Feature Article

Dephosphorization Strategies and Modeling

in Oxygen Steelmaking

P hosphorus, because of its

strong impact on steel
properties, is one of the most
immediately after formation dur-
ing hot metal refining (Figure 1).
Therefore, its activity must be
Today the task and aim of basic
oxygen steelmaking technology
are to supply molten steel
annoying elements in industrial reduced by an offering of liquid produced from hot metal, scrap,
stage production of steelmak- CaO. Since the pure lime has flux and other coolant/fuel
ing. Phosphorus in steel causes a very high melting point of charge just in time to meet the
hot shortness, temper embrittle- >2,800°C, a flux must be used logistic requirements of a modern
ment, ductility and toughness to liquefy the lime. This flux is steel melt and continuous
reduction, and is one of the FetO in today’s state-of-the-art casting shop. This paper
most sensitive elements for grain operations. Of course, SiO2 also reviews the metallurgical basics
boundary segregation.1 Table 1 supports the solution of lime, and discusses the different
gives an overview.2 but lowers the activity. The gen- possibilities to succeed in the
eral equations for the reaction task by comparing the results
are defined as follows: of various steel plants and their
De-P Fundamentals 5 different approaches.
2[P ] +
2
{O2 } ⇔ (P2O5 )
Direct removal of phospho-
rus with oxygen into the BOF (Eq. 1)
slag will not happen because Authors
of thermodynamic restrictions.
Phosphorus pentoxide, P2O5, is 2 [ P ] +5 ( Fe tO ) ⇔ ( P2O5 ) +5 [ Fe t ]
not stable at steelmaking tem-
Wolfgang Urban
peratures and will be reduced (Eq. 2)
senior division manager,
metallurgy, Hüttenwerke Krupp-
Mannesmann GmbH, Duisburg-
Huckingen, Germany
[email protected]
Table 1
Effect of Phosphorus in Steel2
Matthias Weinberg
Property Effect of Phosphorus
general manager, process
Strength Strong increase (ferrite strengthener) technology, Hüttenwerke
Krupp-Mannesmann GmbH,
Bake hardenability Increase Duisburg-Huckingen, Germany
[email protected]
Ductility Strong decrease
Fe-Zn galvanneal May improve resistance to powdering
Phosphatability Increase Jürgen Cappel
Fish scaling Decrease senior consultant, Iron & Steel,
Enameling steels Cappel Stahl Consulting,
Pickling Increase Meerbusch, Germany
juergen.cappel@cappel-
Weldability Not harmful for <0.1 mass % consult.com
Core loss in motor laminations Strong decrease
Fracture toughness Strong decrease

AIST.org  April 2015 ✦ 91

 Figure 1
0 2 [ P ] + 5 ( Fe tO ) + n (CaO ) ⇔ (nCaO × P2O5 ) + 5 [ Fe t ]

e 2O
3 (Eq. 3)
6F
→ CO 2
-200 +O 2 M
O2 →2
e 3O 2C+ The equilibrium constant for Equation 3 is:
4

4F e 3O
4

2F M M
→
+O 2
2FeO
e 3O O→
6F 2Fe+ 2 C+O →CO 61,110
-400
1/2
F e 3O 4 2C+
2 2
log K P = − 23.3
O 2→
O→ TK
RT ln PO2 in kJ

Fe+ S
2 2 CO
3 / 2 B P 2O 5 M
2/5 M
M + O 2→ M
P2 TT (Eq. 4)
-600 2/5 )
T O
P2
5 M
O a O+ MT
2Mn /5(
3C
+ O 2→ 2 Other important factors are the phosphorus dis-
2Mn aO→ T
-800 + 6/5
C tribution (Equations 5–6) and the dephosporization
O2 T
P 2+
2/5 →S
iO 2 O·S
iO 2 (De-P) efficiency factor (Equation 7):
O 2 Ca
Si+
2
O →
i+ 2

-1000 2C
aO
+S
→2
l O3
/3A 2 M B
B
LP =
(%P )
[%P ]
O
Al+
2

4/3 Mg M
O
→2 aO M
+ O2 2 C
g →
2M + O (Eq. 5)
-1200 2C
a
2
T

500 1000 1500 2000

Temperature in °C
LP2O5 =
(%P O )
2 5
Change of state
Melting point
Element
M
Oxide
M
[%P ]
Boiling point B B
(Eq. 6)
Sublimation point S S
Transformation point T T

Richardson diagram for oxides.3 hP =

[ P ]Initial − [ P ]EOB
[ P ]Initial
(Eq. 7)
Figure 2
The positive coefficient of
110 the equilibrium constant K P
Bas 3.0–3.2 Fe 18–20% (Equation 4) shows that the reac-
100 Bas 3.2–3.4 Fe 18–20%
tion is exothermic. Since the tem-
Phosphorus Partition Lp = (%P)/[%P]

Bas 3.4–3.6 Fe 18–20%

90
perature is the denominator, it
is clear that with increasing tem-
80 perature, the reaction will move
to the side of the reactants.
70 When looking into the phase
diagram CaO-FeO-P 2 O 5, it
60
becomes evident that equilibrium
will be achieved at a sufficient
50
CaO/P2O5 ratio of >3. Based on
40 Equation 3, it can be estimated
that De-P is encouraged by:
30
1680 1690 1700 1710 1720 1730 1740 1750 1760 1770 1780 1790
• High oxidizing conditions
Temperature TEOB, °C in the BOF (aFeO ↑).
• High lime activity in the
Phosphorus control and tapping temperature. slag (aCaO ↑).
• Low process temperature
(TEOB ↓).

92 ✦ Iron & Steel Technology A Publication of the Association for Iron & Steel Technology
 Figure 3
Of course, all other factors 100
that enhance lime solution and 1680–1710°C Bas 3.4–3.6
increase the reaction surface 1710–1740°C Bas 3.4–3.6

Phosphorus Partition Lp = (%P)/[%P]

90 1740–1770°C Bas 3.4–3.6
between the metal and slag — like >1770°C Bas 3.4–3.6
reactivity/grain size of the lime
80
or efficient bath stirring ener-
gy — support the De-P process
70
as well. The fundamentals and
the relevant parameters of De-P
60
in industrial application are very
well investigated and understood.
50

Process Temperature TEOB — As

40
mentioned earlier, the strongest
influence on the achievable phos-
30
phorus content of the steel melt is 14 16 18 20 22 24 26 28
temperature. It is well understood (%Fet) Content in BOF Slag, %
that De-P gives the best results
in the temperature range of the
Total iron content in slag (%Fet) and phosphorus distribution.
hot metal (<1,450°C), where hot
metal pre-treatment is operat-
ed. The De-P starts immediately
when the silicon is oxidized from Figure 4
the metal.
100
In the later stage of the BOF 1680–1710°C Fe 18–20%
process, a low tapping tempera- 1710–1740°C Fe 18–20%
90
ture is favorable for phosphorus 1740–1770°C Fe 18–20%
Phosphorus Partition Lp = (%P)/[%P]

>1770°C Fe 18–20%
control (Figure 2).4,5 Therefore, 80
it is understandable that opera-
tions equipped with ladle fur- 70
naces have a competitive advan-
60
tage compared to plants that must
guarantee the melt superheat for 50
treatment based on the melting
aggregate. 40

(%FetO) Content in the Slag 30

— Due to the De-P Equation 1,
20
Equation 3 is not a direct reac- 2.6 2.8 3 3.2 3.4 3.6 3.8 4
tion with the blow oxygen, but Slag Basicity B1 = (%CaO)/(%SiO2)
with iron oxide in the slag, it
is favorable to work at elevated
(%FetO) content. However, as Phosphorus partition LP and slag basicity B1.
shown in Figure 3,4,5 the LP is
initially enhanced with increasing
(%FetO) in the range of 15–22%,
but this effect is reversed at a content over 22%. phosphorus oxide compound during the blow. The
Another negative effect on LP that must be mentioned free lime available for this reaction can be described
is the (%MnO) content of the slag, which also has a by using the slag basicity factor:
declining effect on the LP. The influence of the MnO
is not so important in BOF steelmaking, since the
B1 =
(%CaO )
(%MnO) levels are low (<5% max.), depending on the
iron ore source for hot metal production.
%SiO2 ( )
(Eq. 8)
Slag Basicity (%CaO)/(%SiO2) — As mentioned
before, free, liquid lime is needed to form a stable

AIST.org  April 2015 ✦ 93

 Figure 5
400 At very high basicity, the lime surplus is too high
Temp. to be solute by the slag (%FetO) to liquid (%CaO),
+ 1873 K
1923 K
which increases the viscosity and reduces the reactiv-
300 ity of the slag significantly.
(%P)/[%P]equilibrium

Slag (%MgO) Content — The slag (%MgO) content

200
is an important factor to control the wear of the
furnace refractory during operations and guarantee
100 long vessel lining lifetimes by using the slag-splashing
technology. In this application, the BOF slags are
enriched with (%MgO) by using dololime or MgO
0 pellets/briquettes to increase the viscosity of the slag
0 5 10 15 20
and to improve their sticking and melting properties.
MgO Solubility (mass%) By looking into the details, it can be stated that the
slag liquidus and solidus temperature is influenced
Slag (%MgO) content and phosphorus distribution LP.5,6 by the (%FetO), the (%MgO) and the basicity B1.
(%FetO) strongly decreases the melting temperature
and spreads the melting interval, which means the
which is a common factor to describe the lime surplus slag starts to generate liquid fractions. The basicity
in the slag that overcompensates for the silica genera- is almost neutral, with only a slight decrease in the
tion from the hot metal and scrap silicon charge input melting temperature. The slag (%MgO) content
to the process. Figure 4 shows results for Hüttenwerke generates a minimum melting temperature of the
Krupp-Mannesmann GmbH (HKM). It can be con- slag at 6–7%. At lower (%MgO) content, the melting
cluded that a basicity increase up to a level of 4.0 will temperature increases quickly. At higher (%MgO)
improve the phosphorus partition.5,7 Another inves- content, the precipitation of solid MgO starts and
tigation6 shows that a basicity of over 4.0 reverses the the viscosity increases with negative impact on De-P
positive effect of the lime addition. efficiency. These facts are important to know because
they strongly influence the efficiency of slag splashing,
(%CaO ) (%MgO ) which requires proper (%FetO) and (%MgO) control.
B2 =  At the high (%MgO) end, the negative influence on
(%SiO2 ) the De-P efficiency must be taken into account.
It is clear that high (%MgO) content reduces the
(Eq. 9) reactivity of the slag and, accordingly, the efficiency
of the De-P, as shown from labo-
ratory trials in Figure 5; 5,6 the
Figure 6 “natural” (%MgO)n content (from
charged lime and refractory wear)
1,500
would reach up to 2.0–2.5%. The
1,400 Blow - Stir saturation content of (%MgO)S is
1,300 Top Blow only
varying with the slag basicity B1,
1,200
but can be estimated at 5–6% at
1,100
1,000
a basicity of 3.0. Figure 5 shows
900
a quick decline in the phospho-
[O], ppm

800 rus distribution factor L P with

700 increasing (%MgO) content in
600 the slag.
500
400 Steel [%C] content — For the
300 De-P reaction, strong oxidiz-
[C][O] = 37,5
200
[C][O] = 25,0
ing conditions are favorable.
100
[C][O] = 12,7
Especially at the end of the blow,
0
.000 .010 0.20 0.030 .040 .050 .060 .070 .080 .090 .100 .110 .120 .130 .140 .150 .160 .170 .180 .190 .200 the total oxygen available for the
[C], % reaction is, of course, dependent
on total amount of oxygen blown,
and this influence can best be
Carbon [%C] EOB and oxygen [ppmO] EOB content at end of blow.8 described by the end-of-blow

94 ✦ Iron & Steel Technology A Publication of the Association for Iron & Steel Technology
 Figure 7
carbon content [%C]EOB. The 66 21
lower the [%C]EOB, the higher
the [ppmO]EOB. Both liquid steel
64 20

Phosphorus Partition Lp (%P)/[%P]

components are linked togeth-
er by the [%C][ppmO] product,

(%Fet) Content of Slag, %

which is an operations constant 62 19
describing the equilibrium stage
at the end of the blow (Figure 6). 60 18
The oxygen content in the melt
is directly linked to the (%FetO)
content in the slag. 58 17

It can be considered that a

general overblow of the heats to 56 (P)/[P] 16
low carbon content has the same (Fe)
Lance distance to bath surface = const.
effect on the De-P efficiency as
54 15
a reblow because of overly high 0 100 200 300 400 500 600 700 800 900 1000
phosphorus content. The addi- Heats on Lining, n
tional oxygen offered to the melt
increases the slag (%FetO) and
Phosphorus partition, slag Fet content and converter life.
removes more phosphorus from
the melt into the slag. The aim
for low carbon content offers
additionally only the possibil- Figure 8
ity of more accurate temperature
control.

Blowing Conditions — The effect

of the blowing conditions on the
De-P result is shown in Figure 7.
The figure shows the phospho-
rus partition L P and the total
(%Fet) content of the slag dur-
ing a regular furnace campaign.
Both parameters are declining,
although the lance distance to
the bath surface is always kept
constant. Since in this particular
BOF shop the oxygen flowrate is
also kept constant, the result must
be interpreted as follows: Stirring intensity and phosphorus distribution LP.9
With ongoing campaign life
and the related refractory wear,
the bath gets flat, i.e., the bath
diameter increases, but the bath height decreases. Mixing Intensity — It is well known that efficient De-P
With a constant bath distance and flowrate, the is also strongly dependent on the kinetics offered dur-
penetration depth of the jet remains constant. The ing blowing. Due to the low content of phosphorus
(%FetO) generation during blowing is dependent (240 kg/heat at a 300 t heat and a [P]INI of 0.0800%),
on the percentile ratio of the penetration depth on which is evenly distributed in volumes of almost 43 m3,
the bath height. The higher the percentile ratio, the shall be reduced to 30 kg/heat (= 0.0100%), it is
“harder” the blow. It is well understood that hard blow- crucial to bring the phosphorus molecules to the slag-
ing results in lower (%FetO) content. Because of the metal interface in the BOF vessel.
relationship between LP and (%FetO) as described This can be done either by emulsification of slag
before, the LP is reduced simultaneously. A dynamic droplets into the steel melt or by moving the melt from
blow control is required. the vessel bottom to the surface where the slag would
be on top. Both cases require strong mixing behav-
iors. Figure 8 shows a direct comparison between a

AIST.org  April 2015 ✦ 95

 Figure 9
process results from shop to shop.
100
The reason is that, under floor
shop conditions, there are dif-
Phosphorus Removal ηP = ∆[P]/[P]ini, %

90
150 kg/t
ferences between the ideal ther-
80
modynamic relations and their
70 0.0050% practical application. These dif-
0.0100%
0.0150%
Final
[%P]
P
= 0.010; L = 100
ferences are generated from slag
60 0.0200%
0.0250%
temperature, composition and
50 [P] 0.0300%
Final
150 kg/t 100 kg/t volume, turndown carbon content
m slag and related slag (%FetO) content,
40
50 kg/t hot metal initial [%P]HM content,
30 100 kg/t
and the operations parameters
50 kg/t
like lance height, oxygen flowrate,
20
bottom-stirring intensity, and
10 timing of the flux and iron ore
Final
[%P]
P
= 0.010; L = 50
additions. In consequence, every
0 individual plant usually develops
0.0000 0.0500 0.1000 0.1500 0.2000 0.2500
its own blowing regime and prac-
Initial Phosphorus [P]ini, % tice based on the analysis of indi-
vidual plant data. The selection
Dephosphorization by slag volume. of a general control model is not
a simple task.
In the end, the conclusion is
that every shop must develop
top- and a bottom-blowing BOF operated in the U.S. its own De-P strategy and calculation model using
It becomes evident that the bottom-blowing technol- the typical equation factors valid for operations in
ogy can achieve the same De-P efficiency as the top- that particular shop. The recommendation from the
blowing vessel, but with significantly lower (%FeO) authors is to use the simplest type of equation possible
contents in the slag. The bottom-blowing technology and to carry out a multi-variate analysis with a suffi-
is known for its better mixing behavior. cient volume of operation data. The influence factors
on the phosphorus partition should be implemented
Slag Volume — In practical operation, the tasks of in the analysis according to their effect on the LP.
the process are normally defined by the steel qual- Of course, the data collective must be controlled for
ity program (aim carbon, aim phosphorus and alloy inconsistency before the multi-variate analysis.
content = tapping temperature). The slag composition
is optimized for iron yield (%Fet) and low refractory
wear (%MgO), and the basicity (B1) is restricted to De-P Practice
save flux consumption. With all of these limitations,
the achievable De-P distribution factor is also fixed The BOF operation practice is not uniform in differ-
within only small limits. To achieve the desired end- ent parts of the world. The practice can be differen-
of-blow phosphorus content in the steel, the only way tiated for Europe, Japan and North America, using
left to increase the removal efficiency ηP is to increase special converter technology to complete the picture.
the slag volume. This is especially necessary in case of
low silicon content in the hot metal supplied from the European BOF Practice — In Europe, the com-
blast furnaces. In this case, the slag volume must be mon technology is to process Fe-rich iron ores from
increased by using silica flux or FeSi fuel to increase Brazil, Canada and Australia, which results in a hot
the slag volume to a sufficient level. metal phosphorus content between 0.060 and 0.090%.
Almost all plants are operating a combined blowing
process with top lance and bottom stirring. The heat
De-P Literature Review is blown down in a single-stage process. Because of the
production program, alloy contents are high, which
The distribution of phosphorus between metal and causes high tapping temperatures and an unfavorable
slag is difficult to predict. Many models were inves- De-P condition, which are compensated with higher
tigated and published over the decades (Table 2), basicity and (%FetO) content. (%MgO) enrichment
but all efforts to guarantee a steady-state operation and slag splashing are often not applied.
toward the end of the blow will still result in varying

96 ✦ Iron & Steel Technology A Publication of the Association for Iron & Steel Technology
 Table 2
Various Formulas to Describe the Phosphorus Partition Ratio
Source Correlation formula
(%P ) = −3.113 + 8198.1 − 0.2075 ⋅ log %C + 0.3956 ⋅ log %Fe + 0.6639 ⋅ log  %CaO / SiO 
Gemma, 1987 L [ ] ( total ) ( ) ( 2 )
[%P ] T (K )
(%P ) = 5.41 − 0.00218 ⋅T K + 0.00382 ⋅ %FeO + 0.0228 ⋅  %CaO / SiO  + 0.0029 ⋅ %MgO
Chukwulebe, 1996 L ( ) ( ) ( ) ( 2 ) ( )
[%P ]
(%P ) = −5.71 − 13590 + 0.384 ⋅ log %Fe + 0.431 ⋅  %CaO / SiO  − 0.361 ⋅ log %MgO
ESAI, 2010 L ( total ) ( ) ( 2 ) ( )
[%P ] T (K )
(%P ) = −5.41 − 10173 + 0.0088 ⋅ log %C + 0.855 ⋅ log %Fe + 0.346 ⋅  %CaO / SiO  − 0.144 ⋅ log %MgO
Meishan, 2011 L ( ) ( total ) ( ) ( 2 ) ( )
[%P ] T (K )
(%P ) = 10.6 + 2.5 ⋅ log %FeO + 0.5 ⋅ log %P O + 5.0 ⋅ log %CaO
Turkdogan, 1996 log ( ) ( 2 5) ( )
[%P ]
(%P ) = −0.36 + 0.5 ⋅T K + 2.5 log %FeO + 5.9 log %CaO + 0.5 ⋅ log %P O
Balajiva, 1946 log ( ) ( n) ( ) ( 2 5)
[%P ]
(%P ) = −8.55 + 7710.2 + 2.5 log⋅  %FeO ⋅ 55.8 + 0.0715 ⋅ %CaO + %MgO +  105.1 + 0.0723 ⋅ %C
Ogawa, 1993 log   ( ) T K  [ ]
[%P ] T (K ) 71.8  ( )

(%P ) = 5.9 ⋅ log %CaO + 2.5 ⋅ log %FeO + 0.5 ⋅ log %P O + 0.5 ⋅ C + 0.36
Balajiva, 1947 log ( ) ( ) ( 2 5)
[%P ]
(%P ) = −16 + 22350 + 2.5 log %Fe
Healy, 1970 log ( totaln ) + 0.08 ⋅ (%CaO ) ± 0.4
[%P ] T (K )

(%P ) = −10.52 + 11570 + 2.5 log %Fe

Suito, 2006 log ( totaln ) + 0.072 ⋅ {(%CaO ) + 0.3 ⋅ (%MgO )}
[%P ] T (K )

(%P O ) = −0.69 + 2.5 ⋅ log %FeO ′ − %FeO ′ ⋅ 1.55 ⋅ 10 

+ 9.12 ⋅ 10 −5 ⋅ (%FeOn )′ 
Bannenberg, 1981 log
2 5
( ) ( )  −2

[ ]
P
n n


ln
(%P O ) = 2 5 20, 254
+ 0.3638 ⋅ ln (%FeO ) − 0.0499 ⋅ (%MgO ) − 6.299
Tata, 2007
[P ] (T + 273.15)
(%P O ) = −7.9517 − 13958 − FeO ′ ⋅ 1.43 ⋅ 10
Bannenberg, 1994 L
[P ]
2 5

T (K )
n ( −2
)
+ 1.032 ⋅ 10 −4 ⋅ FeOn ′ + 2.5 ⋅ log FeOn ′

(%P ) 11570
Suito, 1995 log 3 = −10.52 +
T (K )
{
+ 0.72 ⋅ (%CaO ) + 0.3 ⋅ (%MgO ) + 0.6 ⋅ (%P2O5 + %MnO ) }
[%P ] ⋅ (%Fet )2
 (%P )  11, 570
2.2  = 0.072 ⋅ (%CaO ) + 0.3 ⋅ (%MgO ) + 0.6 ⋅ (%P2O5 ) + 0.2 ⋅ (%MnO ) + 1.2 ⋅ (≤ CaF2 ) − 0.5 ⋅ (%Al 2O3 ) +
Suito, 1981 log    − 10.52
 [%P ] ⋅ (%Fe t )  T

1, 400 2.59
Sobadi, 2000 log ( PO2.5 ) =
T
− 5.75 −
(%SiO2 ) {
⋅ (%CaO ) + 0.33 ⋅ (%Me ) + 0.55 ⋅ (%MgO ) − 0.9 ⋅ (%Fe tO ) − 0.77 ⋅ ( PO2.5 ) }
Turkdogan, 2000 (
log (g P2O5 ) = −9.84 − 0.142 ⋅ (%CaO ) + 0.3 ⋅ (%MgO ) )
( P ) = 5.9 x log CaO + 2.5 x log( FeO) + 0.5 x log P O + 10.6
Turkdogan’s model2 log ( ) ( 2 5)
[ P]
( P ) = 22350 + 0.08 × CaO + 2.5 × log Fe − 16
Healy’s model3 log ( ) ( t)
[ P] T
Optical basicity log CP = −18184 + 435.84 Λ − 22.35Λ2 + 22390 ( Λ / T ) − 0.06257 x FeO − 0.04256 x MnO + 0.359 x ( P2O5 )
03

model5,6

log
(P) = 0.720 x (CaO ) + 0.3 ( MgO ) + 0.6 ( P2O5 + MnO ) +
111570
− 10.520
Suito’s model7 5
T
[ P ] x ( Fet ) 2

Suito and Inoue’s log ( K P ) = 0.145 x (CaO ) + 0.3 ( MgO ) + 0.6 ( MnO ) + ( 22810 / T ) − 20.56
model7
Molecular slag (% P2O5 ) = 7.04 log %CaO + 9922 − 20.2
log ( )
model7 [% P ]2 (% Fe)5 Tc + 17.8
Quadratic formalism RT ln aP 2O 5 (l ) = RT ln aP 2O 5( RS ) + 52720 − 230.706T
model9

AIST.org  April 2015 ✦ 97

 Figure 10
800
the mixing intensity increases the
efficiency of the metallurgical
reaction.
Phosphorus Partition Ratio (%P)/[%P]

700
To demonstrate this estimated
600 effect in more detail, an investi-
gation of the operations results
500 from more than 30 BOF shops
worldwide was carried out. The
400
investigation includes all types
300
of BOF processes available today,
which are grouped into the fol-
200 lowing categories:

100 • Top-blow and slag-splash

shops: shops that are apply-
0 ing intensive slag splashing
Healy’s correlation Top blown Combined blown Bottom blown
and top blowing only.
• Blow-stir and slag-splash
Comparison of phosphorus partition ration predicted by Healy’s correlation with shops: shops that are apply-
that practically attained during steelmaking.6,10 ing intensive slag splashing
and use top-blowing and
bottom-stirring technology.
Japanese BOF Practice — In Japan (and Korea and • Blow-stir shops: shops that use top-blowing and
Taiwan), the hot metal phosphorus is much higher bottom-stirring technology and do not apply
(0.090–0.120%) compared to the European condi- slag splashing.
tion. Therefore, in almost all of the plants, a double • Bottom-blow and slag-splash shops: shops that
slag process, whether as a hot metal pre-treatment or use bottom blowing in combination with inten-
a double-BOF process, is applied to control the high sive slag splashing.
phosphorus content and to achieve very low final
product [%P] contents, which are used as a prod- The result of this investigation is shown in Figure 11.
uct differentiation attribute to competitors in other According to the operation results, the lowest phos-
regions. It should be mentioned that Nippon Steel phorus partitions are achieved in the top-blow and
& Sumitomo Metal Corp. (NSSMC) has developed slag-splash operation, represented by the red dots and
and introduced a BOF lime injection technology to trend line. The dominant effect of tapping tempera-
enhance the De-P partition by quick lime solution. ture on the partition ratio is evident. The variation in
the results may be caused by the other factors, such
North American BOF Practice — In North America, as (%FetO), (%MgO), (%CaO)/(%SiO2), blowing
producers have the most comfortable situation with conditions, etc. It is obvious that these shops rely on
respect to the hot metal phosphorus content, which ladle furnace availability because this is the only way
is between 0.030 and 0.060%. These favorable condi- to reduce the tapping temperatures to levels below
tions and the availability of secondary reheating units 1,650°C.
allow the steel plants to operate at low tapping tem- On the other hand, shops that operate the blow-stir
perature, low slag basicity, moderate (%FetO) content process and do not apply slag splashing, represented
and high (%MgO) content as required for slag splash- by the green dots and trend line, achieve significantly
ing. The poor kinetics of the top-blowing process is higher De-P partition ratios. This effect allows them
sufficient to guarantee the steel grade specification to operate at high tapping temperatures of >1,700°C.
requirements. It can be estimated that, due to the higher mixing
energy of the combined process, the phosphorus
Bottom- and Combined-Blowing BOF Practice — partition can be doubled compared to top-blow
The influence of process type on the De-P behavior operation.
was reported earlier by Deo6 and Basu.10 Figure 10 Shops that operate a blow-stir process and apply
gives an indication of the results obtained in different intensive slag splashing are represented by the yellow
process variants compared to the theoretical Healy dots and trend line. It becomes obvious that, in this
correlation mentioned in Table 2. It becomes evident operation mode, metallurgical efficiency is sacrificed
that all industrial process results are below the ther- by refractory campaign life. As is often observed in
modynamic potentials. Furthermore, it is obvious that industrial operation, these plants try to compromise

98 ✦ Iron & Steel Technology A Publication of the Association for Iron & Steel Technology
 Figure 11
the benefits from all possible met- 120
allurgical options. Further cal- Blow stir
110
culations and investigation are y = 5E+35x-10.48 Blow stir-splash

Phosphorus Partition LP = (%P)/[%P]

R2 = 0.7857 Top blow-splash
required to see if this strategy 100
Bottom blow-splash
pays off. 90
It should be mentioned that 80 y = 2E+21x-6.072
the bottom-blowing process, rep- R2 = 0.7962
70
resented by the blue dot again,
shows a clear improvement com- 60
pared to the bottom-stirring oper- 50
ations, which results in higher
40 y = 3E+42x-12.7
De-P efficiency, lower slag (FetO) R2 = 0.4194
content, lower slag volume, and 30

therefore higher yield and lower 20

flux consumption. This process 10
has the highest metallurgical and
0
cost efficiency available in oxygen 1,600 1,650 1,700 1,750
steelmaking. Temperature, °C

Phosphorus partition and BOF operation practice.

De-P Modeling

Based on the above-mentioned

relations, modeling of De-P
always starts with the calculation of the phosphorus The LP formula developed for the special plant
removal level ηP (Equation 7) required to meet the configuration is used to calculate the L P value based
specification of the melt. By using this equation and on the aim temperature, aim [%C] and aim (%MgO)
the formula for LP (Equation 5), the slag volume can content. The tapping temperature is the result of the
be calculated as follows: temperature control model of the plant and is deter-
mined according to the steel composition and the nec-
hP ⋅ [%P ]INI essary metallurgical treatment. The (%MgO) content
m slag = m steel ×
LP [%P ]Steel is adjusted according to the refractory maintenance
strategy. The slag basicity is adjusted according to the
(Eq. 10) aim iron content at the lime saturation line. The aim
iron content is adjusted based on the aim [%C] con-
tent using the [ppmO] – (%FetO) relation at the [%C]
(
LP = f Taim ,[%C ]aim , (%MgO )aim ) [ppmO] product valid for the actual vessel operation.
The result of this model calculation is the slag
(Eq. 11) volume, which is necessary to remove the phospho-
rus successfully from the melt without any demand
for reblow. Since this calculation already includes
(%FetO )aim = f ([ ppmO ]aim ,Taim ) the basicity adjustment, no further corrections for
silicon are necessary. Strategies for how to deal with
(Eq. 12) a minimum and a maximum slag volume must be
implemented further on. Variations from the model
path are corrected by applying endpoint control
[%C ]aim ⋅ [ ppmO ]aim = constant technology.

(Eq. 13)
Specialties (Strategy Applied at HKM)

B1aim = f (%Fe tO )aim HKM has a unique plant configuration with two
blowing stands and a change vessel system, as shown
(Eq. 14) in Figure 12. The process is a blow-stir operation
with automated blow-end control and auto-tap prac-
tice. Because of this special plant configuration, the

AIST.org  April 2015 ✦ 99

process and the logistics in the plant are optimized the lower slag (%FetO) content accompanied with
for productivity. Production is operated continuously. lower basicity.
Maintenance is focused on scheduled stops, which The upper limit for the slag basicity is the slag lime
are also utilized to change out the vessels for refrac- saturation, as shown in Equation 16:
tory repair. The third vessel is cleaned, knocked out
 
and relined in a special relining stand located in a  68.1 − (%Fe tO )′ ⋅  0.3325 + 0.0024 ⋅ (%Fe tO )′ 
separate aisle without disturbing the operation at 
(%CaO )′sat   
=
 %SiO ′  ′
the blowing stand. The time required for a full vessel  ( 2 )  max (%SiO2 )
changeout is 12 hours plus two hours of heating only
from tapping out the last heat on the worn lining until (Eq. 16)
the start of blow of the first heat on the new lining. To
match the requirements of boiler maintenance with with:
the vessel changeout frequency, the lining is balanced  
for 1,000 heats. (%CaO )sat = 68.1 − (%Fe tO )′ ⋅  0.3325 + 0.0024 ⋅ (%Fe tO )′ 
 
To optimize productivity, refractory maintenance is
reduced to a minimum. Only the taphole changeout (Eq. 17)
and mouth cleaning are applied in a furnace cam-
paign. The vessel changeout is scheduled on fixed The calculation method of the required slag vol-
dates. When the date arrives, the vessel is taken out of ume is explained by a nomogram (Figure 13). In the
service despite the lining condition. The task of sched- first step, the amount of phosphorus to be converted
uled maintenance is to guarantee the lowest possible from the metal to the slag is calculated by using the
breakdown frequency during the regular operation lower-left diagram. The upper-left diagram converts
periods of five weeks (~35 days x 30 heats) in a row. the slag phosphorus mass to a total slag mass by using
Since refractory consumption is not the focus of the phosphorus partition LP as defined in Equation 5.
operations, it is also beneficial to take care to maxi- For this purpose, a Healy-like formula for the
mize yield by operations with a low-slag process tech- phosphorus partition was developed by multi-variate
nology. Because of this task, the required De-P also regression analysis of a database of tens of thousands
must be guaranteed at the lowest possible lime con- of heats (Equation 18).
sumption and lowest possible slag (%FetO) content.
Slag splashing is not necessary and is not applied. Also  (P ) k1
Ln  = + k 2 ⋅ ln ( Fe ) + k 3 ⋅ ( Fe ) + k 4 ⋅ Bas + k 5 ⋅ Bas 2 + k 6
slag (%MgO) enrichment, as a state of the art in most  [ P ]  T
BOF shops worldwide to increase the lining campaign
life, is not applied. Therefore, the influence of the slag (Eq. 18)
(%MgO) on De-P is negligible.
Of course, it must be guaranteed that the refractory As one can read from the equation, the phosphorus
wear is controlled within the scheduled changeout partition is defined as a function of the temperature,
periods. Because of this requirement, a minimum the basicity and the slag (FetO) content. Since at HKM
slag basicity B1 = (%CaO)/(%SiO2) is adjusted, which the temperature is a function of the secondary metal-
is not described by a saturation function but by an lurgical treatment required by the grade specification
empiric equation (Equation 15), which is basically a and the basicity is operated in the savings mode, only
linear function of the tapping temperature, the sili- the slag (%FetO) can be varied to change the phos-
con charge with the hot metal and the steel phospho- phorus partition. At HKM, the aim (%FetO) content
rus content [%P]. of the slag is calculated by Equation 18 and achieved
by adding oxygen volume or iron ore amounts accord-
(%CaO ) 
= k1 ⋅T + k2 ⋅  m Si ⋅
100 
− k3  + k4 ⋅ ln[%P ] +k5
ing to the tapping temperature, the aim phosphorus
(%SiO2 )min  m HM  content, basicity and slag amount.
In the upper-right diagram in Figure 13, the slag
(Eq. 15) volume required for De-P is compared with the mini-
mum slag volume and the maximum slag volume, with
The linear function is not directly proportional to three different possible results:
the hot metal silicon content. At high silicon levels,
basicity slightly decreases. Low steel [%P] requirement 1. The required De-P slag volume is lower than
is recognized in this formula by a slag basicity increase the minimum slag volume.
factor. At HKM, the negative impact on refractory 2. The required De-P slag volume is between the
wear caused by lower basicity is overcompensated by minimum slag volume and lime saturation.

100 ✦ Iron & Steel Technology A Publication of the Association for Iron & Steel Technology
 Figure 12
3. The required De-P slag volume is higher than
the maximum slag volume at lime saturation.

In case of a calculation result according to #1, the

slag volume for the heat is adjusted at the minimum
slag basicity required for the lining wear control. In
case of a calculation result according to #2, the slag
volume is adjusted with basicity between the mini-
mum and maximum basicity equivalent to the linear
relation of the slag volumes. In case the calculation
result requires #3, the slag is already lime saturated.
In this case, the slag volume must be increased by the
BOF vessel changeout system at HKM.
addition of lime and silica flux. At HKM, the practice
is to add FeSi fuel in these cases instead of gravel
gangue. Another alternative would be to increase the
aim (%FetO) content, which is unlikely because of the
related yield loss. basics of the reaction and the metallurgical param-
eters influencing the efficiency of the reaction were
discussed in detail. The following conclusions can be
Conclusion summarized from the discussion:

The dephosphorization reaction in the BOF process • The phosphorus partition is a kinetic phenom-
was exemplified. The chemical and thermodynamic enon rather than a chemical one.

Figure 13

130 130
Tapping Temp. °C
120 1770 120

110 1740 110

100 1700 100

Slag Amount kg/t

Slag Amount kg/t

+FeSi
90 90 B = B_sat
Basicity
80 80
min. 1740
70 70
B = B_min*(1+a/(a+b)) b sat. 1740
60 60 a min. 1700
50 50 B = B_min +Lime sat. 1700
40 40
min. 1770
sat. 1770
30 30
50 75 100 125 150 175 200 225 250 0 0.2 0.4 0.6 0.8 1 1.2 1.4

P Slag kg Si Hot Metal %

0.100

P_aim
0.090 0.015%P

0.020%P
0.080 0.012%P
P Hot Metal %

0.070

0.060

0.050

0.040
50 75 100 125 150 175 200 225 250

P Slag kg

Nomogram for slag volume calculation at HKM.

AIST.org  April 2015 ✦ 101

 3. Senk, D. et al., “Material Collection Iron Metallurgy,” RWTH
• BOF vessels equipped with combined blowing/ Aachen, Germany, 1994/1995.
stirring installations have kinetic advantages 4. Falkenreck, U.; Kempgen, J.; and Schlüter, J., “Strategies to
compared to only lance blowing vessels. Achieve Low Phosphorus Content for Customer Applications,”
• All industrial processes operated are far away AISTech 2007 Conference Proceedings, 2007.
from thermodynamic equilibrium, which is a 5. Basu, S., “Studies on Dephosphorization During Steelmaking,”
doctoral thesis, School of Industrial Engineering and
tribute to productivity. Management, Stockholm Sweden, 2007.
• Because of this fact, the individual vessel process 6. Deo, B.; Halder, J.; Snoeujer, B.; Overosch, A.; and Boom, R.,
characteristic is always an integral element of “Effect of MgO and Al2O3 Variations in Oxygen Steelmaking
De-P modeling. (BOF) Slag on Slag Morphology and Phosphorus Distribution,”
VII International Conference on Molten Slags, Fluxes and Salt,
• Since equilibrium-based models do not rep- The South African Institute of Mining and Metallurgy, 2004.
resent the industrial process, empiric models 7. Bannenberg, N., “Effect of P, Si and Mn Contents of Pig Iron
based on statistical evaluation must be devel- on the Attainable Phosphorus Contents in the Converter (in
oped for De-P modeling. German),” Stahl & Eisen, Vol. 111, No. 6, 1981, pp. 71–76.
• Every plant must develop its own De-P model 8. Guogang, Z.; Hüsken, R.; and Cappel, J., ”Experience
With Long BOF Campaign Life and TBM Bottom Stirring
adapted to the individual plant configuration Technology at BAOSTEEL Meishan in China,” AISTech 2012
on-site. Conference Proceedings, Vol. I, 2012, pp. 829–839.
9. Li, Y., “U. S. Steel BOP/Q-BOP Flux Control Model,” pre-
sentation, AIST Oxygen Steelmaking Technology Committee
meeting, 12 February 2012.
References
10. Basu, S.; Lahiri, A.K.; Seetharaman, S.; and Halder, J.,
1. Shukla, A.K., and Deo, B., “Mathematical Modeling of “Change in Phosphorus Partition During Blowing in a
Phosphorus Prediction in BOF Steelmaking — A Commercial BOF,” ISIJ International, Vol. 47, No. 5, 2007, pp.
Fundamental Approach To Produce Low-Phosphorus Steels 766–768. F
and Ensure Direct Tap Practice,” Department of Materials
and Metallurgical Engineering, Indian Institute of Technology
– Kanpur.
2. Bloom, T.A.; Fosnacht, D.R.; and Haezebrouck, “The Influence
of Phosphorus on the Properties of Sheet Steel Products and
Methods Used to Control Steel Phosphorus Levels in Steel
Product Manufacturing — Part I,” D.M., Iron and Steelmaker,
Vol. 17, 1990, pp. 35–41.

To nominate this paper for the AIST Hunt-Kelly Outstanding Paper Award, visit AIST.org/huntkelly.
This paper was presented at AISTech 2014 — The Iron & Steel Technology Conference and Exposition, Indianapolis, Ind., and published in the Conference Proceedings.

Did You Know?

The World Steel Association Renews Calls for a Safer Industry by Making Steel Safety Day an Annual Event
The World Steel Association (worldsteel) announced the launch of the second annual Steel Safety Day. Established
in 2014, Steel Safety Day was created to reinforce awareness of the five most common causes of safety incidents
and to create a safer working environment across the entire steel industry worldwide. By focusing on the five causes
— moving machinery, falling from heights, falling objects, gas and asphyxiation, and moving cranes — worldsteel
intends to create a continuous improvement process and reiterate its commitment to the safety and health of the
people who work in the industry.
Ahead of Steel Safety Day, worldsteel is requesting all of its members and the greater steel industry to carry out
an extensive safety audit on the five main causes of incidents between now and Steel Safety Day on 28 April 2015.
Each year, one of the five causes will be highlighted and more focus will be given to raise awareness of the cause
and how to prevent associated risks. This year’s Steel Safety Day focuses on moving machinery, and worldsteel urges
all steel producers to ensure reliable lockout procedures are in place to disable risks caused by moving machinery.
Edwin Basson, director general of worldsteel, said, “The steel industry’s ultimate goal is to create an injury-free,
illness-free and healthy workplace with zero incidents. This is why we established Steel Safety Day in 2014, and why
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102 ✦ Iron & Steel Technology A Publication of the Association for Iron & Steel Technology