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Published by Maney Publishing (c) IOM Communications Ltd and the Australasian Institute of Mining and Metallurgy
E. Jak*, B. Zhao and P. Hayes
By using recently determined experimental data, a new chemical thermodynamic database for the system FeO–Fe2O3–Al2O3–CaO–SiO2 has been developed. Used in conjunction with the FactSage computer package, phase equilibria and thermodynamic properties can be predicted for the wide range of process conditions relevant to non-ferrous metal processing. In the present paper information on the liquidus temperatures and the fraction of solids present at equilibrium, is presented as a function of slag composition and oxygen partial pressure, for silicate smelting slags. These data can be used to determine the conditions for magnetite formation, the effects of silica and lime additions on the liquidus, and the sensitivity of the proportion of solids in the slags to changes in operating temperature and oxygen partial pressure.
Keywords: Slag, Thermodynamic modelling, Copper smelting
The system FeO–Fe2O3–CaO–SiO2 forms the basis for smelting and reﬁning slags in most non-ferrous smelting processes. The experimental phase equilibrium studies that have been carried out on various aspects of this system have been widely reported in the literature.1–3 The necessity to obtain more detailed information on the phase chemistry of these systems is driven by the need to take practical steps to optimise metallurgical outcomes, and to reduce operating costs. In particular the use and selection of ﬂux additions, refractory wear, control of solid phase formation are of general concern from a pyrometallurgical viewpoint. The chemical and physico–chemical properties of the slag are intimately linked to the phases present and their compositions. Properties such as, the liquidus and proportion of solids, important to many aspects of the process, are controlled by variables, such as, bulk composition, temperature and oxygen partial pressure. To date prediction of the effects of these process variables has largely been carried out with the aid of ternary or pseudoternary phase diagrams, determined under particular experimental conditions. While these diagrams are very useful as a guide to the general behaviour of the slags, they are limited in the range of conditions that can be accurately described. These difﬁculties, largely stemming from the number of compositional and process variables that have to be considered, can be overcome by constructing chemical thermodynamic models of the slag.
Pyrometallurgy Research Centre, School of Engineering, The University of Queensland, Brisbane, Q4072, Australia *Corresponding author, email E.Jak@uq.edu.au
An optimised thermodynamic database has been constructed using a combination of experimental4 and modelling techniques.5 The methodology used for the database development involves a series of related steps. In the initial step, the phase equilibria and other thermodynamic information available on the individual components in this quinary system, and their combinations in the various binary, ternary, quaternary systems, are analysed for their consistency and accuracy. This process is then used to identify compositional areas where further experimental data are required to resolve discrepancies or to provide new information on key aspects of the phase chemistry. The experimental programme is then targeted at obtaining information in these areas. It has been particularly important to provide new data in higher order systems in composition ranges of interest to metallurgical operations. The ﬁnal optimised model parameters are then obtained by simultaneously considering behaviour in low and high order systems, not merely by the extrapolation of parameters obtained from the binaries and the ternaries. The FactSage model has been developed through a collaborative project with researchers at the Centre for Research in Computational Thermochemistry (CRCT), University of Montreal, developers of the FactSage program. Details of the model parameters in the various subsystems will be provided in subsequent publications. It is now possible, using the FactSage computer program in conjunction with the optimised thermodynamic database for the system FeO–Fe2O3–CaO– Al2O3–SiO2, to predict the chemical behaviour of this complex system. The new model can be used to examine the chemistry of the system from a number of viewpoints
ß 2008 Institute of Materials, Minerals and Mining and The AusIMM Published by Maney on behalf of the Institute and The AusIMM Received 21 December 2006; accepted 27 February 2007 DOI 10.1179/174328507X198771
Mineral Processing and Extractive Metallurgy (Trans. Inst. Min Metall. C)
It can be seen that the liquidus does not vary signiﬁcantly with oxygen pressure in the silica.1300uC.3. The absolute and relative values of the liquidus temperatures change with changing oxygen pressure. very sensitive to oxygen partial pressure. 2b–d). . Predicted phase relations The examples given in the present paper illustrate the ways in which this new database can be used to systematically analyse and predict the effects of process variables on the phases present. The formation of magnetite during smelting operations is widely recognised as a major problem in industrial practice. PO2510210 atm. The general shape of the liquidus is retained on lowering the oxygen partial pressures progressively to 1026. By way of comparison the liquidus for the pseudoternary system FeOx–CaO–SiO2 at iron saturation. highly oxidising conditions are present in the smelting shaft and these oxygen pressures are lowered by contact with the matte phase.g. The inﬂuence of SiO2/Fe weight ratio. 2a. is given in Fig. temperature and oxygen partial pressure conditions in the system. The liquidus of iron rich slags is. 1028. Min. and to present the predictions in a number of different ways.Jak et al. Metall. in general.6 The liquidus at 1250uC for the system FeO– Fe2O3–CaO–SiO2 at oxygen partial pressures 1026. The predictions show that increasing SiO2/Fe ratio leads to a decrease in slag liquidus in the spinel primary phase ﬁeld. A feature of the equilibria at this relatively high oxygen partial pressure is that the liquidus temperatures are. The extent of the spinel ﬁeld increases with increasing oxygen partial pressure. their proportions and their compositions. 148 Mineral Processing and Extractive Metallurgy (Trans. Liquidus Of principal concern to smelting operations is the liquidus of the slag. 1028 and 1026 atm: predicted by FactSage model not previously possible. is given in Fig. CaO/SiO2 weight ratio and oxygen partial pressure on the liquidus temperatures of the slags is illustrated in Fig. This is associated primarily with the appearance of the fayalite or olivine primary phase ﬁeld. 1.3 but the use of the FactSage model can be extended to applications in any set of composition. The selected examples refer primarily to the conditions encountered generally in copper smelting and converting technologies. as predicted using the FactSage model. 0?3 at an oxygen partial pressure of 1024 atm is given in Fig. In ﬂash smelting the slag is exposed to a range of oxygen pressures. The predicted slag liquidus as a function of SiO2/Fe ratio for the CaO/SiO2 weight ratios of 0. 0?2. 0?1. 1028 and 10210 atm (Fig. At 10210 atm there is a signiﬁcant range of compositions that are fully liquid at 1200uC. In the iron oxide primary phase ﬁelds lowering the oxygen pressure is accompanied by the lowering of liquidus temperatures. the bounding primary phase ﬁeld of iron-rich slags is wustite. Inst. C) 2008 VOL 117 NO 3 . At low oxygen pressures. while the liquidus temperatures for the silica and fayalite primary phase ﬁelds remain almost unaffected by PO2. At higher oxygen partial pressures the spinel (in this case magnetite) phase becomes stable. 2e. however. Phase equilibria in system FeO–Fe 2 O 3 –Al 2 O 3 –CaO–SiO 2 Published by Maney Publishing (c) IOM Communications Ltd and the Australasian Institute of Mining and Metallurgy 1 Liquidus isotherms at 1250uC in FeO–Fe2O3–CaO–SiO2 system at oxygen partial pressures of 10210. and ultimately reduces bath volume due to the build-up of magnetite deposits on the reactor walls. 10210 atm. e.3 The formation of this solid phase impedes slag/matte separation. wollastonite and dicalcium silicate primary phase ﬁelds. The liquidus increases with increasing SiO2/Fe ratio in the tridymite (SiO2) primary phase ﬁeld. To select operating conditions that avoid or minimise these undesirable effects further detail on the slag chemistry is required. 2. and the range of compositions at which the slags are completely liquid becomes smaller.
b 1026 atm. The data at SiO2/Fe50?6 show that the slags with CaO/SiO2 less than 0?3 are fully liquid for oxygen pressures below 1028 atm. In contrast. 7). 6. at the oxygen partial pressure of 1028 atm. examples of which are given in Fig.7 Subliquidus Figures 4 and 5 show the weight proportion of liquid at 1250uC as a function of oxygen partial pressure for SiO2/ Fe weight ratios of 0?6 and 1?0 respectively. the critical oxygen pressures for the appearance of solid spinel decrease. Small additions of lime lower the proportions of solids present over the same range of oxygen partial pressures. 0?1. 3 at an oxygen partial pressure of 1028 atm for a range of SiO2/Fe ratios. The presence of Al2O3 also signiﬁcantly reduces the critical oxygen pressure for the formation of the spinel solid phase. d 10210 atm and e in equilibrium with metallic iron: predicted by FactSage model Mineral Processing and Extractive Metallurgy (Trans. high viscosity. 2 Slag liquidus as function of SiO2 /Fe weight ratio for CaO/SiO2 weight ratios of 0?0. More importantly the presence of Al2O3 changes the compositions at which silica saturation occurs. With no lime additions. It also illustrates a point apparent from Fig. at various CaO/SiO2 ratios. lime addition does not appear to be useful for this SiO2/Fe ratio. Influence of Al2O3 The effects of minor elements on the phase relations in this system in areas of interest to non-ferrous smelting should not be overlooked. the liquidus in the fayalite phase ﬁeld is lowered by . there is a dramatic reduction in the proportion of liquid present in the system. Note that increasing CaO/SiO2 generally increases slightly the liquidus in the magnetite and wustite primary phase ﬁelds. In general low slag ﬂuidity. and extend the range of oxygen pressures under which the system can be operated without the catastrophic precipitation of the solid phase. Phase equilibria in system FeO–Fe 2 O 3 –Al 2 O 3 –CaO–SiO 2 Published by Maney Publishing (c) IOM Communications Ltd and the Australasian Institute of Mining and Metallurgy The effect of the CaO/SiO2 weight ratio in the slag on the liquidus (Fig. For example (Fig. 2) is also dependent on the primary phase ﬁeld.10 wt-% solids for oxygen pressures in the range 10212–1027 atm.3uC for every 1 wt-%Al2O3 added. As lime is added to these slags. that CaO additions increase the SiO2/Fe ratios at which silica saturation is achieved. Min. The diagram again shows that increasing the lime/silica ratio signiﬁcantly reduces the liquidus temperatures for slags in the silica primary ﬁeld. Inst.8 The effect of Al2O3 on the liquidus temperature at a particular bulk composition is relatively minor. This effect is particularly important for matte smelting operations where the recovery of dissolved metal values into the matte increases as silica saturation is approached. C) 2008 VOL 117 NO 3 149 . and with 6 wt-%Al2O3 under the same conditions over 20 wt-% solids are present. c 1028 atm.Jak et al. once this critical oxygen pressure has been achieved. This has been illustrated in recent experimental work on the effect of Al2O3 on liquidus temperatures in fayalite slags. and tridymite (SiO2) primary phase ﬁelds. the data at SiO2/Fe weight ratio of 1?0 show that the slags with no lime contain . however. solids formation does not occur until oxygen pressures exceed approximately 361027 atm. 0?2 and 0?3 at oxygen partial pressures a 1024 atm. with no Al2O3 the slag is completely liquid. but reduces the liquidus in the olivine or fayalite. 2. is to be expected if the solids content of the slag exceeds 20 wt-%. From the point of view of operating above the liquidus at high oxygen pressures. Metall. The slag liquidus temperature as a function CaO/SiO2 weight ratio is given in Fig.
3 and marked on Figs. have slags 4 Weight percentage of liquid at 1250uC as function of oxygen partial pressure for SiO2/Fe weight ratio of 0?6 and CaO/SiO2 weight ratios of 0?0.0?6 use low CaO additions.Jak et al. 0?1. In general those smelters that operate with SiO2/Fe weight ratio of . Metall. Those smelters that operate with SiO2/Fe weight ratios of . Inst. 0?1. Phase equilibria in system FeO–Fe 2 O 3 –Al 2 O 3 –CaO–SiO 2 Published by Maney Publishing (c) IOM Communications Ltd and the Australasian Institute of Mining and Metallurgy 3 Slag liquidus as function of CaO/SiO2 weight ratio for SiO2/Fe of 0?6. 0?2 and 0?3: predicted by FactSage model 150 Mineral Processing and Extractive Metallurgy (Trans. 0?8. 1?0 and 1?5 at oxygen partial pressure of 1028 atm: predicted by FactSage model Implications for industrial practice Most copper smelting processes operate with slags having SiO2/Fe weight ratios in the range 0?6–1?0. The slag compositions and process conditions used in various copper smelting operations are given in Table 1. Min. C) 2008 VOL 117 NO 3 .1?0 and higher. 0?2 and 0?3: predicted by FactSage model 5 Weight percentage of liquid at 1250uC as function of oxygen partial pressure for SiO2/Fe weight ratio of 1?0 and CaO/SiO2 weight ratios of 0?0. 2 and 3.
Inst. as the oxygen partial pressure increases the extent of the iron oxide primary ﬁeld expands. Phase equilibria in system FeO–Fe 2 O 3 –Al 2 O 3 –CaO–SiO 2 Published by Maney Publishing (c) IOM Communications Ltd and the Australasian Institute of Mining and Metallurgy 6 Experimentally determined liquidus in Al2O3–‘FeO’–CaO–SiO2 system in equilibrium with metallic iron8 containing signiﬁcant CaO concentrations.1025 atm. local excursions above these values occur as the concentrates are contacted with oxidising gases. Min. however. Metall. the slag moves into the region of inﬂuence of this new phase ﬁeld and the Mineral Processing and Extractive Metallurgy (Trans. These compositions have been selected by operators following plant trials to suit the particular process technologies and operating practices in each case. The equilibrium oxygen partial pressures in copper matte smelters are reported to be in the range 10211– 1029 atm.Jak et al. Figure 2a–d shows that. CaO addition will result in a lowering of the liquidus. The calculated liquidus temperatures in the system FeO–Fe2O3–CaO–SiO2 at iron saturation. interesting to compare these practices to the predictions made using the slag model. 2e indicate that at SiO2/Fe weight ratio of 0?6.3 In direct smelting the oxygen partial pressures in equilibrium with copper metal are .5 however. C) 2008 VOL 117 NO 3 151 . shown in Fig. for SiO2/Fe weight ratio of 0?6. The system under these conditions is operating in the region described by the fayalite primary phase ﬁeld. It is.
8. Mater. Jak and P. 191–200. Ecole Polytechnique de Montreal) in the collaborative development of the new FactSage model of the system FeO–Fe2O3–Al2O3–CaO– SiO2.e. 1994.6 Al2O3 4 3 8 5 2 6 4. Phase equilibria in system FeO–Fe 2 O 3 –Al 2 O 3 –CaO–SiO 2 Table 1 Compositions of copper smelting slags and process conditions for various smelting processes. R. Muan and A. 1953. 2?0. and accurate predictions of the equilibrium concentrations. 3rd edn. A. information on the effect of ﬂux additions.3 1 5 1 SiO2/Fe 0. Metall. while CaO additions are beneﬁcial in lowering the liquidus at SiO2/Fe weight ratio of 0?6 for oxygen partial pressures below 1029 atm. E. Mater.crct.6 7 0. 30B. G. uC 1250 1240 1200 1300 1230 1240 1200 Published by Maney Publishing (c) IOM Communications Ltd and the Australasian Institute of Mining and Metallurgy F G properties can be predicted for the wide range of process conditions relevant to non-ferrous metal processing. 44 44 36 24 44 40 37. Zhao. (Korea). and activities. 1965.65 0. E.3 (wt-%) Smelter A B C D E Magma Chino Ilo Mufulira Southern copper Caletones Mt Isa Process Outokumpu flush Inco flash Reverberatory furnace Electric furnace Noranda furnace Teniente furnace Isasmelt Cu 2. The authors wish to acknowledge the financial support for the FactSage model development provided by the Commonwealth Government of Australia. 1. The model can be used to carry out trend and sensitivity analysis of the system. Metall. The new FactSage model is both accurate in its predictions and ﬂexible in the form in which information can be provided. 2. Biswas and W. B. to explore the effects of changes in composition. available at: www. 3.75 0. Osborne: ‘Phase equilibria among oxides in steelmaking’.4 1. The model therefore provides a powerful predictive tool that can be used in the selection of optimum process conditions in metallurgical smelting systems.54 0.15 0. Verlag Stahleisen Gmbh. The calculations. Acknowledgements The authors wish to acknowledge the considerable efforts and support provided by Dr S. 154–156.6 0. 1997.1?0. MA. C.22 Slag temp.. K. in fact. Sridhar. Canada. D.86 CaO/SiO2 0.03 0. References 1. Lee: ‘Improved methodologies for the determination of high temperature phase equilibria’. Kameda: Technic. P. Inst.38 0.73 0.9 5 3 MgO S 1 1 1 0. D. Pelton and W.6 Fe tot. A. of all chemical species present in the system. 28B. 126–130. local over oxidation does not lead to a dramatic increase in the proportion of solids and magnetite is not the ﬁrst solid formed. i. 7. Trans. Metall. A. 2nd edn. 7 Weight percentage of liquid at 1250uC as function of oxygen partial pressure for SiO2/Fe weight ratio of 0?6 and CaO/SiO2 weight ratio of 0?3 and Al2O3 of 0?0. Mater.03 0. 597–605.3 CaO 1 1 5 14 1 1 7.7 2. above this oxygen pressure the addition of CaO increases the liquidus temperatures making it more likely that solid spinel will form. polymtl. 4?0 and 6?0 wt-%: predicted by FactSage model liquidus temperatures increase dramatically.92 1.6 Fe3z 2 1 2 1 5 4 5.04 0. E. 4. W. Hayes and H. F. Simeonov: ‘Thermodynamic considerations in the pyrometallurgical production of copper’. Bale. J.9 0. T. ‘Slag atlas’. Summary By using an optimised model of the system FeO–Fe2O3– Al2O3–CaO–SiO2. Addison Wesley. Degterov and Professor A. 1–8. the liquidus is largely unaffected by oxygen partial pressure. Pelton (CRCT. Min. 79–80. In contrast for those smelters operating at SiO2/Fe weight ratios of . 5. G. 1999. B. Reading. 1995. Report Tohoku Uni.. Hayes: ‘The effect of Al2O3 on the liquidus temperatures of fayalite slags’. C. Montreal. Trans.5 SiO2 32 33 33 37 29 25 32. In addition. In this operating regime the addition of CaO is beneﬁcial in reducing the liquidus temperatures and may lead to improved operability. 40–58. indicate that the liquidus temperatures for the SiO2/Fe weight ratio of 1?0 and the CaO/SiO2 weight ratio of 0?15 are the same as for SiO2/Fe weight ratio of 0?6 with no lime additions. 1995. B. Yazawa and M. 2000. Met. Thompson: ‘Facility for the analysis of chemical thermodynamics (F*A*C*T)’. Ecole Polytechnique.63 0.ca 6. Jak. and the support of the Cooperative Research Centre for Coal in Sustainable Development (CCSD). C. in conjunction with the FactSage computer package. phase equilibria and thermodynamic 152 Mineral Processing and Extractive Metallurgy (Trans. The model can be used to provide phase diagrams over a range of oxygen partial pressures. C) 2008 VOL 117 NO 3 . in the silica primary phase ﬁeld.03 0. through the Cooperative Research Centre programme.75 0. Elsevier Science UK. temperature and oxygen pressure. Toguri and S. Du ¨ sseldorf. 16.Jak et al. Davenport: ‘Extractive metallurgy of copper’.
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