PRE-HEATING AND PRE-REDUCTION OF METAL OXIDE ORE USING HIGH TEMPERATURE OFF-GASES

Abstract: The specification discloses a process for pre-heating and pre-reducing metal oxide ores. The process comprises introducing particles of an oxide ore entrained in a gas through a port into a treatment chamber. Inside the treatment chamber the stream of entrained particles combines with a stream of high temperature reducing gas in such a way that the particles are heated rapidly and enter into flow patterns whereby contact with other particles and the internal surface of the treatment chamber is minimized. The stream of entrained particles and the stream of high temperature reducing gas are substantially co-current. A treatment chamber elongated in the direction of co-current flow is described in the specification. The hot off-gases may be derived from a molten bath reactor and comprise a high concentration of carbon monoxide and hydrogen.

Description: PRE-HEATING AND PRE-REDUCTION OF METAL OXIDE ORE USING HIGH TEMPERATURE OFF-GASES Field of the Invention This invention relates to a process, treatment chamber and apparatus for the pre-heating and pre-reduction of metal oxide ore using hot off-gases, for example, from a furnace. This invention also provides a process for quenching hot off-gases. Background of the Invention Off-gases from smelt-reduction furnaces are of high temperature and may contain significant quantities of reducing gases such as carbon monoxide and hydrogen. It would clearly be of economic advantage to recover at least some of the sensible heat and make use of some of the reducing potential of the gases. A number or prior art processes are known which provide either pre-heating or pre-reduction of metal oxide ores. Two processes, one by the Kawasaki Steel company and the other by the Nippon Kokan company, combine both features. Generally speaking, the known processes entail one or other of the following disadvantages, and sometimes more than one: several treatment steps may be required; • expensive coke or other reductants may be required; or • there may be temperature limitations leading to low pre- reduction, high residence time or low pre-heat temperature achieved. If the temperature to which the oxide ore is exposed is too high, the particles may soften, leading to accretion on the apparatus and/or agglomeration of particles. In the case of chromite ore, the pre-heating and/or pre-reduction processes described in the prior art are generally speaking limited to temperatures of around 1200°C, at which temperature reduction is very slow. In US Patent 4 629 506 to Krupp, a large excess of reductant is used in conjunction with higher temperatures in an attempt to overcome the slow rate of reduction of chromite ore. However, improvement in this rate is achieved at the expense of pre-heat temperature. Additional process steps may be required involving cooling, crushing and screening, where excess reductant is recycled. A process developed by Kawasaki Steel KK uses fine, unagglomerated ore; see JP 59080706. Pre-heating and pre-reduction is performed in a fluidised bed. Heat and carbon monoxide-rich reducing gas are supplied from the smelting reduction furnace off-gas and are supplemented by the injection of hydrocarbon gas. The pre-mixing of the furnace gas at 1350-1400°C with cooler hydrocarbon gas, for example, methane or propane, results in a cooler gas mixture such that the bed temperature is about 1200°C. It is believed that, at this temperature, a residence time of 12-15 hours is required for substantial reduction of South African chromite with a mean particle diameter of 325μ m. It is also believed that only limited reduction of the iron and chromium oxides was achieved when furnace gas, comprising carbon monoxide, was used alone. The hydrocarbon gas makes major contribution to the reduction of the chromite. It is believed that the disadvantages of this process are the need for addition of hydrocarbon gas to achieve substantial reduction, and the low temperature of the fluidised bed, which causes low rates of reaction but is necessary to prevent softening of the chromite feed and subsequent agglomeration of the particles within the fluidised bed. It seems that the consequent high residence time prevents all chromite ore feed from being pre-heated and pre-reduced. (Some chromite ore is injected directly to the smelting reduction furnace.) Brief Summary of the Invention This invention depends upon the observation that, if particles of oxide ore which are entrained in a gas are exposed to high temperature under reducing conditions in such a manner that contact with each other or with a solid surface is minimised, a better rate of reduction is achieved as compared with the prior art. At the same time a greater proportion of particles which retain their integrity results. This desirable object may be achieved by passing the particles of oxide ore entrained in gas through a port or ports into a treatment chamber where the flow of particles combines with a flow of high ' temperature reducing gas in such a manner that the particles are heated rapidly and enter flow patterns whereby contact of the particles with each other and with internal surfaces of the treatment chamber is minimised and the heated particles lose heat. The treated ore may then be conducted to a smelting vessel, treated further (for example, by further pre-reduction) or stored. According to the invention, the particles are heated to a significantly higher temperature compared to prior art pre-reduction processes. Thus the particles are heated very rapidly to a high temperature at which, some pre?reduction to metal occurs together with some melting. Since the particles may then become somewhat 'sticky', they are cooled rapidly to a lower temperature to reduce agglomeration and accretion to the wall of the pre-heating and pre- reduction chamber. The process according to the invention has the following advantages: The metal oxide ores may be pre-heated to a high temperature and some pre-reduction achieved while limiting loss of particle integrity and accretion to surfaces of apparatus. • The retention of fine particle size assists in subsequent processing of the metal oxide ores. This invention also provides a treatment chamber for pre-heating' and pre-reducing metal oxide ores by the process according to the invention. The internal configuration of the chamber and the inlet ducts for reducing gas are chosen to promote pre-heating and pre- reduction while minimising agglomeration and accretion. This invention further provides an apparatus for the smelting of a metal oxide ore, which incorporates the treatment chamber defined above. A surprising advantage of the present invention is that the process provides quenching of the off-gases rapidly enough to ensure that any sticky solids or other entrained material are cooled to temperatures at which agglomeration and accretion is much reduced or prevented altogether. If the off-gases contain a relatively high proportion of sticky solids etc. it may be necessary to alter certain variables of the process such as the rate of injection of fresh solid particles. This invention further provides an apparatus for pre-heating and, pre-reducing metal oxide ores. Brief Description of the Drawings In the accompanying drawings, Fig. 1 illustrates one embodiment of the invention. Off-gases from a molten bath reactor pass to a pre-heating and pre- reduction chamber. Fresh ore is also passed to this chamber and from there to a settling chamber and finally to the molten bath reactor. Fig. 2 illustrates another embodiment of the invention which features two pre-heating and pre-reduction chambers operating in series. Figs. 3 (a) and (b) illustrate another embodiment of the treatment chamber according to invention. Detailed Description of the Invention This invention will be described with particular reference to chromite ore but it can be applied to any other oxide ore. However, it has particular application to oxide ores which have a 'sticking point' at a temperature within or close to the temperature range at which relatively rapid reduction takes place. Certain oxide ores contain more than one metal. For example, chromite contains iron as well as chromium. Pre-reduction of either or both metals is an advantage. It is recognised that pre-reduction may not reduce all the oxides or oxide components. The invention may be used in conjunction with any reactor which produces off-gases at elevated temperature with reducing potential. It is of particular use in conjunction with a molten bath reactor, for example, a molten ferroalloy bath reactor used to reduce chromite ore. Where off-gas is used, the process according to the invention performs the function of reaction and/or heating of the particulate material and the off-gas is itself quenched. Any sticky or molten substance entrained in the off-gas may adhere to the fine particles. In many cases the presence of a certain amount of this substance is quite acceptable. The invention, in one embodiment, utilises some of the chemical energy and sensible heat, derived from a pyrometallurgical reactor, to pre-heat and pre-reduce metal oxide ores. These particles of metal oxide ore may be heated to a very high temperature to obtain enhanced rates of reduction of the metal oxides. Even if the temperatures employed are lower than those at which stickiness of particles is significant, the process according to the invention provides an improvement over the prior art by reducing contact of the particles in the stream of gas with each other and also with interior surfaces. The particles are subsequently cooled rapidly below their sticking temperature. In the specification the term 'sticking temperature' is meant to include the case where stickiness is initiated over a temperature range. Generally speaking hot off-gases from a suitable source are introduced through an inlet duct or ducts located close to one end of an elongated pre-heating and pre-reduction chamber. The duct or ducts are preferably also located axially or close to the axis of the chamber. The cross-sectional area of the pre-heating and pre-reduction chamber should be substantially greater than the corresponding cross-sectional area of the ducts to minimise direct contact of the off- gases with the walls of the chamber. The oxide particles should preferably be introduced into the chamber at a point or points in close proximity to the points of entry of the off-gases. The ore inlet or inlets should preferably be orientated substantially in alignment with the direction of bulk flow of the off- gases and to some extent towards the axis of the chamber. A degree of swirl may also be provided to the gases transporting the oxide particles. The oxide particles may originate from bulk storage or from another chamber operated in conjunction with the first-mentioned chamber. The oxide particles are transported to the chamber by any suitable gas including off-gas which has been completely oxidised. The oxide particles are introduced into the off-gas stream in the treatment chamber in such a manner that they are entrained in the bulk flow of gas, minimising contact between particles and with • interior surfaces. The fine metal oxide particles are heated rapidly to very high temperature through contact with the hot off-gases. It is surmised that certain flow patterns set up within the chamber near the wall of the chamber have a major role in the presentation of accretion and agglomeration. Heat is lost through the wall of the chamber. At the stage of discharge from the chamber, the particles in the flow patterns have dropped in temperature below the sticking temperature. Contact between hot oxide particles may be minimised by varying the relative proportions of hot gas and metal oxide. Usually the quantity of gas available is 'given' and is dependent upon the operation of the furnace, for example. Thus the feed rate of metal oxide is matched to the flow of gas to avoid, so far as possible, undesirable collision between oxide particles and to control the target temperature within the chamber. This factor should also be taken into account in the design of the chamber, for example, to avoid unnecessary choke-points and topromote gas flow, which after entry into the chamber, should be substantially axial. The chamber may be fitted with a riser and in this case, the particles will cool further before entering the means to conduct the particles to the next treatment stage. As mentioned previously, the internal configuration of the chamber and the inlet ports is chosen to promote pre-heating and pre- reduction and to minimise agglomeration of particles and accretion on interior surfaces. The shape of the or each port or inlet duct is selected to provide smooth, rounded interior surfaces with the minimum of dead space to reduce or eliminate agglomeration of particles from the molten bath reactor around the port or duct. Once the particles have been reduced to the desired temperature they may be withdrawn from the chamber and passed to further processing, for example, in a cyclone. A suitable temperature gradient may be achieved by means of external cooling. The residence time of the particles in the region of elevated temperature may be controlled by adjusting flow rates of one or both of the furnace off-gases and the carrier gas. It should be noted that the oxide particles may be passed once through the chamber or more than once, as required. In one embodiment of the invention a flux or fluxes may be added to either the fresh oxide feed or the recycled oxide feed, the flux or fluxes being entrained in the entrainment gas. It may be advantageous to inject some carbonaceous material and oxygen-containing gas which, when combusted, may be used to boost the temperature within the chamber to increase the rate of reduction. Turning now to a more detailed consideration of the use of off-gases from, for example, a molten bath reactor, which contain a relatively high concentration of carbon monoxide and hydrogen, the exit temperature of these gases may range from 1400 to 1800°C . These off-gases are passed to a treatment chamber 1 as shown in Fig. 1, where they exit from inlet duct 2 into the chamber. Duct 2 is shown located upstream from ports 3 and 4 through which pass fresh ore in a carrier gas. (Location upstream is the usual location.) The spatial relationship of duct 2 to port 3 and 4 and the internal dimensions of 1 are chosen to promote rapid reduction of the ore particles in the general region near ports 3 and 4, followed by cooling as they penetrate further into the chamber. In this way melting of the particles is minimised and stickiness reduced. The geometry of duct 2 and ports 3 and 4 and their spatial relationship are chosen to reduce contact of the particles with the wall of the chamber, reducing or preventing build-up on the wall. Gas and entrained solids pass to separator 5 from which waste gas passes to gas cleaning. Solids from 5, still entrained in gas, pass to stream divider 6. All of the solids may be passed to a molten bath reactor 7 or a proportion may be returned to treatment chamber 1. Turning now to Fig. 2, two treatment chambers 8 and 9 are provided in series. Off-gases from molten bath reactor 10 pass to chamber 8 where they combine with entrained solids originating from separator, chamber 9 and ultimately from a fresh feed source (not shown). Gas and solids from chamber 8 are passed to separator 12, the separated gas being passed to chamber 9 and the solids to splitter 13., The solids from splitter 13 are divided, one portion being passed to reactor 10 and the other portion to chamber 9. Ducts and ports in chambers 8 and 9 are similar to those in chamber 1 in the embodiment shown in Fig 1. In the embodiment shown in Fig 2, the fresh solids are injected into the cooler treatment chamber 9, before being passed via separator 1 1 to hotter chamber 8. In both of the embodiments shown in Figs 1 and 2, the solids which are passed to the respective molten bath reactor are conveniently admitted through the top of the reactor but may be injected at other points in the reactor. At the top of the reactor the entry port may be separate or " combined with the entry port for oxygen-containing gas, for example, through an annulus surrounding the entry port for oxygen-containing gas. In the embodiment of Figs 3(a) and (b), cooler particulate material is introduced into chamber 14 near the chamber exit but in proximity to the chamber walls, so as to provide a falling curtain of cooler particles adjacent to the interior surface. These particles, as they fall towards the off-gas entry duct of the chamber become entrained in the flow of off-gas, and leave the chamber through the gas and solids exit duct. The particles enter chamber 14 through internal, annular distributer 15. The falling curtain is designated 16 in Fig. 3 (b), which represents a cross-sectional view along line A — A of Fig 3(a). Duct 17 and ports 18 and 19 are similar to those shown in Figs 1. Generally speaking, hot solids, which have a tendency to agglomerate during prior processing, are not readily amenable to introduction into molten baths via tuyeres or injectors. In consequence of their fine particle size, the pre-heated solids produced according to this invention are well-suited to conveying and injecting into a molten bath process. In both of the embodiments shown in Figs. 1 and 2, the dotted arrow to the left of the figure indicates injection of carbonaceous material and oxygen-containing gas. However, the region of injection must be carefully selected so as not to interfere with the mechanism of rapid heating of the particles following by cooling. The rate of reduction may also be boosted by injection of, for example, carbon monoxide, through duct 2. In the specification the term Oxygen-containing gas' refers to pure oxygen and gas containing oxygen, including air and oxygen-enriched air. In the specification the term 'carbonaceous material' refers to any carbon-based material which can be burned to produce a suitably high temperature and includes: anthracite, bituminous or sub- bituminous coal, coking or steaming coal, coke, lignite or brown coal, lignite or brown coal-derived char, heavy petroleum residues and natural gas. The lignite or brown coal may have been densified using the process disclosed in Australian patents no. 561584 and 588565 and lapsed application no 52422/86. A process for preparing a char from such a densified product is disclosed in Australian patent application no 52234/86. In the specification the molten bath reactor from which the hot off- gases are supplied may, for example, be any of the following: molten iron bath reactor, deep slag process reactor, ferroalloy bath reactor, non-ferrous bath reactor, or any other pyrometallurgical process bath reactor that discharges hot off-gases. This invention also provides a treatment chamber for the pre¬ heating and pre-reduction of oxide ore, which comprises: 1. a vessel adapted to confine and direct a flow of oxide particles and high temperature reducing gas; 2. a port or ports for oxide particles entrained in carrier gas; and 3. an inlet duct or ducts for reducing gases, the port (s) and the inlet duct(s) being so arranged that the oxide particles are initially exposed to reducing conditions and subsequently cooled to control agglomeration and sticking. This invention also provides an apparatus for the smelting of a metal oxide ore, which comprises in combination: 1 . a molten bath reactor for the smelting of the ore; 2. means to conduct off-gas from the reactor to 3. a treatment chamber or chambers as defined above; 4. means to inject fresh metal oxide ore, or metal oxide ore which has been pre-heated and partially pre-reduced, to the chamber or chambers; 5. means to conduct the oxide particles entrained in gas from the chamber or chambers to a gas solid separator or separators; and 6. means to conduct at least a proportion of the separated solids and some entraining gas to the reactor, and if desired, a proportion to the chamber or chambers. It will be clearly understood that the invention in its general aspects is not limited to the specific details referred to hereinabove.

Claims: AMENDED CLAIMS [received by the International Bureau on 19 October 1990 (19.10.90); original claims 1-17 replaced by CLAIMS amended claims 1-10 (2 pages)] 1. A process for pre-heating and pre-reducing a metal oxide which process comprises forming a stream of metal oxide particles and hot reducing gas to heat and to reduce, at least partially, the metal oxide particles wherein the hot reducing gas has a temperature in excess of that at which the metal oxide particles, particles contained in the stream of reducing gas or both exhibit sticky characteristics. 2. A process according to claim 1 wherein the metal oxide particles are heated to a temperature in excess of that at which they exhibit sticky characteristics and are thereafter quenched to a temperature below that at which they exhibit sticky characteristics. 3. A process according to either claim 1 or claim 2 wherein the stream is formed in a chamber and the process further comprises the steps of causing the particles in the stream to enter flow patterns in which inter-particle contact is minimized and sticky particles are cooled below their sticky temperature before contacting internal walls of the chamber. 4. A process according to claim 3 comprising the additional steps of entraining the metal oxide particles in a gas to form a stream of entrained metal oxide particles and causing the stream of entrained metal oxide particles to mix with a stream of the hot reducing gas to form the stream of metal oxide particles and hot reducing gas. 5. A process according to claim 3 or claim 4 wherein the particles are caused to enter the flow patterns desired by progressively reducing the velocity of the stream of metal oxide particles and hot reducing gas as the stream travels through the chamber from a first end towards a second end of the chamber and then causing the velocity to increase as the second end is approached. 6. A process according to any one of claim 1 to 5, wherein the hot reducing gas is an off-gas from a smelting reduction furnace. 7. A process according to claim 6, wherein the temperature of the off-gas is in the range from 1400 C to 1800 C. 8. A process according to any one of the preceding claims, wherein the metal oxide is a chromite ore. 9. A process according to claim 4, wherein a degree of swirl is imparted to the stream of metal oxide particles and hot reducing gas by the stream of entrained metal oxide particles. 10. A process according to any one of the preceeding claims, wherein portion of the metal oxide comprises recycled particles of metal oxide. STATEMENTUNDERARTICLE19 Claim 1 has been amended in order to clearly identify the essential features of the process of the invention. Consequential amendments have been made to the subsidiary claims. The subsidiary claims have also been amended in order clearly identify additional process steps. Apparatus claims have been deleted. Consequential changes would also need to be made to the description in order to clarify the essential features of the process of the invention.

Inventors: BATTERHAM ROBIN JOHN, GRANT RODERICK MACPHERSON, HAPP JAMES VINCENT, THIELE GLENN ASHLEY, BATTERHAM, ROBIN, JOHN, GRANT, RODERICK, MACPHERSON, HAPP, JAMES, VINCENT, THIELE, GLENN, ASHLEY
Applicants: CRA SERVICES, CRA SERVICES LIMITED
Application year: 1990
Main classification: C22B5
IPC codes: B01J8, B22F9, C21B13, C22B1, C22B5, C22B34