Direct smelting process

Abstract

A molten bath-based direct smelting process comprises controlling the process conditions in a direct smelting vessel so that molten slag in a molten bath of metal and slag in the vessel has a viscosity in a range of 0.5-5 poise when the slag temperature is in the range of 1400-1550 C. in the molten bath in the vessel.

Claims

1. A slag product of a direct smelting process, the slag product comprising molten slag that includes: TiO.sub.2: at least 15 wt. %, SiO.sub.2: at least 15 to 20 wt. %, CaO: at least 15 to 30 wt. %, Al.sub.2O.sub.3: at least 10 to 20 wt. %, FeO: at least 3 to 10 wt. %, carbon content: 3-5 wt. %, and vanadium oxide comprising more than 50% of a total vanadium output from the direct smelting process.

2. The slag product defined in claim 1, wherein vanadium in the slag product comprises more than 65% of the total vanadium output from the direct smelting process.

3. The slag product defined in claim 1, wherein vanadium in the slag product comprises more than 80% of the total vanadium output from the direct smelting process.

4. The slag product defined in claim 1, wherein the molten slag comprises at least 20 wt. % TiO.sub.2.

5. The slag product defined in claim 1, wherein the molten slag comprises at least 50 wt. % TiO.sub.2.

6. The slag product defined in claim 1, wherein the molten slag further comprises manganese oxide.

7. A feed material for a sulphate process for producing pigment-grade titania, the feed material being a product of a directing smelting process and having a microstructure that is amenable to processing in the sulphate process and wherein the feed material comprises: TiO.sub.2: at least 15 wt. %, SiO.sub.2: at least 15 to 20 wt. %, CaO: at least 15 to 30 wt. %, Al.sub.2O.sub.3: at least 10 to 20 wt. %, FeO: at least 3 to 10 wt. %, carbon content: 3-5 wt %, and vanadium oxide comprising more than 50% of a total vanadium output from the direct smelting process.

8. The feed material defined in claim 7, wherein vanadium in the vanadium oxide comprises more than 65% of the total vanadium output from the direct smelting process.

9. The feed material defined in claim 7, wherein vanadium in the vanadium oxide comprises more than 80% of the total vanadium output from the direct smelting process.

10. The feed material defined in claim 7, wherein the feed material comprises at least 20 wt. % TiO.sub.2.

11. The feed material defined in claim 7, wherein the feed material comprises at least 50 wt. % TiO.sub.2.

12. The feed material defined in claim 7, wherein the feed material further comprises manganese oxide.

Description

(1) The present invention is described in more detail hereinafter with reference to the accompanying drawings, of which:

(2) FIG. 1 is a diagrammatic view of a direct smelting vessel operating in accordance with one embodiment of a direct smelting process of the present invention;

(3) FIG. 2 is a tertiary phase diagram for calcia, alumina, and silica in slag in one embodiment of the direct smelting process of the present invention; and

(4) FIG. 3 is a pseudo-tertiary phase diagram for a slag and separate slag liquidus plots for two marked sections of the phase diagram for a high titanium oxide feed material in one embodiment of the direct smelting process of the present invention.

(5) The following description is in the context of smelting titanomagnetite to produce molten iron via the HIsmelt process. The present invention is not limited to smelting titanomagnetite and extends to smelting any suitable metalliferous feed material that contains iron oxides and titanium oxides. For example, the present invention extends to smelting titanium-vanadium magnetite. In addition, the present invention is not limited to the HIsmelt process and extends to any molten bath-based process of the HIsmelt type of process that can generate the necessary process conditions. In particular, by way of example, the present invention extends to variants of the HIsmelt Process that include (a) a smelt cyclone on a direct smelting vessel, such as described in U.S. Pat. No. 6,440,195 and (b) pre-reduction of the metalliferous feed material prior to supplying the feed material to the direct smelting vessel.

(6) As is indicated above, the HIsmelt process is described in a considerable number of patents and patent applications in the name of the applicant. By way of example, the HIsmelt process is described in International application PCT/AU96/00197 in the name of the applicant. The disclosure in the patent specification lodged with the International application is incorporated herein by cross-reference.

(7) The process is based on the use of a direct smelting vessel 3.

(8) The vessel 3 is of the type described in detail in International applications PCT/AU2004/000472 and PCT/AU2004/000473 in the name of the applicant. The disclosure in the patent specifications lodged with these applications is incorporated herein by cross-reference.

(9) The vessel 3 has a hearth 51 that includes a base and sides formed from refractory bricks, a side wall 53 which form a generally cylindrical barrel extending upwardly from the sides of the hearth and include an upper barrel section and a lower barrel section, a roof 55, an off-gas duct 9 in an upper section of the vessel 3, a forehearth 67 for discharging molten metal continuously from the vessel 3, and a tap hole (not shown) for discharging molten slag periodically from the vessel 3.

(10) In use, the vessel contains a molten bath of iron and slag which includes a layer 15 of molten metal and a layer 16 of molten slag on the metal layer 15. The arrow marked by the numeral 17 indicates the position of the nominal quiescent surface of the metal layer 15 and the arrow marked by the numeral 19 indicates the position of nominal quiescent surface of the slag layer 16. The term quiescent surface is understood to mean the surface when there is no injection of gas and solid materials into the vessel. Typically, the temperature of the molten bath is in a range of 1400-1550 C.

(11) The vessel 3 is fitted with a downwardly extending water-cooled hot air blast (HAB) lance 7 extending into a top space of the vessel 3 and a plurality of water-cooled solids injection lances 5 extending downwardly and inwardly through a side wall and into the slag. The lances 5 extend downwardly and inwardly at an angle of 30-60 to the vertical through the side wall and into the slag layer 16 in the molten bath. The position of the lances 5 is selected so that the lower ends are above the quiescent surface 17 of the metal layer 15 of the molten bath.

(12) In use, titanomagnetite and coal and slag additives entrained in a carrier gas (typically N.sub.2) are directly injected into the bath via the solids injection lances 5.

(13) The momentum of the injected solid materials/carrier gas causes the solid material and gas to penetrate the metal layer 15. The coal is devolatilised and thereby produces substantial volumes of gas in the metal layer 15. Carbon partially dissolves into the metal and partially remains as solid carbon. The iron oxides in the titanomagnetite are smelted to molten metal and the smelting reaction generates carbon monoxide gas. The gases transported into the metal layer 15 and generated via devolatilisation and smelting produce significant buoyancy uplift of molten metal, solid carbon, unreacted solid material in the titanomagnetite (predominantly TiO.sub.2), and slag (drawn into the metal layer 15 as a consequence of solid/gas/injection) from the metal layer 15 which generates an upward movement of splashes, droplets and streams of molten metal and slag and entrained unreacted titanomagetite, and these splashes, and droplets, and streams entrain slag as they move through the slag layer 16.

(14) The buoyancy uplift of the above-described material causes substantial agitation in the metal layer 15 and the slag layer 16, with the result that the slag layer 16 expands in volume and has a surface indicated by the arrow 30. The extent of agitation is such that there is reasonably uniform temperature in the metal and the slag regionstypically, 1400-1550 C. with a temperature variation of the order of 30 in each region.

(15) In addition, the upward movement of the above-described material extends into a top space 31 of the vessel 3 that is above the molten bath in the vessel and: (a) forms a transition zone 23; and (b) projects some molten material (predominantly slag) beyond the transition zone and onto the section of the side wall of the vessel 3 that is above the transition zone 23.

(16) In general terms, the slag layer 16 is a liquid continuous volume, with solid material and gas bubbles, and the transition zone 23 is a gas continuous volume with splashes, droplets, and streams of molten metal and slag. Alternatively, the slag layer 16 may be described as a slurry of solid material in a liquid phase with a dispersion of gas bubbles in the liquid phase.

(17) The position of the oxygen-containing gas lance 7 and the gas flow rate through the lance 7 are selected so that the oxygen-containing gas penetrates the central region of the transition zone 23 and maintains an essentially metal/slag free space (not shown) around the end of the lance 7. The lance 7 includes an assembly which causes the oxygen-containing gas to be injected in a swirling motion into the vessel.

(18) The injection of the oxygen-containing gas via the lance 7 post-combusts reaction gases CO and Hz in the transition zone 23 and in the free space around the end of the lance 7 and generates high temperatures of the order of 2000 C. or higher in the gas space. The heat is transferred to the ascending and descending splashes droplets, and streams, of material from the metal layer and the heat is then partially transferred to the metal layer 15 when the material falls downwardly to the metal layer 15.

(19) The described embodiment of the process of the present invention comprises controlling the process conditions so that the molten slag (a) is within a selected composition range so that the slag is a molten slag, as described herein, (b) has a high oxygen potential, and (c) has a viscosity in a range of 1-5 poise when the slag temperature is in a range of 1400-1550 C. in the molten bath in the vessel 3.

(20) The necessary control of process conditions can be achieved by one or more than one of a range of options, including but not limited to controlling the FeO content of the molten slag to achieve the required high oxygen potential and controlling the CaO content of the molten slag to achieve the required viscosity in the range of 1-5 poise when the slag temperature is in the range of 1400-1550 C. in the molten bath in the vessel 3.

(21) More particularly, in the described embodiment the necessary control of process conditions includes selecting the feed materials and operating conditions so that the molten slag has the following constituents in the stated range of 1400-1550 C. of the molten bath:

(22) TiO.sub.2: at least 15 wt. %,

(23) SiO.sub.2: at least 15 wt. %,

(24) CaO: at least 15 wt. %,

(25) Al.sub.2O.sub.3: at least 10 wt. %, and

(26) FeO: at least 3 wt. %.

(27) More particularly, in the described embodiment the necessary control of process conditions includes controlling the slag composition so that the molten slag is sub-liquidus, preferably slightly sub-liquidus, for that slag composition in the stated range of 1400-1550 C. of the molten bath so that a solid oxide phase precipitates from the liquid slag in an amount of 5-25% by volume of the slag. The resultant molten slag is a slurry of a solid oxide phase in a liquid slag phase. The precipitated solid oxide phase contributes to controlling the viscosity of the molten slag as required for the described embodiment of the process. In addition, the viscous molten slag, is well-suited to form a protective coating on the refractories of the vessel in contact with the slag.

(28) FIG. 2 is a tertiary phase diagram for three main slag constituents of calcia, alumina, and silica in one embodiment of the direct smelting process of the present invention. More particularly, the phase diagram focuses on two main gangue constituents of alumina and silica and a flux additive, namely calcia. The phase diagram was sourced from FactSage 6.1. The phase diagram illustrates the impact of the slag composition on the phases in the slag. In particular, it can be determined from FIG. 2 that if a higher viscosity slag (i.e. a slag having a viscosity of at least 2.5 poise) is required, this can be achieved by controlling the slag composition, for example by adjusting the calcia addition, and other process conditions to precipitate melilite solid phase from the molten slag.

(29) FIG. 3 is a pseudo-tertiary phase diagram for a slag and separate slag liquidus plots for two marked sections of the phase diagram for a high titanium oxide feed material in one embodiment of the direct smelting process of the present invention. The phase diagram focuses on (a) three main gangue constituents, namely alumina, magnesia, and silica, (b) a flux additive, namely calcia, and (c) titania. The phase diagram was sourced from University of Queensland researchers. The phase diagram defines an operating window for slag compositions that provide the required slag viscosities of 1-5 poise for the process. The Figure highlights two sections of the phase diagram and these sections show the significant change in liquidus temperatures across the selected compositions. It is particularly evident from these sections the considerable scope to precipitate out solid phases and thereby change the viscosity of the slag within the temperature range of 1400-1550 C. of the molten bath.

(30) In more general terms, the following process features, separately or in combination, are relevant control parameters of the process. (a) Controlling the slag inventory, i.e. the depth of the slag layer and/or the slag/metal ratio (typically the weight ratio of metal:slag to be between 3:1 and 1:1), to balance the positive effect of metal in the transition zone 23 on heat transfer with the negative effect of metal in the transition zone 23 on post combustion due to back reactions in the transition zone 23. If the slag inventory is too low the exposure of metal to oxygen is too high and there is reduced potential for post combustion. On the other hand, if the slag inventory is too high the lance 7 will be buried in the transition zone 23 and there will be reduced entrainment of gas into the free space 25 and reduced potential for post combustion. (b) Selecting the position of the lance 7 and controlling injection rates of oxygen-containing gas and solids via the lance 7 and the lances 5 to maintain the essentially metal/slag free region around the end of the lance 7 and to form the transition zone 23 around the lower section of the lance 7. (c) Controlling heat loss from the vessel by splashing with slag the sections of the side wall of the vessel 3 that are in contact with the transition zone 23 or are above the transition zone 23 by adjusting one or more of: (i) the slag inventory; and (ii) the injection flow rate through the lance 7 and the lances 5.

(31) Many modifications may be made to the embodiment of the present invention described above without departing from the spirit and scope of the invention.