing periods for the AOD refining process


of stainless steel, and the reasonability and reliability

solved in the molten steel for three heats (No. 266,

and 0 . 1 3 % , 0 . 0 0 %

0.8[-

281 and 354) are shown in Fig. 6.

.,,r.'l

2"~-.~, I

~,. ~

.,.I. I

=o
0
0
0

400
0.8

800

1200

1600

~" ~

,,-

2000

2400

2800

1-'---t..

0.6
04

0.2

-- ~
'

4(~0

'

860

'

12100

n
1600

....

ij

0.6

20{00

I~t/2

2400

......o--

,~" "

No.354

0.4

"i _ _ - - ' ,

00 t_
0

-;-..,...,..
400

800

12100

|6100

~90001

9400

Blowing time (s)


Fig.6

Distribution ratios of blown oxygen among C, Cr, Si and Mn during the refining process
C-C r - - - - S i - - ' - - Mn ......
1--Adding alloy agents or crop ends and scrap; 2--Endpoint of blowing period I; 3--Endpoint of blowing period II

Journal of Shanghai University

18

The critical carbon content fluctuates in the range


of 0.1 mass- % - 0 . 6 mass- % for the oxygen converter process [57-59]. The corresponding values obtained
by Roichel and Szekely [zSl are 0 . 1 5 mass-% and 0 . 5
mass-% for the refining processes of austenitic stainless steel respectively, in a 75 t VOD furnace and a 75
t AOD vessel. The results given by this model indicated that for the refining process of austenitic stainless
steel in an 18 t AOD vessel, the critical carbon concentration is in the range of 0. 25 mass-% - 0 . 4 0
m a s s - % , which should possess a higher precision.
3.3.4
Changes in c o m p o s i t i o n and temperature of

It is necessary to point out that after Xsi and XMn


are equal to zero, Mn and Si are still taking part in the
oxidation-reduction reactions in the system and influence the distribution of oxygen between C and Cr, although they no longer consume oxygen. Under a certain condition, a small amount of MnO or Si02 may
even be reduced, and appropriately, XM~ or Xsi possesses a minus value (Fig. 6).
It should also be emphasized that the values of xi
given are determined not only by the Gibbs free energies of oxidation reactions, but also by the effects of
the bath composition and t e m p e r a t u r e . The latter are
closely related to many factors, such as the kinetics of
the refining process, the mass and heat balances,
etc.
3.3.3
Deearburization rate and critical carbon con-

molten steel

The changes in the concentrations of C, Cr, Si,


and Mn in the liquid steel and the bath t e m p e r a t u r e
during the refining process (for heat 307) are given in
Fig. 8. It can be seen from this figure that, throughout, there exist the competitive oxidation and reduction reactions among C, Cr, Si, and Mn. The changes
in their concentrations and the bath t e m p e r a t u r e occur
just in this kind of competition.
3.3.5
Influence of blowing gas rate on decarburiza-

centration

Fig. 7 demonstrates the changes in the decarburization rates for three heats (No. 266, 281, and 354)
during the refining process with time. It must be
pointed out that at high carbon levels, the carbon concentration in the steel can also influence the decarburization rate by changing Xc, although its role is smaller. When the decarburization process is controlled by
the liquid-phase mass transfer of carbon, its rate also
concerns the supplied oxygen r a t e , only its influence
is greatly weakened. T h a t is one more feature of the
model.
IE-2 I

tion

The blown gas flow rate is closely related to the


oxidation of the elements in the bath, and strongly influences the refining process. As shown clearly in
Fig. 7, the critical point always arises before the end
of blowing period I in the existing blowing practice.

I/

Critical point

No.266

21

1
IE-4 I0

400

800

1200

'E2I
IE-4~
IE-2

1600

2000

2400

Critical point

'

I
400

800

1600

1200

2000

Z~0

'

800

21
I

1200

2400

No.354

,l \
I

2800

No.281

Critical point

1E-3

1E-4~

1600

31
I

2000

2400

Blowing time (s)


Fig.7 Changes in decarburization rate (for three heats) predicted by the model with refining time
1--Adding crop ends and scrap or alloy agents; 2--Endpoint of blowing period I; 3--Endpoint of blowing period II
Critical point: for No. 266, 1626 s, 6. 1790 x 10- 4 mass-%/s; for No. 281, 1425 s, 7. 4102 10- 4 mass-%/s; for No. 354, 1143 s, 9. 3923 x
10 - 4mass-%/s

Vol. 6 No. 1 Mar. 2002

WEI J. H. :

Physical and Mathematical Modeling of the Argon-Oxygen Decarburization ...


18

0.8

"~

',

,.

.......

t.A'i~.,'"" "

19

41
20

Mn

Delermined

E
'-~
O

data

19

0.0

.I ......
700

18
| 400

2100

2800

Blowing time (s)

i
0

I
700

I
1400

Determined
data
~

I
2100

I
2800

Blowing time (s)

Predicted changes in concentrations of C, Cr, Si, Mn in liquid steel and bath temperature during the AOD refining process
by the model (for heat of No. 307)
1--Adding crop ends and scrap or alloyagents; 2--Endpointof blowing period I; 3--Endpoint of blowing period II; 4--Endpoint of blowing period III
Fig.8

The surplus oxygen is almost all consumed for the oxidation of the chromium after the critical point. This
means that the time of blowing period I is excessively
long. On the other hand, it is often demonstrated that
the supplied oxygen before the critical point is insufficient in this practice. From the viewpoint of process
optimization, obviously, this kind of blowing practice
is not reasonable.
It can be suggested from the model predictions
that, under the prerequisite of ensuring that violent
splashing of the liquid on the bath surface does not
take place, raising suitably the blowing flow rates of
oxygen and nitrogen (or argon) will be beneficial to
heightening the rising rate of the bath temperature
and to intensifying the decarburization in blowing period I. For blowing period II, lowering appropriately
the ratio of oxygen to argon may decrease the loss of
Cr, thus avoiding an excessively high bath temperature. Also, the dilution role of argon to carbon
monoxide and the agitation of the gas stream to the
bath may be fully utilized, thus making the decarburization at low carbon levels progress smoothly.
Assuming a change of only the blowing mode and
taking the additional three sets of different 02:Nz and
Oz:Ar values from the existing practice for heat 281,
modeling calculations have also been carried out using
this model; the results are presented in Fig. 9.

It can clearly been seen from Fig. 9 that, for the


fourth blowing operation, with O2:N2 = 9 0 0 : 5 0 0
(Nm a- h- 1 ) in blowing period I and 02 : Ar = 200 : 800
(Nm 3- h -1) in blowing period II, the results much
better than those with the existing blowing practice
may be obtained, the carbon concentration of the
blowing period II endpoint may be decreased to a lower value (0.0255 m a s s - % ) , and the corresponding
chromium content is higher (16. 5365 mass-% ) , with
a bath temperature decrease of 30 K. This means that
there may he a better efficiency of removing the carbon with preserving the chromium in this case.
Thus, adjusting continuously the ratios of the oxygen to nitrogen (argon) and their flow rates, in terms
of the changes in the bath temperature and composition in the blowing process, to match the supplied
gases to the demand of the refining reactions can effectively promote the decarburization process. Also,
it can obviously decrease the consumption of gases and
the loss of Cr and ensure going on smoothly to the follow-up treatment procedures. The model can offer a
reliable control basis for this purpose.
Moreover, the other operating factors, such as the
initial temperature and mass of liquid steel and the addition of crop ends, scrap, and alloy agents, e t c . ,
can, to different degrees, directly influence the decarburization and other refining reactions too. The

Journal o.f Shanghai University

20

21

1.4

1.2

,--..///]

":~::..-..:.,

1.0

0.8

O~ 20

-:

',

"\

".....

\
,

0.4
-

.......

,,,

",...

",,

~
~

L)

:\

.\
"\

/'"

'2--

"
16.5

/ /: j " ~ /

""..

\~"
~.~.~
I

600

17.0 E

"".%

:""

d
I

7":".,
///'\

18

"-..

19

1200

1800

600

2400

............

.....

1200

1800

16.0
2400

Blowing time (s)

Blowing time (s)


Fig. 9

"'/

/'

0.2

. . ......

17.5

e~

.......
\

ForlC~J//

~ . :.,
: " ..,.,.
: ,//,..'"/--<f/,,,

\ ,,
\ '..:
",,
\ -.... ,,,

~-~ 0.6

0.0

18.0

Changes in concentrations of carbon and c h r o m i u m in molten steel and bath t e m p e r a t u r e at given flow r a t e s of o x y g e n
and n i t r o g e n ( a r g o n ) and their ratio values for heat of No. 281

1--Adding alloy agents or crop ends and scrap; 2--Endpoint of blowing period I; 3--Endpoint of blowing period II
a - - Oz:Nz = 800:400 (Nm3.h -1) for blowing period I and 02:Ar = 600:600 (Nm3-h - l ) for period II (existing practice)
b - - 02:Nz = 400:800 (Nm3.h i) for blowing period I and Oz:Ar = 400:800 (Nm3"h -1) for period II
c - - 02:N2 = 600:600 (Nm3.h -1) for blowing period 1 and 0z:Ar = 600:600 (Nm3"h ' l ) for period II
d - - Oz:N2 = 900:500 (Nm3.h -1) for blowing period I and 02:Ar = 200:800 (Nm3-h -1) for period II

model can also provide very useful and reliable information for these operations.

4 Summary Remarks
The latest studies and advances made by the author
with his research group on physical and mathematical
modeling for the AOD process have been summarized.
These studies have clearly and successfully brought to
light the fluid flow and mixing characteristics in the
bath and the overall features of the back-attack phenomena of gas jets during the refining process, and
offered a better understanding of the process.
The bath fluids undergo very vigorous stirring and
circulatory motion conditions during gas blowing
through two annular tuyeres with straight-tube type;
there is no obvious dead zone in the bath, thus providing an excellent mixing effectiveness and a short mixing time. The gas flow rate of the main tuyere has a
governing influence on the fluid flow and mixing in
the bath; the gas stream of the subtuyere evidently
has a physical shielding effect on the main tuyere jet.
A suitable increase in the gas flow rate of the sub-

tuyere would increase mixing efficiency. The angle


included between the two tuyeres has a marked influence on the fluid flow and mixing characteristics in the
bath. An excessively large or small angle separation
would reduce the stability of blowing and would also
be unfavorable to mixing. The range of 60 - 100 is
suitable for an 18 t AOD vessel.
At a given gas flow rate, a rotating gas jet will
have a higher mixing efficiency in an AOD bath than a
non-rotating gas jet because it provides stronger agitation and causes a more vigorous swirling and circulatory motion of the fluids. The rotating gas jet from the
spiral main tuyere has a larger influence on the fluid
flow and mixing in the A0D bath than the non-rotating
gas jet from the straight main tuyere. The non-rotating gas jet from the subtuyere also has a physical
shielding effect on the rotating gas jet of the main
tuyere, but compared to that on a non-rotating jet,
the action is evidently weakened owing to the rotating
motion of the main tuyere jet. The angle included between the two tuyeres has a greater influence on the
fluid flow and the stability of the blowing process

Vol. 6

No. 1

Mar. 2002

WEI J.H. :

Physical and Mathematical Modeling of the Argon-Oxygen Decarburization . . .

when using rotating jets than when using non-rotating


jets. The usable range of the angular separation between the two tuyeres is narrower when using rotating jets than when using non-rotating jets. The optimum angle between the two tuyeres for rotating jets
is 80 .
The relationships between mixing time and related
parameters respectively for a non-rotating and rotating gas jet have been obtained.
The back-attack phenomena of the horizontal rotating and non-rotating gas jets have individually different features from that in the bottom blowing process.
With an annular-tube tuyere, the gas stream of the
main tuyere has a governing influence on the back-attack action of a horizontal jet. The subtuyere stream
demonstrates appropriately a marked alleviation and
suppression effect on it, which is in form of an enhanced tendency with an increase in its relative flow
rate to that of the main-tuyere. The circulatory motion of the liquid in the bath would be another important reason to bring about the back-attack phenomenon of a gas jet. This is true especially for a horizontal jet. The buoyancy shows a considerable influence on the back-attack action of a gas jet with the
submerged blowing; it can not only increase the backattack intensity of a horizontal gas jet, but also enlarge the locally eroded and worn zone of the refractory lining. The rotating motion of a horizontal gas jet
can decrease the frequency and intensity of the backattack action and reduce the eroded and worn rate and
area of the refractory lining under a same blowing
pressure, relatively to the situation of a non-rotating
jet. Use of a gas jet with a suitable rotating intensity
is feasible and an annular spiral-tube tuyere with a
reasonable structure is well suited for improving the
AOD refining.
The carbon concentrations and bath temperatures
at the endpoints of blowing periods calculated by using
the new model developed recently are in excellent
agreement with the determined data. The Cr content
after the pre-deoxidization obtained from the model
predictions also agrees very well with the observed
value. The changes in the bath composition and temperature during the AOD refining process of stainless
steel with time can be accurately predicted by using
this model. The assumptions made to develop the
model can well reflect the real situations in the AOD

21

process. T h e r e exists throughout competitive oxidation among the various elements during the refining
process. The Gibbs free energies of the oxidation reactions of elements can be used to characterize fully
this kind of competition and to determine reasonably
the distribution ratios of oxygen among the elements.
The critical carbon concentration of decarburization
(after which the decarburization changes to become
controlled by the mass transfer of carbon in molten
steel) for the A0D refining process of austenitic stainless steel in an 18 t A0D vessel is in the range of 0 . 2 5
mass- % - 0.40 mass- %. The ratio of oxygen to argon
(or nitrogen) and the blowing gas flow rate can
strongly influence the changes in the bath composition
and temperature. For the existing blowing mode of
02 :N2 = 800:400 (Nm3"h -1) in the first blowing period and 02 :Ar = 600 : 600 (Nm 3" h- 1 ) in the second
blowing period, appropriately raising the oxygen and
nitrogen flow rates in the first period and decreasing
the oxygen flow rate and increasing the supplied argon
rate in the second blowing period can not only heighten the rising rate of the bath temperature and intensify the decarburization in the first period, but also reduce the loss of chromium, and avoid the excessively
high bath temperature, and remove the carbon in the
liquid steel to a lower level in the second period. Other operating factors, such as the initial temperature
and mass of liquid steel, the addition of crop ends,
scrap, and alloy agents, etc. can also change the decarburization progress. All of these factors should be
reasonably controlled. The model can provide very
useful information and a reliable basis for optimization
of the technology of the AOD refining process of stainless steel and control of the process in real time and
online.

References
I1]

Leach J C C, Rodgers A and Sheehan G. Operation of the


AOD process in BSC [J ]. Ironmaking Steelmaking,
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[ 4 ] ZHANG Mao-Huai, LIN Qi-Zeng, ZHU Ben-Li, et al.
Hydro-simulation o[ AOD vessel[A]. Proc. The National
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