ISIJ International, Vol. 49 (2009), No. 4, pp.

505511

Distribution of P2O5 between Solid Dicalcium Silicate and Liquid

Phases in CaOSiO2Fe2O3 System
Ken-ichi SHIMAUCHI,1) Shin-ya KITAMURA2) and Hiroyuki SHIBATA2)
1) Formerly Student, Graduate School of Engineering, Tohoku University. Now, Sumitomo Steel Wire Corp.,1-1-1 Koya-kita,
Itami, Hyogo 6640016 Japan.
2) Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 21-1 Katahira, Aoba-ku, Sendai, Miyagi 9808577 Japan.
(Received on November 12, 2008; accepted on January 14, 2009; originally published in Tetsu-toHagan, Vol. 95, 2009, No. 3, pp. 229235)

In most cases, the slag used in hot metal dephosphorization is saturated with dicalcium silicate (C2S) and
contains two phasessolid C2S and liquid. It is known that C2S and tricalcium phosphate (C3P) form a solid
solution over a wide range of composition. The distribution ratio of P2O5 between the solid solution and the
liquid slag phase has been reported to be very high. In order to determine the maximum possible concentration of P2O5 in the solid solution, the distribution ratio of P2O5 in slag containing a high concentration of P2O5
was measured in this study, and the influence of MgO and MnO on the distribution ratio was also investigated. CaOSiO2Fe2O3 slag containing up to 18 % P2O5 was melted at 1 873 K and then cooled to 1 673 K
at a rate of 10 K/min. During cooling, the solid solution of C2S and C3P precipitated from the liquid slag. A linear relationship, which was independent of the lime/silica ratio and P2O5 content, was found to exist between the distribution ratio of P2O5 and the T Fe content. On the contrary, the concentration of P2O5 in the
solid solution was strongly influenced by the lime/silica ratio and P2O5 content. If the P2O5 content was high
enough and the T Fe content was controlled to show the high distribution ratio, the concentration of C3P in
the solid solution can be increased to 100 %. No significant change was observed in the distribution ratio
upon the addition of MgO and MnO.
KEY WORDS: hot metal pretreatment; slag; dephosphorization; solid solution; precipitation.

1.

the liquid phaseas pointed out by Kitamura et al.4)

In addition, research to utilize the slag as a resource of
phosphate has been reported.5) Although phosphorus is one
of the indispensable elements for the growth of crops, the
obtainable natural resource of high grade phosphate ore
scarce in Japan. The C2SC3P solid solution in the slag,
which has a high phosphorous content, can be looked upon
as an alternative source of phosphate. The use of magnetic
forces to separate the solid solution from the bulk phase for
the slag which was powdered after the solidification has
been investigated.5)
In order to increase the efficiency of dephosphorization
and to use the slag as an alternative source of phosphate
ores, it is important to increase the distribution ratio of
phosphorous between the liquid slag and the solid solution.
Ito et al. measured this distribution ratio for CaOSiO2
P2O5FeO and CaOSiO2P2O5Fe2O3 systems, which contained 3% and 8% of P2O5.2) They clarified that the distribution ratio expressed in Eq. (1) is proportional to the T Fe
content in the liquid phase and that this relation remained
unchanged, irrespective of the type of iron oxide, i.e., FeO
or Fe2O3.

Introduction

The hot metal dephosphorization process was first invented in Japan. Further development of this process is still
underway, since it can be used to decrease slag generation
and production costs and increase productivity during the
production of high-purity steel. Initially, a highly basic slag
was formed by the injection of CaOCaF2 flux into the desiliconized hot metal. However, recently, treatment with
less basic slag containing a high amount of T Fe has become more common, as the use of fluorspar has been eliminated because of concerns for the environment. Normally,
the hot metal dephosphorization slag consists of CaO
SiO2FeOP2O5 system, and the industrial operation is
mainly carried out in the dicalcium silicate (C2S) saturated
composition range. It is well known that C2S forms a solid
solution with tricalcium phosphate (C3P) at the treatment
temperature over a wide composition range.1) This implies
that the product of the dephosphorization reaction can be
dissolved into the solid phase in slag. Measurements of the
equilibrium distribution ratio of P2O5 between the solid solution and the liquid phase revealed that P2O5 is concentrated in the solid solution with a high distribution ratio.2,3)
On the basis of these results the solid solution plays an important role in efficient dephosphorizationby acting as a
sink for phosphorus and lowering the phosphorus content in

LP 

505

(%P2O5 )SS
............................(1)
(%P2O5 )L
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Table 1. Slag composition (mass%).

where the subscripts SS and L denote the solid solution and

liquid phase, respectively.
Inoue et al. also measured the distribution ratio of P2O5
in slag prepared by various procedures.3) Their reported
values were very similar to those reported by Ito et al., and
they have shown that the distribution ratio reached the equilibrium value in less than 10 s, irrespective of the experimental procedures.
In these experiments the maximum P2O5 content in the
solid solution of C2SC3P was 20%, so that the upper limit
of P2O5 content in the solid solution has not yet been determined. For this purpose, it is necessary to carry out distribution ratio measurements using slag containing a very
high P2O5 content. Industrial slag also contains other oxides
such as MgO and MnO; therefore, the influence of these
oxides on the distribution ratio must also be clarified. In
this research, the distribution ratios for CaOSiO2P2O5
Fe2O3 systems containing a maximum of 18 mass% P2O5
were measured to determine the maximum P2O5 content in
the solid solution. The influence of oxides such as MgO
and MnO on the distribution ratio was also investigated.
2.

Experimental Methods

Reagent-grade SiO2, Fe2O3, CaCO3, and 3[3CaO P2O5]

Ca(OH)2 were used to produce slag. CaCO3 was first heated
at 1 273 K for 60 min or more under air atmosphere in an
Al2O3 or MgO crucible to produce CaO. Then, the reagents
were mixed in various ratios. The slag consisted of CaO
SiO2Fe2O3 system and 6, 12 and 18 mass% of P2O5 was
added to it. To study the influence of MgO and MnO on the
distribution ratio,10 mass% of MgO or MnO was added to
the slag. The mixing conditions are summarized in Table 1.
Figure 1 shows the composition ranges of the slag on the
CaOSiO2Fe2O3 phase diagram, and named A, B and C
respectively. The initial composition of CaO, SiO2, and
Fe2O3 was decided after preliminary experiments so that
homogeneous liquid was in fact formed at 1 873 K and so
that a C2S saturated liquid and solid were formed during the
cooling to 1 673 K. The composition of the slag quenched
from 1 873 K analyzed by EPMA (electron prove micro analyzer) were almost the same as the initial composition.
Therefore, in this study, the initial slag composition was
used.
The mixed reagents were put in a Pt crucible whose dimensions were F 5 mm5 mm. The Pt crucible was inserted into an Al2O3 crucible and heated in an electric resistance furnace. First, the sample was heated up to 1 873 K
at a rate of 10 K/min and kept for 60 to 120 min. Then, it
was cooled to 1 673 K at a rate of 10 K/min and kept for 0
to 60 min. Finally, the sample was quenched into the oil
bath. The heat treatment pattern is shown in Fig. 2.
According to the following reasons, Fe2O3 was used as
iron oxide in this experiment and the heating was carried
out under the air atmosphere, although in steelmaking condition, most of the iron oxide would be in the form of FeO.
1) Ito et al.2) has shown that the distribution behavior of
P2O5 between solid solution and liquid phases was not
different, when the iron oxide was changed from FeO
to Fe2O3.
2) By the preliminary experiments, it was found that FeO
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Fig. 1. Observed slag composition in the ternary phase diagram

of the CaOSiO2Fe2O3 system.

Fig. 2. Experimental conditions for precipitation of C2SC3P

solid solution.

was solved into the solid solution but the content of

Fe2O3 in solid solution was negligible small.
3) When FeO was used as iron oxide, Pt crucible can not
be used as Fe was precipitated in the slag. If MgO crucible was used, MgO content in the slag would become
very high and the experiments in CaOSiO2P2O5
FeOx system were not be able to carried out.
The quenched sample was mounted and polished. The
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composition of each phase was measured by EPMA. The

distribution ratio of P2O5 (LP) was calculated from the
EPMA analysis using the following methods.
The composition of the solid solution could be directly
analyzed by EPMA, as the average diameter of the solid solution precipitate was more than 10 m m. When the matrix
phase became glassy, liquid phase composition was analyzed by EPMA, also. In this case, LP could be directly calculated from the results obtained from the analysis. This
method was termed Method a.
In some cases, some crystallized phases were observed
in the matrix phase although the slag was quenched. When
the particles in each phase in the matrix were large enough
to be analyzed by EPMA, the liquid phase composition at
temperature was calculated from Eq. (2), using the composition and area fraction of each phase.

composition from Eq. (2)this method was termed

Method b.
When the particles in each phase in the matrix were too
small to be analyzed by EPMA, the matrix phase composition was calculated by Eq. (4) using the mass balance of
P2O5 shown in Eq. (3). Again, LP was calculated under the
assumption that the matrix corresponds to the liquid phase
at 1 673 K; this method was called Method c.
(%P2O5)T(%P2O5)LAM(%P2O5)SSASS........(3)
(%P2O5 )L 

(%P2O5 )T  (%P2O5 )SS  ASS

........(4)
AM

where (%P2O5)T and (%P2O5)SS represent the P2O5 concentration in the total slag and the solid solution, respectively.
AM and ASS represent the area fraction of the matrix and the
solid solution, respectively.

(%P2O5 )L 

[(%P O )  A ] ................(2)
2

5 i

3.

where Ai and (%P2O5)i are the area fraction and P2O5 concentration of phase i in the matrix, respectively.
In this case, LP was calculated using the liquid phase

Experimental Results

When the slag was quenched from 1 873 K, a uniform

glassy structure was observed, but when it was quenched
from 1 673 K, the solid phases had precipitated under all the

Table 2. Composition of liquid and solid phases in slag (mass%).

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experimental conditions. The compositions of the precipitated solid phases and matrix liquid phases at temperature
are summarized in Table 2. In this table, the distribution
ratio of P2O5 and the method of calculating it are also
shown. It can be seen that most of the solid phases are solid
solution of C2SC3P.
Figure 3 shows the influence of holding time on the P2O5
content in the solid and liquid phases in sample A-1 (6%
P2O5). Since the composition of each phase did not show a
notable change with the holding time, it was presumed that
equilibrium was attained between the liquid phase and the
precipitated solid solution during the cooling from 1 873 to
1 673 K. The rate of P2O5 distribution between the solid solution and liquid phase by the precipitation can be considered to be quite high. Also, it can be said that the precipitation as the solid solution of C2SC3P is more stable than the
precipitation as C2S without C3P.
The results obtained for the CaOSiO2Fe2O3 system for
various P2O5 content are summarized in Figs. 4 and 5. In
Fig. 4, the composition of the liquid phase is plotted in the
CaOSiO2Fe2O3 phase diagram. The observed liquid composition was close to the liquidus at 1 673 K even for the
P2O5-rich slag. This implies that the addition of P2O5 does
not cause any notable change in the composition of the liquidus. In Fig. 5, the composition of the solid solution is
plotted in the CaOSiO2P2O5 phase diagram. The compo-

sition of the solid solution was close to the pseudo-binary

relation of C2S and C3P. This result can be considered to be
reasonable because the Fe2O3 content in the solid solution is
less than 2%, as shown in Table 2.
As shown in Fig. 6, the P2O5 concentration in the solid
solution increased with the P2O5 content and also when the
slag composition changed from C to B to A. In the case of
slag A with 18% P2O5, the precipitated solid was found be
nearly pure C3P, whose composition is shown by the dotted
line in Fig. 6. This implies that the concentration of C3P in
the solid solution can be increased to 100% by controlling
the slag composition. A linear relationship was found to

Fig. 5. Composition of solid solution for each slag with various

P2O5 content in CaOSiO2P2O5 ternary phase diagram.

Fig. 3. Change in the concentration of P2O5 in the solid solution

and liquid phases with the holding time.
Fig. 6. Influence of slag composition on P2O5 content in solid
solution.

Fig. 4. Composition of liquid phase for each slag with various

P2O5 content in CaOSiO2Fe2O3 ternary phase diagram.

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Fig. 7. Relationship of P2O5 distribution ratio between the solid

solution and the liquid phases with T Fe content.

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exist between the distribution ratio and the T Fe content in

the liquid phase, which was independent of the lime/silica
ratio and P2O5 content, as shown in Fig. 7. This result is almost the same as that obtained by Ito et al.2) The change in
the distribution ratio with the slag composition, which is
shown in Fig. 6, can be explained by the change in the T Fe
content in each slag.
The results obtained by the addition of 10 mass% of
MgO or MnO to the abovementioned slag systems are discussed in the following paragraphs.
The compositions of the liquid phase and solid solutions
are summarized in Fig. 8 for the MgO-containing slag, and
in Fig. 9 for the MnO-containing slag. The composition of
the liquid phase was almost the same as the liquidus line of
the CaSSiO2Fe2O3 system, and no notable effect of the
MgO or MnO addition was seen. On the other hand, the
composition of the solid solution did not lie on the
C2SC3P pseudo-binary. As the MgO and MnO can be dissolved in the solid solution up to 6 mass%, shown in Table
2, the composition of the solid solution became different
from that of the pure solid solution of C2S and C3P. The ad-

dition of MgO or MnO brought about a slight decrease in

the P2O5 content in the solid solution, as shown in Fig. 10.
No clear influence of these additions was observed on the
distribution ratio of P2O5, as can be seen in Fig. 11.
4.

Discussion

As the liquid phase and precipitated solid phase are in

equilibrium, the activities of P2O5 in both phases are the
same. Then, the observed distribution ratio is proportional
to the activity coefficient of P2O5 in each phase, as shown in
Eq. (5), where a is the activity; g , the activity coefficient;
and k, the coefficient for the conversion of mass percentage
to mol fraction. Subscripts P2O5(Liq) and P2O5(SS) denote
the activity and activity coefficient of P2O5 in the liquid
phase and the solid solution, respectively.
LP 

aP O (SS)  P2O5 (L)

P O (L)
(%P2O5 )SS
k 2 5
k 2 5
....(5)
(%P2O5 )L
aP2O5 (L)  P2O5 (SS)
P2O5 (SS)

The activity of P2O5 in the liquid phase is calculated

Fig. 8. Composition of liquid phase in the ternary phase diagram of the CaOSiO2Fe2O3 system (a) and solid solution
in the ternary phase diagram of the CaOSiO2P2O5 system (b) of the MgO-containing slag.

Fig. 9. Composition of liquid phase in the ternary phase diagram of the CaOSiO2Fe2O3 system (a) and solid solution
in the ternary phase diagram of the CaOSiO2P2O5 system (b) of the MnO-containing slag.

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Fig. 10. Influence of MgO and MnO addition on the P2O5 content in solid solution.

Fig. 12. Relationship between T Fe content and the activity coefficient of P2O5 in liquid phase calculated by using the
regular solution model.

Fig. 11. Influence of MgO and MnO addition on the P2O5 distribution ratio between the liquid and the solid solution
phases.

Fig. 13. Influence of P2O5 content on the activity coefficient of

P2O5 in the solid solution.

using a regular solution model6) under the assumption that

all iron oxides are in the form of Fe2O3. Equations (6) and
(7) are used for the calculation of PO2.5 for the CaOSiO2
Fe2O3P2O5MgO and CaOSiO2Fe2O3P2O5MnO systems, respectively, where X is the mol fraction. The conversion from PO2.5 to P2O5 is shown in Eq. (8), where the subscript indicates the reference state of the activity, and (R.S.)
indicates the pure PO2.5 liquid under the assumption that
the regular solution and (L) represent the pure P2O5 liquid.

Figure 12 shows the relationship between the activity coefficients of P2O5 in the liquid phase obtained using the regular solution model and T Fe. The activity coefficient increases with the T Fe content when P2O5 content is the
same and with P2O5 content when the T Fe is in the similar
concentration range. By the addition of MgO and MnO, the
activity coefficient increased, although it was not so clear in
the case of MnO addition.
An increase in the T Fe content was expected to cause
an increase in the activity coefficient of P2O5 because of a
decrease in the CaO concentration and the basicity of the
liquid slag. Ito et al.2) considered that the decrease in the
CaO concentration caused by an increase in the T Fe content is the probable reason for the linear relationship between the T Fe content and the distribution ratio, which is
shown in Figs. 7 and 11. From the result shown in Fig. 12,
it could be stated that the activity coefficient of P2O5 in the
liquid phase was affected not only by the T Fe content but
also by the addition of P2O5, MgO, and MnO.
From the activity of P2O5 in the liquid phase obtained by
the regular solution model, the activity coefficient of P2O5
in the solid solution, where pure liquid P2O5 is in the standard state, can be calculated using Eq. (9).

RT ln PO2.5 (R.S.)
2
2
2
 14 640 X FeO
 251040 X CaO
 37 660 X MgO
1.5

2
 83 680 X SiO
 140 590 X FeO1.5 X CaO  20 090 X FeO1.5 X MgO
2

 65 680 X FeO1.5 X SiO2  188 280 X CaO X MgO

 33 470 X CaO X SiO2  112 960 X MgO X SiO2 (J) ...............(6)
RT ln PO2.5 (R.S.)
2
2
2
14 640 X FeO
 251040 X CaO
 84 940 X MnO
1.5

2
 83 680 X SiO
 140 590 X FeO1.5 X CaO 13 820 X FeO1.5 X MnO
2

 65 680 X FeO1.5 X SiO2  243 930 X CaO X MnO

 33 470 X CaO X SiO2  74 050 X MnO X SiO2 (J ) ..................(7)

aP2O5 (SS)  aP2O5 (Liq) ............................(9)

RT ln aP2O5 (L)  2 RT ln aPO2.5 (R.S.)  52 720  230.706T

(J / mol) ..........(8)

Figure 13 shows that the activity coefficient of P2O5 in

the solid solution increases with P2O5 content. Further, the
activity coefficient in the solid solution increases with the
addition of MgO and MnO. The increase in the activity co-

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efficient caused by the addition of MgO is greater than that

caused by the addition of MnO.
As shown in Fig.12, the activity coefficients of P2O5 in
the liquid phase and the solid solution increase with the
P2O5 content and with the addition of MgO and MnO. As a
result, the relationship between the distribution ratio and
T Fe is not influenced by the addition of P2O5, MgO, and
MnO, as shown in Figs. 7 and 11.

tween the distribution ratio of P2O5 and the T Fe content.

On the contrary, the concentration of P2O5 in the solid solution was strongly influenced by the lime/silica ratio and
P2O5 content. If the P2O5 content was high enough and the
T Fe content was controlled to show the high distribution
ratio, the concentration of C3P in the solid solution can be
increased to 100%.
(3) No significant change was observed in the distribution ratio upon the addition of MgO and MnO.

5.

Acknowledgement
This study was supported by the Iron and Steel Institute
of Japan and Steel Industry Foundation for the Advancement of Environmental Protection Technology, Japan. The
authors would like to thank Professor D. G. C. Robertson,
Missouri University of Science and Technology, USA, for
the useful advice during his stay in Japan as a Visiting Professor of Tohoku University.

Conclusions

In order to determine the maximum concentration of

P2O5 in the solid solution phase, the distribution ratio of
P2O5 in P2O5-rich slag was measured, and the influence of
MgO and MnO on the distribution ratio was also investigated. CaOSiO2Fe2O3 slag containing a maximum of
18% P2O5 was melted at 1 873 K and cooled to 1 673 K at a
cooling rate of 10 K/min. During cooling, the solid solution
of C2S and C3P precipitated from the liquid slag. The
EPMA results of the compositions of the precipitated solid
phase and the matrix liquid phase are as follows:
(1) The composition of the liquid phase and solid solution hardly changed with the holding time at 1 673 K. Equilibrium was probably established during cooling of the slag
from 1 873 to 1 673 K. It can be considered that the rate of
P2O5 distribution between the solid solution and liquid
phase by the precipitation is quite high.
(2) A linear relationship, which was independent of the
lime/silica ratio and P2O5 content, was found to exist be-

REFERENCES
1) W. Fix, H. Heymann and R. Heinke: J. Am. Ceram. Soc., 52 (1969),
346.
2) K. Ito, M. Yanagisawa and N. Sano: Tetsu-to-Hagan, 68 (1982),
342.
3) R. Inoue and H. Suito: ISIJ Int., 46 (2006), 174.
4) S. Kitamura, H. Shibata and N. Maruoka: Steel Res., 79 (2008), 586.
5) K. Yokoyama, H. Kubo, K. Mori, H. Okada, S. Takeuchi and T. Nagasaka: Tetsu-to-Hagan, 92 (2006), 683.
6) S. Ban-ya: ISIJ Int., 33 (1993), 2.

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