Physico-Chemical Properties of Titaniferous Slags

McRae, L. B. ; Pothas, E. ; Jochens, P. R. ; Howat, D. D.
Organization: The Southern African Institute of Mining and Metallurgy
Pages: 5
Publication Date: Jan 6, 1969
Discussion H. J. S. Kriek*: During 1956 Iscor became interested in the acid smelting in a blast furnace of siliceous ores containing 15 per cent silica. This interest was as a result of the successful acid smelting in Germany at a CaO/SiO2-ratio of between 0.4 and 0.8. Acid smelting can become an economic proposition due to a reduction in slag volume accompanied by a lowering of the coke rate. Paschke and Hannel1 found that a free flowing slag (i.e. viscosities of less than two poise) would not be obtained at C/S-ratios lower than 0.82 and that the addition of 3 to 4 per cent alkalies became necessary. In titanium bearing slags it was established that maximum fluidity is obtained with 10 per cent TiO2. Acid smelting resulted in increased sulphur pickup with decreasing O/S-ratio and desulphurization with soda-ash outside the blast furnace was necessary. At Iscor Mr B. B. Segal established that, for slags with (CaO+MgO)/SiO2-ratios of 0.5, 0.6 and 0.7, the addition of alkalies and TiO2 resulted in a substantial decrease in melting point and also of viscosity. At a (CaO+ MgO)/ ratio of 0.53 the addition of 10 per cent TiO2 is as effective as the addition of 3.75 per cent alkalies. This means that a blast furnace can be run without the addition of alkalies and consequently the detrimental effect of alkalies on the lining can be avoided; also that fluid slags with 5 to 15 per cent MgO and 8 to 10 per cent Al203 can be obtained with 10 per cent TiO present. (CaO+ MgO)/SiO2-ratios smaller than 0.5 the addition of titania resulted in a decrease in melting point and also in an increase in viscosity. In ceramic crucibles the slag did not become more viscous with time but thickened appreciably when held in graphite crucibles. No titanium carbonitride could be detected and only Ti20a was found. Prof Howat also did not obtain the TiC-TiN solid solution and therefore it appears that the thickening of the slag is not solely due to the formation of the titanium carbonitrides. This is in agreement with the work of Michailov and Belyakova2 who found that TiO2 decreased the viscosity of acid slags and increased the viscosity of basic slags; that titanium sesquioxide (Ti203) and titanium monoxide (TiO) increased the viscosity of both acid and basic slags and that titanium carbide, which is found in larger amounts in basic slags than in acid slags, considerably increases the viscosity of both acid and basic slags. Patzak et al3 describes the following oxygen deficient titanias, viz Ti2O, TiO, Ti203, Ti3O5, Ti4O7, Ti5O9, Ti6O11- Ti10O9,Ti7O13,Ti8O15 and Ti9O17. Until about 1959 a fair amount of data was available on the viscosity of normal slags to which titania was added2, 4, 5, 6, 7, 8, 9. At Iscor an electromagnetic viscometer based on the viscometer developed by Bockris10 was built. Progress was very slow as our main attention was centred around problems associated with the operation of the Rotor process. During 1962 and 1963 two papers containing fundamental work on the viscosities of slags in the systems CaO-SiO2-TiO211 and CaO-SiO2-TiO2 at 0 per cent A1203, 10 per cent Al203 and 20 per cent Al20312 appeared. The work of Ross and Ohno obviated the necessity of any further work by Iscor on the viscosity of blast furnace slags containing titania. Ross gave the following optimum compositions for blast furnace slags containing titania. Titania % Lime % Silica % Lime/Silica-ratio 20 30-42 38-50 0.6-1.10 30 27-36 34-43 0.63-1.06 40 24-32 28-36 0.66-1.14 The optimum temperature is 1,500°C because at this temperature the largest workable composition range exists. Higher temperatures result in narrower optimum composition ranges and in increased rates of thickening. The factors affecting the rate of thickening were also investigated by Ross and Ohno, as the main problem with slags containing titania is not finding compositions which are fluid at operating temperatures but the thickening due to a lack of oxygen. With these slags when there is insufficient oxygen to co-ordinate each silicon atom with its own individual shell of four oxygen ions, some sharing of oxygen ions must occur, resulting in the formation of large silicate ions and a rise in viscosity. The formation of oxygen deficient titania can be prevented as long as iron oxide or manganese oxide remain in the liquid slag. Iwase13 and also Viens, Camp bell and Rogers14 obtained in the experimental smelting of ilmenite ores fluid slags with more than 3 to 5 per cent manganese oxide and ferrous oxide in the slags. It appears that titaniferous ores can be smelted in blast furnaces under the following conditions: (1) Acid slag operation, i.e. at C/S-ratios from O.6-1.0. (2) Dolomite can be used as a flux as MgO is a network modifier. (3) The Al2O3-content must be less than 15 per cent as alumina promotes thickening of the slag and decreases the optimum composition range. (4) The hearth temperature must not exceed 1,500°C. According to Ross a definite amount of energy is required for each ton of iron produced and in order to increase production an increase in heat
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