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#2003 The Japan Institute of Metals
Liquidus Surface of FeO-Fe2 O3 -SiO2 -CaO Slags at Constant CO2 /CO Ratios
Florian Kongoli1 * and Akira Yazawa2
1
2
FLOGEN Technologies Inc., www.flogen.com, 5757 Decelles Ave., Suite 511, Montreal, Quebec, H3S 2C3, Canada
Tohoku University, Sendai 981-0934 Japan
Liquidus surface of FeO-Fe2 O3 -SiO2 -CaO slags is an important parameter in various smelting and converting processes. It helps not only
to optimize the slag chemistry of current processes and their fluxing strategies but also to determine the availability of new slags for more
advanced technologies. In our previous publications, the liquidus surface of some multicomponent iron oxide slags has been quantified at several
constant oxygen potentials and the effect of the latter, ignored until that moment, was quantified along with the effect of some minor
components. In this work, the liquidus surface of some iron oxide slags is quantified at constant CO2 /CO ratios. This is a new convenient way for
the quantitative description of the slag liquidus surface and the effect of several fluxes, especially in those processes, such as slag solidification,
where oxygen potential changes continuously. This type of diagram also describes more dynamically the effect of oxygen potential, clarifies the
relation between CO2 /CO ratio and oxygen potential in terms of the liquidus surface (not widely understood by metallurgists today) and reduces
the gap between laboratory work and industrial experience.
(Received June 30, 2003; Accepted August 14, 2003)
Keywords: liquidus, FeOx-SiO2 based slag, iron oxides, oxygen potential, CO2 /CO, slag solidification, smelting, converting
1.
Introduction
Liquidus Surface of FeO-Fe2 O3 -SiO2 -CaO Slags at Constant CO2 /CO Ratios
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Fig. 4 Variation of pO2 and CO2 /CO ratio with temperature according to
3FeO(l)+O2 (g) = Fe3 O4 (s) and 3FeO(l)+CO2 (g) = Fe3 O4 (s)+ CO(g) at
a constant aFeO(l) and during the equilibrium cooling of a real slag X of
composition 46.3 mass% FeO, 6.7 mass% Fe2 O3 , 37 mass% SiO2 and
10 mass% CaO from 1623 to 1373 K.
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3.
Figure 5 presents the liquidus surface of FeO-Fe2 O3 -SiO2 CaO slag at a constant ratio of log(CO2 /CO) = 2 by the
means of a new format of multicomponent phase diagrams
whose basis has been previously described.1) This is in fact
the slag liquidus surface during slow equilibrium cooling
from 1623 to 1373 K where the oxygen potentials change
continuously from about 10!5 to around 10!8 . It can be
seen that at these conditions several primary phases are
present, i.e., magnetite (spinel), alpha-Ca2 SiO4 , Ca3 Si2 O7 ,
wollastonite/pseudo-wollastonite and silica and each of them
has its own characteristics. Some important points can be
easily made from this diagram. First, during continuous
cooling of these slags, the magnetite spinel phase is the
dominant primary precipitate phase. There is no stable
olivine or fayalite at these conditions, which suggest that
the name fayalite slag is not adequate at this particular
case. A meaningful name would be magnetite or spinel
slag if the primary precipitate phase is to be used to name the
slag. At these conditions the mineralogy of a slow cooled
solidified slag with an overall liquid composition of Fe/
SiO2 =1.1 and CaO=10 mass% (point X in the diagram)
would mostly contain primary magnetite. Second, lime does
not decrease, but instead, increases the liquidus temperature
of the slag at spinel saturation area and consequently
increases the risk of the magnetite (spinel) precipitation
which makes lime not a good flux in terms of the liquidus
temperature. This effect is much more pronounced in this
kind of diagrams compared to the diagrams at constant pO2
presented previously4) and this reflects the sensitivity of the
liquidus temperature toward changes on the oxygen potentials. It should be mentioned however that lime decreases the
liquidus temperature only in the region of newly proposed
FCS slag5,6) where it may be used as a good flux. Third, at
constant CaO an increase of Fe/SiO2 ratio in the magnetite
saturation area would increase the risk of magnetite
precipitation. This effect is more pronounced in this diagram
compared to the one given at constant pO2 , which again
reflects the sensitivity of the liquidus temperature toward
Liquidus Surface of FeO-Fe2 O3 -SiO2 -CaO Slags at Constant CO2 /CO Ratios
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DeltaH
DeltaS
DeltaG
(kJ)
(J/K)
(kJ)
Log(PO2 )
Log (K)
Log(CO2 /CO)
2
0.3
stable phase, but all other primary phases are present i.e.
olivine, wustite, alpha-Ca2 SiO4 , Ca3 Si2 O7 , wollastonite/
pseudo-wollastonite and silica. It can be seen that lime
decreases the liquidus temperature of these slags in the
olivine saturation area but increases it in almost all other
areas. At these conditions the mineralogy of a slow cooled
solidified slag with an overall liquid composition of Fe/
SiO2 =1.1 and CaO=10 mass% (point X in the diagram)
would mostly contain primary olivine.
4.
!9:34 !10:74
!8:99 !10:39
!8:66 !10:06
!8:34
!9:74
!8:03
!9:43
!9:73 !5:73
!7:73
!9:13
!9:44 !5:44
!7:44
!8:84
!9:16 !5:16
!7:16
!8:56
!9:69 !11:09
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metallic iron and in air where the oxygen potential does not
change (in air) or change only slightly (in equilibrium with
metallic iron). This is clearly reflected on the difference that
exists between the diagrams at constant oxygen potentials4)
and those at constant CO2 /CO, as given in this work.
6.
Conclusions
Liquidus Surface of FeO-Fe2 O3 -SiO2 -CaO Slags at Constant CO2 /CO Ratios
ed. by G. Kaiura, C. Pickles, T. Utigard and A. Vahed, (The Canadian
Institute of Mining, Metallurgy and Petroleum, Ottawa, 2000) pp 107121.
4) F. Kongoli and A. Yazawa: Metall. Mater. Trans. B 32 (2001) 583-592.
5) A. Yazawa and F. Kongoli: High Temperature Materials and Processes
20 (2001) 201-207.
6) F. Kongoli and A. Yazawa: James M. Toguri Symposium on the
Fundamentals of Metallurgical Processing, ed. by G. Kaiura, C. Pickles,
T. Utigard and A. Vahed, (The Canadian Institute of Mining, Metallurgy
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