ISIJ International, Vol. 36 (1 996). Supplement, pp.

S69-S72

Reaction Areas during OombinedBlowing in the AOD-converter

Piotr R. and Franz-Josef WAHLERS

SCHELLER
Krupp Thyssen Nirosta GmbH,D-44782 Bochum.Germany.
(Received on May16. 1996, accepted in final form on July 15. 1996)

In the KCB-Sprocess-a modified AOD process-process gases are bfown into a metal bath through
bottom tuy~res and onto the bath surface by a lance. Depending on the distribution of the gas volume flow
rates to the two blowing devices, differing reaction spaces and reaction areas are formed,
The change in the reaction areas for nitrogen absorption and their ratio in the metal bath and on the bath
surface, includfng meta[ droplets, has been determined from an investigation into the reactfon kinetics of
nitrogen absorption under modified blowing conditions.
The investigation wascarried out in the final stage of lance use with carbon contents of between 0.5 and
0.2•/•. The composition and volumetric flow rate of the process gases was varied during the decarburization
of AISI 304. The reaction areas increase as the volumetric gas flow rates rise. The reaction area of the gas
bubbles is considerablv greater than that of the metal droplets and the bath surface. Owing to the higher
reaction rate of oxygen with the metallic melt, rising gas bubbles have a smaller reaction area for oxidation
than for nitrogen transfer. Using the test technique presented here it is possible to optimize partial reaction
areas and thus process control.
KEYWORDS:
reaction areas; combined blowing; AOD,KCB-S; stainless steel; process control; nitrogen
alloying.

tents which actually slow nitrogen transfer down-that

allowance must be madefor mass transfer on the gas
l .
Introduction
side.6) This applies particularly whenN2 concentrations
A combined blowing process in the AODconverter are low in the gas phase.
through tuy~res and lance was developed to increase The mass flow of nitrogen from one phase to the
reaction areas and thus decarburization rate. As carbon other, thN, is proportional to the size of the interface
content diminishes, nitrogen or argon is added to the area A and the difference between activities AaNat the
oxygen in both blowing devices in order to reduce the boundaries of the reaction area. The mass transfer co-
pco Partial pressure. The total quantity and mixture efficient
X represents constant. The
a proportionality
ratio of the gases blown through lance and tuy~res are possibility of using activity
or chemical
potential as a
adapted to the diminishing carbon content of the metal measure of driving force has been previously discussed
bath, taking into account thermodynamic equilibriums for other metallurgical reactions,1 1'12) For the diffusion-
and reaction kinetics. Owing to the reductions in im-
pulse as the gas flow rate diminishes, the efficiency of the
controlled reaction
(I
st order reaction) the massflow is

= X1 A AaN,M_M
thN ' '
..........(1)
lance declines as the process continues.1) To assess the
efficiency of combined blowing, rate constants from the and for the 2nd order reaction caused by chemical
decarburization reaction achieved with and without use reactions on the interface
of the lance are compared.1-3) At higher carbon con-
= X2 A Aa~,G-M
thN ' ' •(2)
tents, costs dictate that the inert gas argon be replaced •• ••• • •
• •

by nitrogen. The absorbed nitrogen is largely expelled The following formula applies for penetration of the
as the process continues. interface layer on the metal side
The aim of the experiments in question was to de-
termine the change in the reaction areas for nitrogen
d[oloN]
=ftl'- A (aN -aN~) ..........(3)
.....
absorption under varied blowing conditions in the final dt V s,~
stage of lance use. This information is to be used as a and for the interface reaction
basis for control of partial reaction areas and thus for
further optimizing the process. d[oloN]
dt = p2 '
(a~
s,* -
2
)
aN*,M ....... •• •••••
•••(4)

2. Fundamentals of Nitrogen Transfer Similar inter-relations apply to the gas phase side as
Numerousinvestigations have already beencarried out described in formula (3); these have, however, not been
into the kinetics of nitrogen absorption in iron and iron taken into consideration for the purposes of this ex-
alloys.4~9) Whereasnitrogen absorption, assuming the amination, although they could be of significance under
N2 concentration in the gas phase is high enough, is the given conditions (gas mixture). ,

often perceived as being controlled by diffusion in the Should the entire masstransfer be diffusion-controlled,
melt, desorption is controlled by the chemical reaction under certain circumstances the following mayapply7)
at the interface.10)In technical processes, both steps of d[oloN] •tfN([o/oN]s~
the overall reaction have a role to play. If the melt has ~pl [o/oN]) .............(5)
dt
a high chromiumcontent, interface reactions mayoccur
so quickly~iespite increased oxygen and sulphur con- and for mass transfer occurring due to reaction at the

s69 O 1996 ISIJ

 ISIJ International, Vol. 36 (1 996), Supplement

interf ace: Toplance process gas

'02
-

d[o/oN] A
~;fi2'7;fN2([o/oN]~-[o/oN]2) ..........(6)
~
oL~E Ar
dt oa
5E subla nce N2
u'a'
Following integration and conversion, the following
forms of the above equations can be used to represent
e
a):';L
~VOE ~~'(
Q'

:~
ll
/1/~iwaste
99s
expermje~tal results:
A I In [o/oN]s ~ [o/oN]o ...............(7)
•(:~'
kl=p1•-=
V t'fN [o/oN]s~[oloN]
50 (In [o/oN]s~[oloN]o
k2=-p 2 A - 1
~~
• •

V tfN2 [~N]s
oo . [yoN]s+[yoN]
o o
o ~~~!>,
~(
[o/oN]s + [o/oN] ......(8)
~•"I'." ~=
+ In [o/oN]s [oloN] ""' j ~~=
~~f**~~
~
Wehave evaluated
two cases.
our experimental results for these
}~~

i ~r
-
~
(_)
1~
-
"'~~~~
~~~ T~y"'
p'0
~
g'=

The rate constant k also contains all the influences of 02

2
the fiows which have an effect on the distribution of the A,
reaction area in the metal and in the whole reactor and N
Qn the thickness of the flow boundary layer. For the Fig. 1. Schematic of combinedblowing in the AODconverter
reactor examined and the process condjtions involved, (KCB-Sprocess)
the rate constant thus has a specific value, using which
the process can be described and modelled mathemati- decarburization and metal oxidization the same. Thetests
cally .
were carried out during the melting of AISI 304.
To calculate rate constants it is first necessary to
calculate the equilibrium solubility corresponding to the
partial pressure of the nitrogen. For a nitrogen partial
4. Reaction Areas during CombinedBlowing in the AOD
Converter
I
pressure of bar, the nitrogen equilibrium solubility isl
3)

In the combined blowing process it is possible to

log[oloN]s(T)
= (~ 188/ T- I .25) - Iog fN(T)
**.....**(9)
differentiate between two reaction areas: a) inside the
with fN(T) as per the formula indicated in Ref. 7). The metallic melt and b) on the melt surface including metal
equilibrium solubility for AISI 304 increases as the dro plets.
temperature and the [C]-content fall. The rising gas bubbles induce turbulence which is
The equilibrium solubility of the nitrogen in rising gas dependent on the amount of gas injected and the ge-
bubbles at time t of the process is calculated from ometry of the vessel. The gas jet from the lance causes
droplets of varying size to splash off the liquid metal,
[oloN]s(T)
= [o/oN]s(T,p~. = I b*r) thus greatly increasing the reaction area. Independently
'=H ~N2 of this, meta] splashes are also caused on the surface by
x
1 f.=0 [P+pMg(H z)]dz ......(lO) bursting gas bubbles. Decarburization, nitrogen absorp-
~l r~Gas
tion and desorption take place simultaneously in all these
and used in Eqs. (7) and (8). reaction areas. By determining the rate constants for
masstransfer k
(in which reaction area A is included) in
3. Experimental Aspects partial reactor areas, it is possible to control and optimize
the process.
The experiments were carried out using an 80 tonne
AODconverter equipped with four bottom tuy~res and 5. Results and Discussion
a top-arranged lance (KCB-S process) and depicted
schematically in Fig. l. The ratio of bath height to Figure 2
depicts an example of the change in [N]
diameter was approx. 0.5. concentration during the process with differing methods
The tests were performed with C concentrations of of blowing as a result of simultaneous absorption and
between O.5 and O.2 o/o, i.e. after the decarburization rate desorption. Figure 2a) shows the development of [N]
has shifted from the constant to the exponential phase. concentration when no N2 is used during the process.
Oxygenand sulphur activity in the metal bath was 0.01 Figures 2b) and 2c) indicate the development of [N]
at ao and O02 at a In this part of the process, nitrogen
.
concentrations whenaddedto the lance and tuy~re gases,
is added to the
oxygen over a period of 5min. respectively. In test~ where N2 Wasadded to the lance
In the part of the process under examination, the com- gas (Fig. 2b)), the amount of [N] absorbed matched
position and the blowing rate of the gases was varied. the amount of [N] expelled, and consequently the [N]
Whenthe (02 +N2) mixture was injected through the concentration hardly changed. If N2 is added to both
bottom tuy~res, the (02+Ar) mixture was used in the the tuy~re gas and the lance gas, nitrogen absorption is
l~nce,.and vice versa. The ratio of the gas flow volumes greater (see Fig. 2d)).
ga~2. Th~.A, was ~ I : I
Vo VN in both the tuy~re and the lance The nitrogen efficiency for both methods of blowing
kinetics of nitrogen absorption in this stage of
was calculated from the injected quantity of N2 and the
the process was examined. The variation in the type of change in concentration. The degree of efficiency for the
lance gas used was selected in order to keep both the gas fiow rates examinedwas independent of the specific
flow ratios in the metal bath and the reaction areas for blowing rate; when using nitrogen in the tuy~re gas it

C 1996 ISIJ S70

 ISIJ Internationaf. Vol. 36 (1996), Supplement

O10 o020 05
a] a)
O08 E o
Lance: 02, 02 + Ar, Ar o 04 E
~ 006 TuyereT 02, 02 + Ar, Ar ? O015 o
C
o 004
o
e 03
~ O02 do
- OOID
r~T~l::::~J;:::
02
0,00 o 'p o k' (tuyere) o
a, O005
O10 aZ
ol
b)
o(
O08 Sta eA
Lance: 02 + N2 (iOO Nm3N2) OOOO Oo

~~
~:
OOe Tuyefe: 02 + Ar
S A 40 800
o
o 004 b)
z e o
O02 E o E
30 600
1~
o ~~
OOO
O10 co F1:::~Jyefej
O08
c)
~^~ Sta e A
~ 20
11.
400

~;
Lance: 02 + Ar
S!
Ok2 (tuyere)
006 Tuyere: 02 + N2 (140 Nm3N2) o 10 200
o
o 0.04
o aC O~
z
O02
o ol 02 03 04 05 06 0.7

OOO N*' t" ~i~~*

sp.*ifi* N, fto~ ,at* th,.~gh t~ye"
" I'nc* ,

O10 Frg. 3. Rate constants a) kl and b) k2 With N2 addition

O08
d)
~A~ Sta e A
in the lance
N, flow
and tuy~re gas as a function of the specific
Lance: 02 + N2 (60 Nm3N2) rate.
~
1,
OOe Tuyere: 02 + N2 (140 Nm3N2)
the rising gas bubbles before they reach the surface of
o 004
o the bath. In contrast, nitrogen transfer occurs until the
z
0,02 bubbles burst at the surface of the bath. The surface of
the bubbles is subjected to strong fluctuations in the
OOO
1o 20 30 40 50 60 highly-turbulent fiow. In gas bubbles with an equivalent
P,.*.*. ti*., *i* diameter of 2.5 cm, as observed in the ladle whenargon
Fig. 2. Changesin [N] concentration during the process with was injected,14) these processes occur every time. As the
different blowing variations. A= tested process section. gas-injection rate increases, so does the coalescence and
was approx. and in the lance gas ~ I olo.
23 o/o disintegration rate of the bubbles, which also contributes
In order to calculate the rate constants, a partial to an increase in the interface area. The shear stresses
pressure for the nitrogen in rising bubbles was assumed occurring cause the oxide film to be constantly broken
as per formula (10) and an overall pressure at the bath up and shifted, resulting in new, uncovered interfaces.
surface and for the metal droplets of I bar applied for In addition, oxide layers can be washed away as the
the entire reaction area. It was further assumedthat the bubbles rise, providing a larger reaction area for nitrogen
gas mixture (N2+02) was fully blended and that the in the upper part of the melt than in the lower part. The
kinetics of the gas-metal reaction in all reaction areas equilibrium of the oxide layers is then determined by po,
dependedonly on the difference in activity (taking into or pco/pco,' These fluctuations promote further nitrogen
account the partial pressure) and the specific mass transfer. This means that after the oxygen has been
transfer area. consumedin the rising gas bubbles, nitrogen transfer
In Figs. 3a) and 3b) the rate constants kl and k2 are continues to take place. It thus follows that on the whole
plotted as a function of the specific N2 injection rate. In the reaction area for the reaction of the oxygen with the
the case of both blowing methods, kl and k2 become melt (with respect to the higher reaction rate) must be
greater as the blowing rate increases, which, on the basis smaller than that for the reaction with nitrogen.
of the above-mentionedassumptions, signifies an increase In contrast, the oxidized surface of the fine metal
in the reaction area. When injecting through tuy~res this droplets splashed over the surface of the bath undergoes
means that despite the fact that the bubbles rise at a virtually no deformation. The metal droplets have a low
higher speed and thus have a shorter retention time in massand are subjected only to very weak shear forces
the melt, the gas-injected area and the gas hold-up on their trajectories outside the immediate gas jet area.
increase. This is in line with earlier experiments.8.14) This prevents the creation or regeneration of interfaces
Whenblowing with the lance, increasing the blowing rate and thus hinders further reactions. This meansthat the
leads to an increase in metal splashing. The great reaction area for the oxygen reaction and the nitrogen
difference in nitrogen efficiency and in the rate constants transfer must be roughly equal.
of the two blowing methods can be explained in each In the section of the process under examination the
case by the state of the oxide layer on the interface of ratio of the overall gas flow rates ~~Gas /V
L ~G**, T Was ,
the rising bubbles or on the metal droplets. This will be between l/2 and l/4. In this area, the ratio of rate
observed first on the rising gas bubbles in the metal bath. constants kL/kT increases as the rate of N2 flow rates
The enormousdifference in the degree of efficiency of ~N.,L/ PN.,T rises, Fig. 4. With
an equal flow rate through
reaction gases (approx. 23 o/o for N2 and approx. 100010 tuy~res and lance of, e.g., 0.5 Nm3 N2t - I min~ I , the ratio
for 02) would appear to indicate that 02 is absorbed by kl,L/kl,T=0.08. On the basis of the above assumptions

s71 O 1996 ISIJ

 ISIJ International, Vol. 36 (1 996), Supplement

OiO
possible to exert targeted influence on the masstransfer
V [Nm t mln J 07 .' 05.- o3. without making any major changeto the flow conditions.
O08
07 By determining the rate constants it is possible to
calculate changes in the partial reaction areas and the

~ 006
E] 05
reaction technique can be optimized in line with the
required targets.
o.3
O04 Acknowledgment
The authors wish to thank Prof. E. Steinmetz, HdT
O02 E] Essen, for his valuable suggestions on this work and for
reading the manuscript.
ooo
oo 02 OA 06 08 Io Nomenclature
VN,,L IV N,,T a: activity

Fig. 4. Ratio of rate constants for nitrogen absorption as a A: reaction area

function of the quotient of specific N, flow rates fN : activitycoefficient of nitrogen
through lance V~,,* and tuyires V~..*. H: bath height
kl : rate constant (Ist order reaction)
this
meansthat the reaction area of the splashed metal k2 : rate constant (2nd order reaction)
droplets and of the surface area of the bath for nitrogen
absorption must account for approx. 0.08 of the reac-
rh: massflow rate
tion area of the bubbles in the metal bath. Reducing the
P: atmospheric pressure
N2 flow rate throug.h the lance by half, i.e. to 0.25 p: partial pressure
Nm3 t : time
N2t-1 min~1 (VN=,L/rN,,T=0.5), reduces this pro- V: volumetric gas flow rate
portion to 0.02. Taking the calculation for k2 as a basis distance above the vessel bottom
for this observation, the dependency is greater (corre- z:
sponding to O. 15and O.04). The different dependencyof
P1 : masstransfer coefficient (Ist order reaction)
the k2,L/k2.T ratio on the ratio of gas fiow rates is
p2 : masstransfer coefficient (2nd order reaction)
efficiency
attributed to the fact that the k2 values contain a different n:
X1 : masstransfer coefficient xl = pl •
pM
masstransfer coefficient than that of the kl values and X2 : masstransfer coefficient X2 = pM P2 •

their calculation is based on a different driving force. density

This must be taken into account whendeveloping process p:
models. [ I: solved in liquid metal
Subscripts
6. Conclusions G: gas
(1) The efficiency
ofthe nitrogen was 23 o/o whenN2 L: Iance

was added to the tuy~re gas and I o/o WhenN2 was M:

O:
metal
start value
added to the lance gas.
(2) The reaction area for nitrogen absorption in- T: tuy~re

creases as the gas flow rate is increased. This applies

S: equilibrium
both to the tuy~re-injection and lance-blowing methods.
REFERENCES
(3) -If lance and tuy~res have the
sameN2 flow rate,
the reaction area of the metal droplets and the bath
l) R. Heinke, H
-U. Lindenberg. W. Rubens, K.-H. Schubert and
H. Z6rcher: Int. Oxygen Steelmaking Cong., Preprints,
surface for nitrogen transfer represents approx. 0.08 or Technisch-wiss. Verein, Eisenhutte Osterreich, Linz, (1987), 346.
O.15 (depending on method of evaluation) of the reac- 2) Y. Kato, T. Fujii, N. Harada, H. Nakamura, T. Sakuraya and
tion area of the gas bubbles in the bath. This statement Y. Habu: The 19th Comm.(Steelmaking), the Japan Society for
applies under the given conditions at a specified lance the Promotion of Science (JSPS), Rep. No. 10471, (Feb. 1983).
3) R. Tsujino, H. Hirata. S. Mizoguchi, H. Kajioka and R. Nakao:
setting and gas blowing rate (VN,,L.T =0.5Nm3N2 t-1
lron Steelmak~r, 21 (1994). Sept., 63.
min~1). At other stages of blowing, especially at the 4) M. Inouye and T. Choh: Trans. Iron Steellnst. Jpn., 8(1968), 134.
beginning of the process, other conditions apply. Owing 5) K. Kadoguchi, M. Sano and K. Mori: Tetsu-to-Hagan~, 71
(1985), 70.
to the higher reaction rate of the oxygen with the metal
6) P. C. Glawsand R. J. Fruehan: Metall. Trans. B, 17B(1986), 317.
bath, the reaction area of the bubbles used for oxidation 7) E. Steinmetz and P. R. Scheller: Stee/ Res.,58 (1987), 303.
is lower than for the nitrogen transfer, and the above- 8) E Steinmetz and P. R. Scheller: Steel Res., 58 (1987), 310.
mentioned proportion is thus higher. 9) T. Harada and D. Janke: Steel Res., 60 (1989). 337.
(4) For the development of process models it is of 10) Ban-Ya, T. Shinohara, H. Tozalii and T. Fuwa: Tetsu-to-
S.

significance whether the nitrogen transfer is seen as Hagan~, 60 (1974), 21.

no l 1) H. Schenck: Comment on W. Hess; Stahl Eisen, 79 (1959), 1567.
a Ist or 2nd order reaction. Dependencieson the varying l 2) E. Steinmetz: RadexRundschau, (1969), 605
process parameters remain the same, but different figures 13) R. D. Pehlke and J. F. Elliott: Trans. Metall. Soc. AIME, 218
are arrived at for the reaction constants. (1960), 1088.
14) E. Steinmetz and P. R. Scheller: Stah/ Eisen, 107 (1987), 417.
(5) By substituting an inert gas (Ar) for the reaction
gas (N2) in individual partial reaction areas it was

O 1996 ISIJ S72