Kho Swinbourne10 Mpm188 EAF
Kho Swinbourne10 Mpm188 EAF
Kho Swinbourne10 Mpm188 EAF
net/publication/230816525
Article in Mineral Processing and Extractive Metallurgy IMM Transactions section C · March 2010
DOI: 10.1179/174328509X431454
CITATIONS READS
14 1,481
5 authors, including:
Some of the authors of this publication are also working on these related projects:
Geopolymerisation: a generic solution for the valorisation of high-temperature residues View project
All content following this page was uploaded by Sander Arnout on 30 May 2014.
1 Ellingham diagram for relevant iron, chromium and car- et al.6 and was intended to understand the chemistry of
bon oxidation reactions: range of steelmaking tempera- the process as well as to be used as an aid to control
tures is shaded stainless steelmaking operations. This work has an
educational focus and will utilise the HSC Chemistry
Stainless steelmaking technology for Windows software package as a tool for gaining an
understanding of the chemical changes taking place
In the early days of stainless steel production carbon within the EAF. A subsequent paper will take the same
steel scrap, iron ore and lime (CaO) were charged into approach to examine decarburisation of molten stainless
an electric arc furnace (EAF). When the charge was steel in AOD and VOD converters.
molten, ferrosilicon, lime and fluorspar (CaF2) were The duty of the EAF is to efficiently and economically
added and the temperature of the bath was increased so deliver molten metal of the required composition and
that a large amount of low carbon ferrochromium could temperature to a converter. The EAF is the most widely
be added.5 With the advent of tonnage oxygen, oxygen employed melter due to its ability to process a wide
injection into the molten steel using a lance greatly variety of raw materials.5 An EAF, as shown schema-
improved the rate of decarburisation. However, the tically in Fig. 2, consists of a refractory lined hearth,
more oxidising conditions had the expected adverse vertical cylindrical sidewalls, and a removable roof.7
effect of extensive oxidation of chromium to the slag. A Graphite electrodes pass through holes in the roof and
reduction period using ferrosilicon to reduce the are clamped to arms which move vertically on masts
oxidised chromium from the slag became necessary mounted to the furnace assembly. This allows the
before low carbon ferrochromium could be added. electrodes and roof to be raised and swung to one side
Modern stainless steelmaking practice does not to allow furnace charging. Conventional furnaces have a
attempt to make stainless steel in an EAF alone. The horizontal tapping spout where the entire furnace can be
EAF is used to provide a molten steel charge for tilted for tapping, while some prefer eccentric bottom
converters, without any significant decarburisation of tapping furnace because it allows slag free tapping and
the melt and with minimum chromium oxidation to the decreased steel temperature losses during tapping.8
slag. The melt is then decarburised in a variety of Power is supplied from a three-phase, multivoltage tap
converters, with argon oxygen decarburisation (AOD) transformer to three carbon electrodes, though some
and vacuum oxygen decarburisation (VOD) being the furnaces use dc power and have only one or two
most widely used. As a result, these practices are electrodes.
classified as ‘duplex’ in that there are two stages in the Many modern EAFs are equipped with oxy fuel
production of stainless steel. Sometimes further refining burners and lances for injecting oxygen, lime and carbon
takes place under vacuum to produce stainless steels to increase the energy input into the furnace and reduce
which have very low carbon and nitrogen requirements melting cycle times. In such furnaces y60% of the
and this is known as ‘triplex’ practice.5 energy input is electrical with the remainder being
In this work, only the chemical reactions taking place chemical energy from oxy fuel combustion, oxidation of
during EAF melting will be discussed and modelled silicon and carbon and other chemical reactions.7
using computational thermodynamics. A mathematical Carbon and oxygen injection also generates a large
model designed to predict the compositions of slag and volume of carbon monoxide gas and so can cause the
steel as a function of time has been described by Arnout slag to foam around the electrodes, as will be discussed
later.
Table 1 Composition ranges for typical grades of A typical heat commences with the charging of a total
stainless steels,2 wt-% of y10 t carbon steel scrap, 90 t stainless steel scrap and
Grade Classification C Mn Cr Ni Mo 10 t high carbon ferrochromium (50 Cr, 7 C, 4 Si,
balance Fe, wt-%) through the open roof of the furnace.
304 Austenitic 0.05 1.5 18.5 9 … The roof is then swung into place, the electrodes are
310 Austenitic 0.08 1.5 25 20 … lowered and current flow is initiated so that the
316 Austenitic 0.05 1 17 11 2 electrodes bore through the scrap to form a pool of
410 Martensitic 0.1 0.5 12 … …
liquid metal. About 5 t fluxes containing mostly lime
430 Ferritic 0.03 0.4 16.5 … …
(CaO) and some magnesia (MgO) are added soon after.
2 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2010 VOL 119 NO 1
Kho et al. Understanding stainless steelmaking through computational thermodynamics: Part 1
Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2010 VOL 119 NO 1 3
Kho et al. Understanding stainless steelmaking through computational thermodynamics: Part 1
4 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2010 VOL 119 NO 1
Kho et al. Understanding stainless steelmaking through computational thermodynamics: Part 1
provide valuable information on the effects of process infinite dilution can be calculated from the Gibbs free
variables on the amounts and compositions of molten energy conversion from the pure substance to the wt-%
phases as a function of temperature or the amount of standard states by the following equation
one or more of the inputs. :
One problem associated with modelling stainless 0 5585c0i
DGr?wt ~RT ln (8)
steelmaking is that while the software thermodynamic Mi
database is very large, it does not contain data for the where Mi is the atomic weight of species i in g mol21.
species CrO(l). However it is possible to add the required The Gibbs free energies for converting from the pure
data from information in the literature. Toker et al.26 substance to the wt-% standard states were taken from
gave the Gibbs standard free energy change for the the literature.32 All activity coefficients used for species
formation of CrO(l) as follows in the slag and molten steel are given in Table 2. The
3 activity coefficients are given to only two significant
Cr(s)z O2 (g)~CrO(l) figures because they were calculated for representative
2
0 compositions of both phases, so greater precision cannot
DG ~{334218z63:18T J at 1938 to 2023K (5) be justified. Slag was assumed to be 50 CaO–25 SiO2–
Data in the form given in equation (5) is easily entered by 7 CrOx–7 AlO1?5–5 MgO–5 MnO–1 FeO. Steel was assumed
selecting ‘Database’ then ‘Convert data to HSC format’ and to be Fe–18 Cr–8 Ni–1 Mn–0?8 C–0?3 Si (wt-%). It can
following the prompts. The data entry for CrO(l) in the be seen that most of the activity coefficients are not very
standard HSC format has the following parameters: H5 sensitive to temperature, with the notable exceptions
2334?218 kJ mol21, S562?400 J mol21 K21, A532?430, being CrO(l) and CrO1?5(s) in the slag and silicon in the
B520?958, C520?381, D522?623. molten steel.
The most difficult issue in modelling is the selection of During the EAF cycle there are two periods during
appropriate values for the activity coefficients of all which chemical changes take place in the melt. The first
species in all phases. Activity coefficients are a function period is when oxygen is blown into the molten steel,
of the concentration of the species in a solution phase, and the second is when ferrosilicon is added to return
but are acceptably close to constant if the species are chromium to the molten steel. These two periods were
expressed in the monocation form.27 The gas phase can modelled separately.
be considered to be an ideal solution at high tempera-
tures so the activity coefficients of all gas species are Oxygen blowing
unity. The activity coefficients of species in the slag The masses of input species were calculated on a per
phase were estimated using the regular solution model,28 tonne of scrap charged basis from the mass balance data
in which the activity coefficients are given by the for a typical heat from ArcelorMittal Stainless Genk in
following equation Belgium. Elements present in small amounts, such as
X molybdenum, were omitted. Fluorspar and borax fluxes
RT ln ci ~ aij Xj2 were also inconsequential to the modelling and so were
XX omitted. The phases and species considered, together
z aij zaik {ajk Xj Xk zDGconv (6) with their input masses and activity coefficients, are
where ci is the activity coefficient of species i, aij is the listed in Table 3. The temperature was taken to be
interaction coefficient between species i and j, Xi is the 1600uC throughout this period. Carbon and oxygen
cation fraction of species i and DGconv is the Gibbs free were considered to be injected simultaneously, with the
energy for conversion from the hypothetical regular oxygen being raised incrementally by 0?035 Nm3 steps
solution standard state to the pure solid or pure liquid and the carbon by 0?05 kg, for 80 steps. Oxidation of
standard states. The interaction energies and conversion scrap by air ingress during melting was simulated by
Gibbs free energies were taken from the literature.28,29 initially adding 3 kg/tonne (2?1 Nm3) of oxygen, this
Interaction energies for CrO–MgO and CrO1?5–MgO small amount being found to satisfactorily reproduce the
were estimated by multiple regression of equation (6) CrOx evolution in the slag observed by Guo et al.9
with the data of Pei and Wijk.19 Activity coefficients during oxygen injection.
were not calculated for NiO because it is expected that
those of FeO could be used for NiO, nor for AlO1?5 Table 2 Calculated activity coefficients for species in
because in the modelling it was not considered to slag and molten steel
partition to any other phase.
Temperature,
Activity coefficients in the molten iron phase were
uC 1550 1600 1650 1700 1750 1800
estimated using the dilute solution model described by
Sigworth and Elliott,30 using the tabulation of Lupis31 CrO (l) 12 10 8.6 7.3 6.3 5.5
for the interaction coefficients. The activity coefficients CrO1?5 (s) 27 22 18 15 12 10
are given by the following equation FeO (l) 1.8 1.8 1.8 1.8 1.8 1.9
X j MnO 0.21 0.24 0.27 0.31 0.34 0.38
ln ci ~ ln c0i z eX (7) CaO (s) 0.048 0.048 0.048 0.049 0.049 0.049
j i j MgO (s) 0.074 0.075 0.076 0.078 0.079 0.080
SiO2 (s) 0.14 0.14 0.15 0.15 0.15 0.15
where ci is the Raoultian activity coefficient, c0i is the Cr (l) 0.83 0.83 0.83 0.83 0.83 0.83
Raoultian activity coefficient at infinite dilution, eji is the Ni (l) 0.72 0.74 0.77 0.79 0.82 0.85
binary first order interaction coefficient between species i Mn (l) 1.19 1.18 1.17 1.17 1.16 1.15
and j, and Xj is the mole fraction of species j. The Si (l) 0.0017 0.0021 0.0026 0.0032 0.0039 0.0048
C (g) 0.37 0.36 0.35 0.33 0.32 0.31
temperature variation of the activity coefficient at
Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2010 VOL 119 NO 1 5
Kho et al. Understanding stainless steelmaking through computational thermodynamics: Part 1
6 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2010 VOL 119 NO 1
Kho et al. Understanding stainless steelmaking through computational thermodynamics: Part 1
Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2010 VOL 119 NO 1 7
Kho et al. Understanding stainless steelmaking through computational thermodynamics: Part 1
8. J. A. T. Jones, B. Bowman, and P. A. LeFrank: ‘Electric furnace 21. A. Roine: ‘HSC Chemistry 3?0 in metallurgical applications’, in
steelmaking’, in ‘The making, shaping and treating of steel’, 11th ‘Sulfide smelting ’98: current and future practices’, (ed. J. A.
edn, 525–660; 1998, Pittsburgh, PA, Association of Iron and Steel Asteljoki and R. L. Stephens), 49–58; 1998, Warrendale, PA, TMS.
Engineers. 22. D. R. Swinbourne: ‘Computational thermodynamics modelling of
9. M. Guo, D. Durinck, P. T. Jones, G. Heylen, R. Hendrickx, R. indium behaviour during KIVCET smelting’, Proc. EMC 2007,
Baeten, B. Blanpain and P. Wollants: ‘EAF stainless steel refining. Vol. 3; 1241–1254; 2007, Dusseldorf, GDMB Gesellschaft für
Part I: observational study on chromium recovery in an eccentric Bergbau, Metallurgie, Rohstoff- und Umwelttechnik.
bottom tapping furnace and a spout tapping furnace’, Steel Res. 23. D. R. Swinbourne, S. Yan and A. Yazawa: ‘Behaviour of thallium
Int., 2007, 78, (2), 117–124. during lead smelting’, Proc. Int. Symp. on ‘Metallurgical and
10. D. C. Hilty: ‘The relation between chromium and carbon in materials processing: principles and technologies’, (ed. F. Kongoli
chromium steel refining’, Trans. AIME, 1949, 185, 91–95. et al.), 1111–1122; 2003, Warrendale, PA, TMS.
11. W. E. Dennis and F. D. Richardson: ‘The equilibrium controlling 24. K. Yamaguchi, D. R. Swinbourne and A. Yazawa: ‘Behaviour of
the decarburisation of iron-chromium-carbon melts’, J. Iron Steel minor species during oxidation smelting of lead concentrate’, in
Inst., 1953, 175, 264–266. ‘Lead–zinc 2005’, (ed. T. Fujisawa), 1231–1246; 2005, Kyoto,
12. E. T. Turkdogan and R. J. Fruehan: ‘Fundamentals of iron and MMIJ.
steelmaking’, in ‘The making, shaping and treating of steel’, 11th 25. E. C. Vanderstaay, D. R. Swinbourne and M. Monteiro: ‘A
edn, 13–157; 1998, Pittsburgh, PA, Association of Iron and Steel computational thermodynamics model of submerged arc electric
Engineers. furnace ferromanganese smelting’, Miner. Process. Extr. Metall.,
2004, 113, (1), C38–C44.
13. J. J. Kerr and R. J. Fruehan: ‘Additions to generate foam in
26. N. Y. Toker, L. S. Darken and A. Muan: ‘Equilibrium phase
stainless steelmaking’, Metall. Mater. Trans. B, 2004, 35B, 643–
relations and thermodynamics of the Cr–O system in the
650.
temperature range of 1500uC to 1825uC’, Metall. Mater. Trans.
14. L. Voj, V. Risonarta, I. Wagenknecht and H. Pfeifer: ‘Control of
B, 1991, 22B, 225–232.
chromium slagging in stainless steel production at EAF’, Proc.
27. A. Yazawa, S. Nakazawa and Y. Takeda: ‘Distribution behaviour
AISTech 2007, Indianapolis, IN, USA, May 2007, ISS, 1057–
of various elements in copper smelting systems’, in ‘Advances in
1063.
sulfide smelting’, (ed. H.Y. Sohn et al.), 99–117; 1983, Warrendale,
15. S. Sun, P. Uguccioni, M. Bryant and M. Ackroyd: ‘Chromium PA, TMS.
control in the EAF during stainless steelmaking’, Proc. Conf. on 28. S. Ban-Ya: ‘Mathematical expression of slag-metal reactions in
‘Electric furnace’, 297–302; 1997, Warrendale, PA, TMS. steelmaking process by quadratic formalism based on the regular
16. D. Springorum (ed.): ‘Slag Atlas’, 2nd edn, 156; 1995, Dusseldorf, solution model’, ISIJ Int., 1993, 33, 2–11.
Verlag Stahleisen GmbH. 29. Y. Xiao, L. Holappa and M. A. Reuter: ‘Oxidation state and
17. E. B. Pretorius and R. C. Nunnington: ‘Stainless steel slag activities of chromium oxides in CaO–SiO2–CrOx slag system’,
fundamentals: from furnace to tundish’, Ironmaking Steelmaking, Metall. Mater. Trans. B, 2002, 33B, 595–603.
2002, 29, (2), 133–139. 30. G. K. Sigworth and J. F. Elliott: ‘The thermodynamics of dilute
18. E. B. Pretorius and A. Muan: ‘Activity-composition relations of iron alloys’, Met. Sci., 1974, 8, 298–310.
chromium oxide in silicate melts at 1500uC under strongly reducing 31. C. H. P Lupis: ‘Chemical thermodynamics of materials’, 524–527;
conditions’, J. Am. Ceram. Soc., 1992, 75, (6), 1364–1377. 1983, Englewood Cliffs, NJ, Prentice Hall.
19. W. Pei and O. Wijk: ‘Experimental study on the activity of 32. Y. K. Rao: ‘Stoichiometry and thermodynamics of metallurgical
chromium oxide in the CaO–SiO2–Al2O3–MgOsat–CrOx slag’, processes’, 892; 1985, Cambridge, Cambridge University Press.
Scand. J. Metall., 1994, 23, 228–235. 33. C. W. McCoy and F. C. Langenburg: ‘A key to greater chromium
20. M. Gőrnerup and H. Jacobsson: ‘Foaming slag practice in electric recovery: slag-metal equilibrium during stainless steel melting’,
stainless steelmaking’, Iron Steelmaker, 1998, 25, (6), 59–66. J. Met., 1964, 421–424.
8 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2010 VOL 119 NO 1