AU2007309609B2 - Microwave heating method and apparatus for iron oxide reduction - Google Patents
Microwave heating method and apparatus for iron oxide reduction Download PDFInfo
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- AU2007309609B2 AU2007309609B2 AU2007309609A AU2007309609A AU2007309609B2 AU 2007309609 B2 AU2007309609 B2 AU 2007309609B2 AU 2007309609 A AU2007309609 A AU 2007309609A AU 2007309609 A AU2007309609 A AU 2007309609A AU 2007309609 B2 AU2007309609 B2 AU 2007309609B2
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/56—Manufacture of steel by other methods
- C21C5/567—Manufacture of steel by other methods operating in a continuous way
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0046—Making spongy iron or liquid steel, by direct processes making metallised agglomerates or iron oxide
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/08—Making spongy iron or liquid steel, by direct processes in rotary furnaces
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/10—Making spongy iron or liquid steel, by direct processes in hearth-type furnaces
- C21B13/105—Rotary hearth-type furnaces
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/14—Multi-stage processes processes carried out in different vessels or furnaces
- C21B13/143—Injection of partially reduced ore into a molten bath
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/20—Details, accessories, or equipment peculiar to rotary-drum furnaces
- F27B7/34—Arrangements of heating devices
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B9/00—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity
- F27B9/14—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment
- F27B9/16—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment the charge moving in a circular or arcuate path
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B9/00—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity
- F27B9/30—Details, accessories, or equipment peculiar to furnaces of these types
- F27B9/36—Arrangements of heating devices
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
- C21B2100/40—Gas purification of exhaust gases to be recirculated or used in other metallurgical processes
- C21B2100/42—Sulphur removal
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
- C21B2100/60—Process control or energy utilisation in the manufacture of iron or steel
- C21B2100/66—Heat exchange
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/122—Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Furnace Details (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Manufacture Of Iron (AREA)
Abstract
A method and apparatus for reducing iron oxides using microwave heating in a furnace chamber which is sealed against the entrance of air reduces trie energy required and produces a low temperature reduction and allows the recovery of combustible synthetic gas as a byproduct of the process. Avoidance of the reduction of sulfur, phorphorus and silica is also insured, as is the need to reduce the silica content of the feed material prior to reducing the ore. A continuous rotary hearth furnace, a rotary kiln, a linear conveyor and vertical shaft furnace chamber configurations are described. A secondary heating zone can also be included to process the reduced iron into iron nuggets or liquid metallic iron.
Description
WO 2008/051356 PCT/US2007/021254 MICROWAVE HEATING METHOD AND APPARATUS FOR IRON OXIDE REDUCTION CROSS REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. provisional patent application Serial No. 60/849,098 filed on October 3, 2006 and Serial No. 60/865,672 filed on November 14, 2006, and is a continuation in part of U.S. patent application Serial No. 11/220,358 filed on September 6, 2005 which claimed the benefit of U.S. provisional patent application Serial No. 60/607,381 filed on September 3, 2004 and U.S. provisional patent application Serial No. 60/607,140 filed on September 3, 2004. BACKGROUND OF THE INVENTION Currently steel is produced by two types of operations: integrated mills and minimills. In the integrated mill, sintered iron ore pellets, coke and lime are charged into a blast furnace (BF). Air is blown in at high speed to combust the coke to generate carbon monoxide and heat. Sintered iron ore pellets are reduced to hot metal by the carbon monoxide and melted to form liquid iron. The liquid iron is then sent to a basic oxygen furnace (BOF) where pure oxygen is blown into the liquid iron to remove excessive carbon and convert iron into steel. The fundamental problems associated with this production route are the needs for coke and intense high temperature combustion. Coke making is one of the most polluting of industrial processes and high temperature combustion generates a great amount of dust and wastes energy in the exhaust gases. Minimills employ electric arc furnaces (EAF) to melt steel scrap with or without DRI (Direct Reduced Iron) and produce generally lower quality steel. Minimills traditionally enjoyed an abundant supply of steel scrap, however, the recent strong demand for scrap internationally
I
WO 2008/051356 PCT/US2007/021254 has doubled the price. DRI prices have also significantly increased due to high cost of reformed natural gas, causing many DRI plant closings. A revolutionary steelmaking technology has been developed by the present inventors based on the use of microwave energy (U.S. Patent No. 6,277,168). This technology can produce DRI, iron or steel from a mixture, consisting of iron oxide fines, powdered carbon and fluxing agents. This technology is projected to eliminate many current intermediate steelmaking steps, such as coking, sintering, BF ironmaking, and BOF steelmaking. This technology has the potential to save up to 50% of the energy consumed by conventional steelmaking; dramatically reduce the emission of CO 2 , S02, NOx, VOCs, fine particulates, and air toxics; substantially reduce waste and emission control costs; greatly lower capital cost; and considerably reduce steel production costs. Microwave heating technology has the advantage over blast ovens relying on combustion in being faster to heat the iron oxide feed materials since it does not rely on conducting heat into the material through air or other gases but rather it generates heat internally directly by absorbing the microwave radiation. Furthermore, microwave heating is selective, i.e., it only heats components of the material that needs to be heated, i.e., to reduce the hematite or magnetite and does not heat the silica, phosphorus, sulfur or other non ferrous components of the feed material directly, so that the energy is much more efficiently used and the maximum temperature reached can be much lower. The feed material does not need to be electrically conductive to be heated with microwave radiation in being reduced. Another problem with iron and steel making has been the retention of sulfur and phosphorus in the iron which may reduce the quality of the iron or steel produced. This problem results from the much higher temperatures typically reached in conventional reducing of iron 2 WO 2008/051356 PCT/US2007/021254 oxide by combustion of natural gas or coal. These higher temperatures result since the outside of the pellets or green balls or other feed material is raised to a temperature much higher than needed to carry out reduction because of the need to achieve proper heating throughout the entire pellet or ball and to reduce the time required to raise the entire mass to the level required for reducing the iron oxide. At these higher temperatures, phosphorus and sulfur are also reduced and this results in elemental phosphorus and sulfur being retained in the iron or steel. This problem is exacerbated if coal is used to reduce the ore or other feedstock since coal sometimes contains sulfur, and this would further increase the level of sulfur in the iron. A further problem resulting from the high temperatures required in conventional reduction processes is that expensive refractory material must be employed in the furnace increasing the capital costs. Also, any silica present may also be reduced, which will also contaminate the iron and have a deleterious effect on its quality in many cases. Another problem encountered concerns excess silica being present in the feed material either from the mining operations or in the ore deposits. Silica content varies in iron ore from different deposits. While silica will be eliminated by being part of the slag forming on molten metal, if excessive slag forms this will block attempts to inject a gas into the molten metal and thus interfere with the process. Thus, in instances where excessive silica is present in the ore or the pellets, the silica content must first be removed or at least minimized. This has heretofore required grinding of the ore into a very fine powder in order to mechanically separate the silica from the ore, a quite costly process representing a major expense item and energy consumer in processing such ore. In fact, too high levels of silica can render some ores commercially worthless. 3 Another disadvantage arises from the air injection of conventional practice and blast heating to reduce iron ore as this generally results in combustion of all the carbon associated with the feed material into carbon dioxide. This represents a waste of potentially useful carbon combustibles and adds to the carbon "footprint" of the process. 5 It is the object of the present invention to provide apparatus and methods for the production of metals and in particular iron and steel which utilize microwave heating in such a way to realize the potential benefits of using microwave heating in iron and steel production. SUMMARY OF THE INVENTION 10 The above recited objects and other objects which will be understood upon a reading of the following specification and claims are accomplished by carrying out the reduction phase of iron oxide at a relatively moderate temperature by the use of microwave radiation while excluding air. In an embodiment, there is provided a method of reducing iron oxide comprising 15 including charging a feed material comprised of iron oxide and coal powder containing hydrocarbon volatiles including methane into a first zone of a furnace chamber and irradiating the same with microwave radiation of sufficient intensity to reduce said iron oxide in said feed material into direct reduced iron (DRI) while sealing said furnace chamber against the entrance of air, said reducing carried out by reaction of said carbon 20 in said coal with said iron oxide to produce carbon dioxide and also reducing said iron oxide by reaction with carbon monoxide produced from reaction of said carbon with said carbon dioxide, transporting said DRI into a second zone of said furnace and further heating said DRI sufficiently to melt said ORI to form iron nuggets, additional carbon in said coal of said feed material converting carbon dioxide product from said 25 iron oxide reduction reaction by carbon monoxide producing additional carbon monoxide, reacting methane vaporized from said coal during said reduction of said iron oxide with carbon dioxide in the presence of said melted DRI as a catalyst to form hydrogen and carbon monoxide, said carbon monoxide and hydrogen collected as an off gas from said second zone of said furnace. 30 The microwave radiation heats only the iron containing constituents of the feed material for maximum efficiency in the use of energy and the moderate temperatures avoid reduction of phosphorus, sulfur or silica present to minimize contamination of the 4 3084492_1 (GHMatters) P80694.AU 31/01/12 iron with those elements. Volatile gases from coal and carbon combustibles are produced and can be recovered for use as a fuel or as a reducing gas. Continuous processing at moderate temperatures becomes practical due to the speed of microwave heating of the material to reach reduction temperatures. According, to the invention, feed materials may be reduced in a rotary hearth furnace, a linear conveyor furnace, a rotary kiln, or in vertical shaft furnaces which each enable multiple microwave wave guide mountings to readily achieve the necessary heating capacity for a given application. The DRI produced can be discharged into a collecting container or directly into an electric arc furnace for producing steel. The microwave heating reduction may be combined with a secondary heating of the reduced ore (DRI) to obtain iron nuggets. An induction melting furnace to produce liquid iron can also be used to receive the DRI. The rotary kiln (and all of the other furnaces can utilize a combination of microwave and combustion heating to produce DRI or solely by multiple microwave sources. A linear conveyor associated with a conveyor can produce either DRI or iron nuggets with secondary heating after the reduction phase which may also be accomplished with microwave heating or by burner heating, radio frequency radiation, etc. A vertical shaft furnace can also be used in which the ore pellets or other feed material is introduced at the top of a refractory lined cylinder. Microwave heating is carried out as the material descends down the furnace. An induction heater may be provided at the bottom which receives DRI and produces melted iron discharged therefrom and is slag drawn off from the melted iron. Alternatively, injection of natural gas or other reducing gas can be done to produce DRI in the shaft furnace without carbon material in the feed. The use of microwave energy to reduce the feed materials allows reduction to be carried out at lower a temperature since the entire mass is heated at once such that overheating of any portion is not necessary. 5 WO 2008/051356 PCT/US2007/021254 If the phosphorus and sulfur remain as oxides in the feed material, they form part of the slag when the reduced feed material is melted and are thereby eliminated from the metal with the slag. Continuous processing is rendered easier by using microwave energy to reduce the feedstock while avoiding any problem with retention of sulfur and or phosphorus. By microwave heating at lower temperatures, reduction of silica is minimized. However, the major benefit of the approach is that gas injection is not required such that a reduction of silica in the slag by a mechanical removal of the silica prior to processing is not required. Even relatively large quantities of silica can be removed in the slag and need not be removed by costly fine grinding and mechanical separation as practiced conventionally to reduce silica content prior to reduction of the ore. DESCRIPTION OF THE DRAWINGS Figure 1 is a diagrammatic sectional view through a rotary hearth furnace and related components according to the present invention. Figure IA is an enlarged view of a section taken through one side of the rotary hearth furnace showing constructional details. Figure 2 is a diagrammatic plan view of the rotary hearth furnace shown in Figure 1. Figure 3 is a view of a vertical section through the rotating base of the rotary hearth furnace of Figures 1 and 2. Figure 4 is a plan view of the rotating base shown in Figure 5. Figure 5 is an enlarged view of a section taken through one side of the rotary furnace shown in Figure 1 showing a DRI discharge and microwave guide. 6 WO 2008/051356 PCT/US2007/021254 Figure 6 is a vertical section through an electric arc furnace alternatively receiving the DRI for melting. Figure 7 is a diagrammatic view of a vertical section through an induction melting furnace arranged to receive the DRI discharge. Figure 8 is a diagrammatic plan view of an alternate form of rotary hearth furnace according to the invention and showing components for recovery for synthetic gas. Figure 9 is a diagrammatic section view of a rotary kiln version of a microwave heated reduction furnace according to the invention. Figure 10 is a diagram of a conveyor or traveling grate embodiment of a furnace chamber according to the present invention with secondary heating. Figure 11 is a diagram of a vertical shaft furnace chamber according to the present invention. Figure 12 is a diagram of an alternate form of vertical shaft furnace chamber according to the present invention. Figure 13 is a diagrammatic depiction of an overall installation according to the present invention. DETAILED DESCRIPTION In the following detailed description, certain specific terminology will be employed for the sake of clarity and a particular embodiment described in accordance with the requirements of 35 USC 112, but it is to be understood that the same is not intended to be limiting and should not be so construed inasmuch as the invention is capable of taking many forms and variations within the scope of the appended claims. 7 WO 2008/051356 PCT/US2007/021254 Referring to the drawings and particularly Figures 1-5, a rotary hearth furnace 10 according to the present invention is depicted. This comprises a stationary annular upper chamber 12 having outer walls 14 of a refractory insulating material and an inner skin 16 of stainless steel attached to embedded anchors 17 in the refractory walls 14. A rotating base assembly 18 supports a ring shaped hearth 20 which is rotated beneath the stationary annular chamber 12 by a motor- right angle drive 24 and chain 26. A series of main rollers 27 are mounted on a base plate 21 and beneath a support plate 23 rotatable about a pivot 25. A series of inside and outside secondary rollers 29 attached to brackets 29A transfer the weight of the upper chamber 12 onto bracket flanges 31 on the base assembly 18. A refractory material hearth base 22 holds a hearth layer of such material such as silica, limestone etc. dispensed from a feed opening 28. Feedstock material is dispensed onto the hearth layer through a dispenser 30. Such feed material may include iron ore pellets admixed with ground coal or other carbonaceous material to supply carbon for reduction of the ore, and other components to form "green" balls in the well known manner, creating a bed of feed material on the hearth base 22. Flux, binders and other components are used to create such feed material. Cross pipes 15 can be included to reinforce the chamber 22 particularly during shipping. Refractory divider walls 32, 34 of refractory material define a furnace reduction subchamber 36 within the annular chamber 12 wherein the reduction of the iron oxide feed material takes place. A refractory rope air seal 38 resting on bracket flange 31 encircles the rotating hearth structure 20 to prevent air from entering the chamber 12 and a metal rope microwave seal 40 8 WO 2008/051356 PCT/US2007/021254 prevents the escape of microwaves during operation. Similar seals are provided at the material charge and discharge ports for air and microwave sealing. Microwaves from a generator 46 are introduced into the annular chamber 12 through a pair of waveguides 42, 44 which are preferably oriented at 900 to each other to create homogeneous microwave distribution in chamber 12. A microwave "stirrer" blade (not shown) can also be included for even greater homogeneousness of the microwave irradiation. Additional waveguides 48 can be employed if greater power is required for a particular application. A viewing window 49 is also provided. The power level is set to raise the temperatures to that at which reduction will occur i.e., approximately 600 - 1200*C, which as discussed above is much lower than the temperatures in excess of 1600*C reached in conventional combustion reducing processes. It will be understood by those skilled in the art that one or more pyrometers 45 and gas probes 47 will be used to monitor the process conditions for control and safety reasons. The speed of microwave heating is much greater than combustion heaters since the microwave radiation heats the material from the inside and only heats the iron bearing material (not the silica). Thus, a continuous process operated at relatively low temperatures is made practical. The feed material is reduced to direct reduced iron (DRI) by this heating in the present of carbon and then moved to a discharge port and chute 50 (Figure 5). A steel plow (or screw) 52 causes the DRI to be discharged through the port so where it is collected in a container 54 for further processing. 9 WO 2008/051356 PCT/US2007/021254 A refractory guide block 56 may be used to adjust the width and depth of feed material on the hearth 22. As shown in Figure 6, the DRI may alternatively be directly discharged into an electric arc furnace 58 for the production of steel from the DRI. As another alternative shown in Figure 7, the DRI may be discharged into an induction melting furnace 60 with discharge ports for liquid metal and slag (not shown). A liquid bath must first be formed using iron prior to initiating the process using DRI. Figure 8 shows an alternative embodiment in which a secondary heating source 64 is provided in order to increase the DRI temperature about 200*C in a secondary heating zone 68 within the chamber furnace. This temperature increase along with a proper recipe of the feed material and the hearth layer material can produce iron nuggets as the end product. The secondary heating source could include microwave radiation but microwave absorbing material such as carbon must be added, as the DRI material does not absorb microwave energy. Other heating means could be employed. As discussed above, since the furnace chamber 12 is sealed, preventing air from entering, volatile components of coal (primarily methane) gassed off and the carbon monoxide generated from the carbon reducing the iron oxides by the lower temperature reduction process can be collected via a discharge duct 62 (Figure 8) for use elsewhere. That gas can be used to fuel a burner (not shown) comprising the secondary heat source after removal of dust by a cleaning system such as a bag house 68. The dust can contain byproducts such as zinc or zinc oxide which may be recovered as indicated. Figure 9 shows a rotary kiln 70 embodiment of the invention in which a cylindrical housing 72 is rotatably mounted and driven with its axis inclined shallowly from the horizontal. 10 WO 2008/051356 PCT/US2007/021254 The feed material (iron ore pellets with coal) is loaded via a charging port 74 into the furnace chamber 76 defined in the housing 72. Microwave radiation from a generator 78 is introduced via a longitudinally aligned waveguide 80. Mating flanges at 77, 79 have interposed microwave and air seals 81, 83. Additional waveguides can be provided on the side via microwave transparent windows 82 (which can be constructed of a refractory material). A burner 84 can augment the heat of the microwaves to produce DRI discharged at discharge port 86. An auger device 77 may also be provided to assist movement of the feed material. Figure 10 shows a linear conveyor furnace 88 in which a furnace chamber defining structure 90 has an endless conveyor 92 (which can be composed of a traveling grate) with an upper run 94 extending beneath it supported on a support structure 96. Feed material is loaded at one end and carried into a furnace chamber 98. Furnace chamber 98 has a primary zone 98A irradiated by microwaves radiation from a generator 100 introduced via wave guides 102. In a secondary zone 98B further heating of the reduced iron is carried out, as by radio frequency radiation, burners, etc.,which can optionally be provided to produce iron nuggets. The DRI or iron nuggets are off loaded at the other end of the conveyor 92. Microwave seals 104 are comprised of an array of steel bars or rods, spaced apart in a pattern which will block microwave leakage through the end openings by well known techniques. Furnace gas can be collected through duct 106. A screw conveyor 105 may be employed to assist in advance of the feed material. 11 WO 2008/051356 PCT/US2007/021254 Figure 11 shows a vertical shaft embodiment of the invention, in which a tubular housing 108 defines a furnace chamber 110. The housing 108 can be constructed of a steel grille cover with a refractory shell, allowing penetration of microwaves from generators 112 directed through an outer enclosure 114. Feed material such as pellets or a mixture as described is fed into a charging port 116. An induction heater 118 at the lower end of furnace chamber 108 receives the DRI produced by the microwave heating in the upper region of the chamber 100 and heats it sufficiently to produce molten iron discharged at port 120. Slag is discharged at the top through port 122. The synthetic gas produced is discharged at the top through port 124. Figure 12 shows a variation in which DRI is discharged via a bottom opening 126. The DRI can be produced without carbon in the feed material by injecting natural or other reducing gas into bottom ports 128. Figure 13 illustrates an integrated apparatus for concurrent production of steel and syngas. Coal is used as both reducing agent and gasification material. Ore from a source A is loaded into a first dispenser 130 positioned over a conveyor 132, coal from a source B into a second dispenser 134, (via a pulverizerl35) additives such as flux from source C into a third dispenser 136 (via a pulverizer 137), and binder from source D in a fourth dispenser 138. The conveyor discharges all of these materials into a mixer which discharges the mixed ingredients into a pulverizer 142 which in turn charges a dispenser 144. Carbon particles are also deposited in a layer onto a conveyor 148 by a second dispenser 146. A rotary conveyor or traveling grate 148 is disposed in a sealed housing 150 (the conveyor perimeter shown in Figure 13 is developed into a straight line). 12 WO 2008/051356 PCT/US2007/021254 The pellets are dispensed to form a bed 152 on top of a carbon particle bed 155 on the conveyor 148 via a charging port 154. The carbon particles are deposited onto the conveyor 148 via a charging port 156. An organic binder is used to agglomerate iron ore concentrate, pulverized coal and fluxing agent into pellets. The feed material is dispensed onto the conveyor 148 in a layer leveled by the lower end of the dispenser 154 and is transported from the entrance to the exit of the furnace chamber 168. Microwave radiation from generators 160 is introduced into the furnace through waveguides 158 to heat the feed material to reduce the iron oxide. Iron oxides and many carbon bearing materials are excellent microwave absorbers and can be readily heated by microwave irradiation. Upon microwave heating, volatiles, primarily methane in the coal, are released into the off-gasses to form a portion of the syngas. Continuous heating will cause the following reactions: C+0 2 = CO 2 C0 2 +C =2CO 3Fe 2
O
3 + CO =2Fe 3 O4 + CO 2 FeO + CO =Fe + CO 2 H2O + C= CO + H 2 C0 2 + CH 4 Fe _,2CO +2H 2
H
2 0 + CH 4 Fe_.CO + 3H 2 Thus, iron ore is reduced into metallic iron or DRI in the reduction zone 168. At the elevated temperature and carbon rich environment which are required for fast and complete iron 13 WO 2008/051356 PCT/US2007/021254 ore reduction, most of the water and carbon dioxide are reacted with carbon to form hydrogen and carbon monoxide. The process is a continuous operation. The produced DRI also function as a catalyst to promote the transformation of methane into hydrogen and carbon monoxide. The off-gases eventually reach a steady composition, a mixture of volatiles and iron ore reduction spent gas. Due to no oxygen or air required for combustion as in a ordinary gasifier or a combustion furnace, the off-gas composition can be readily controlled and a high quality syngas can be produced and collected. The coal volatile content and the equilibrium phase diagram or iron oxides, iron, CO, and
CO
2 vs. temperature can be used as references for controlling the off-gas composition. The exhaust port 166 can be located either near the feed material charging port or the product discharging port to form a countercurrent or concurrent flow. The countercurrent flow transfers gas heat better to the feed material and the concurrent flow generates a higher quality syngas. After DRI is formed, the feed material becomes a poor microwave absorber due to formation of networked metallic iron. Therefore, the underling carbon layer or coating, preferably made of pyrolyzed carbon particles such as coke, graphite, activated carbon, or fly ash carbon in dry or slurry form, is layered or applied before charging iron ore agglomerates into the furnace by the dispenser 156. The carbon layer 155 or coating becomes the major microwave receptor/susceptor to be heated by microwave and to transfer heat to the above disposed DRI in the smelting zone. The smelting zone 170 is separated from the reduction zone by refractory dividers 152 to reduce interference between the two zones. As an alternative, such carbon microwave receptor material can be applied over the agglomerates/DRI at an appropriate location. The carbon material is heated by microwave and transfers heat to the underneath agglomerates/DRI. A 14 powdered poor microwave absorbing material also can be used to cover the agglomerates/DRI to reduce convection and radiation heat loss. The DRI's temperature continues to rise and the DRI reacts with the remaining internal carbon and the underlying or covering carbon to form molten iron nuggets and associated slag. The eutectic iron and 5 carbon composition (4.26%C) helps to lower the melting point of the iron to 11 54*C. The associated slag has a composition suitable for desulphurization and dephosphorization with lower melting point, lower viscosity, proper plasticity, and easy separation of iron nuggets from slag after cooling. The remaining underlying carbon layer also functions as an isolator between the 10 molten nuggets/slag and the refractory base to prevent erosion of the molten nuggets/slag to the refractory and facilitates discharging the produced nuggets/slag from the refractory base. If necessary, another refractory coating made of oxides, borides, carbides and/or nitrides can be applied between the carbon layer and the refractory base. The produced iron nuggets can be used as a feed material for steelmaking by EAF or 15 a feed material for ferrous foundries. Because of no major combustion heating, the off-gas is of lower temperature and contains less particulate. The off-gas is passed through a cleaning system 164 to further cool down, remove and collect particulates in a container 172, recover and collect sulfur in a container 172, and separate H 2 0 and CO 2 if any and necessary, becoming a syngas. 20 Because of no steam and combustion requirements, the syngas production has fewer problems of H 2 0 separation and NO, formation. The syngas can be used as a fuel for ordinary heating, a raw material for production of chemicals and liquid fuels, a hydrogen source after separation, a fuel to drive a power plant, or a reducing gas for iron ore reduction. Various heat exchangers can be installed along the line to utilize waste heat. 25 It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country. In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the 30 word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention. 15 3084492_1 (GHMatters) P80694.AU 31/01/12
Claims (6)
1. A method of reducing iron oxide comprising including charging a feed material comprised of iron oxide and coal powder containing hydrocarbon volatiles including 5 methane into a first zone of a furnace chamber and irradiating the same with microwave radiation of sufficient intensity to reduce said iron oxide in said feed material into direct reduced iron (DRI) while sealing said furnace chamber against the entrance of air, said reducing carried out by reaction of said carbon in said coal with said iron oxide to produce carbon dioxide and also reducing said iron oxide by reaction with carbon monoxide 10 produced from reaction of said carbon with said carbon dioxide, transporting said DRI into a second zone of said furnace and further heating said DRI sufficiently to melt said DRI to form iron nuggets, additional carbon in said coal of said feed material converting carbon dioxide product from said iron oxide reduction reaction by carbon monoxide producing additional carbon monoxide, reacting methane vaporized from said coal during said 15 reduction of said iron oxide with carbon dioxide in the presence of said melted DRI as a catalyst to form hydrogen and carbon monoxide, said carbon monoxide and hydrogen collected as an off gas from said second zone of said furnace.
2. The method according to claim I wherein said microwave irradiation is set to be 20 not intensive enough to reduce sulfur or phosphorus contained in said feed material.
3. The method according to either claim 1 or 2 wherein said coal powder is mixed with said iron oxide prior to entering said first zone of said furnace. 25
4. The method according to any one of the preceding claims wherein said furnace chamber extends linearly and a conveyor is disposed along said furnace chamber and said feed material is deposited at one end of said conveyor to carry feed material along said furnace chamber by said conveyor. 16 3084492_1 (GHMatters) P80694.AU 31/01/12
5. The method according to any one of the preceding claims wherein said coal also contains moisture and further including reacting vaporized moisture from said coal with carbon and methane in said second chamber to produce addition carbon monoxide and hydrogen also collected from said second zone of said furnace. 5
6. A method of reducing iron oxide substantially as herein described with reference to Figures I to 5 and 8 to 13. 17 3084492_1 (GHMattere) P80694.AU 31/01/12
Applications Claiming Priority (5)
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US84909806P | 2006-10-03 | 2006-10-03 | |
US60/849,098 | 2006-10-03 | ||
US86567206P | 2006-11-14 | 2006-11-14 | |
US60/865,672 | 2006-11-14 | ||
PCT/US2007/021254 WO2008051356A2 (en) | 2006-10-03 | 2007-10-03 | Microwave heating method and apparatus for iron oxide reduction |
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AU2007309609B2 true AU2007309609B2 (en) | 2012-03-15 |
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EP (1) | EP2089549A4 (en) |
CN (1) | CN101548024B (en) |
AU (1) | AU2007309609B2 (en) |
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AU2011286470A1 (en) | 2010-08-03 | 2013-03-21 | Xiaodi Huang | Method and apparatus for coproduction of pig iron and high quality syngas |
US8741023B2 (en) | 2011-08-01 | 2014-06-03 | Superior Mineral Resources LLC | Ore beneficiation |
US8545594B2 (en) | 2011-08-01 | 2013-10-01 | Superior Mineral Resources LLC | Ore beneficiation |
JP5729278B2 (en) * | 2011-11-30 | 2015-06-03 | 新日鐵住金株式会社 | Solid reduction furnace |
JP5729277B2 (en) * | 2011-11-30 | 2015-06-03 | 新日鐵住金株式会社 | Solid reduction furnace |
CN102425934B (en) * | 2011-12-20 | 2013-06-26 | 湖南省中晟热能科技有限公司 | Microwave heating high-temperature vertical kiln |
EP2628805A1 (en) * | 2012-02-14 | 2013-08-21 | Siemens VAI Metals Technologies GmbH | Method and device for reducing the raw materials containing iron oxide in a high-pressure reduction unit |
CN102837932B (en) * | 2012-08-03 | 2015-04-15 | 莱芜钢铁集团有限公司 | Continuous flat-pushing type discharge device and discharge method thereof |
CN103205519B (en) * | 2013-04-25 | 2014-12-03 | 石家庄市宏晟环保科技有限公司 | Technology for extracting iron from steel-making and ironmaking fly ash by micro-wave heating |
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CN106011458B (en) * | 2016-06-24 | 2017-11-17 | 长沙有色冶金设计研究院有限公司 | The method and its equipment of high arsenic multi-metal complex material dearsenification |
CN108285261B (en) * | 2018-03-20 | 2024-02-06 | 中国石油大学(北京) | Device for treating oily sludge by microwaves and treatment method thereof |
CN108239688B (en) * | 2018-03-30 | 2023-05-30 | 株洲聚润合微波工业炉有限公司 | Microwave reduction vertical kiln and reduction method thereof |
CN110016532A (en) * | 2018-12-25 | 2019-07-16 | 武汉桂坤科技有限公司 | A kind of carbon and the reduction of natural gas joint and molten point of integrated process for making |
TWI765545B (en) * | 2021-01-27 | 2022-05-21 | 永虹先進材料股份有限公司 | Microwave mixing device |
CN114525373B (en) * | 2022-01-20 | 2023-12-08 | 华北理工大学 | Method for desulfurizing and phosphorus by reducing iron ore powder with microwave hydrogen |
WO2024047553A1 (en) * | 2022-09-01 | 2024-03-07 | Harald Noack | Device and method for the gaseous extraction of reducible constituents from a starting material, and extraction system |
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JP2003183716A (en) * | 2001-12-13 | 2003-07-03 | Nippon Steel Corp | Method for manufacturing reduced iron by using rotary bed furnace |
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- 2007-10-03 BR BRPI0717798-4A2A patent/BRPI0717798A2/en not_active Application Discontinuation
- 2007-10-03 EP EP07839202A patent/EP2089549A4/en not_active Withdrawn
- 2007-10-03 AU AU2007309609A patent/AU2007309609B2/en not_active Ceased
- 2007-10-03 WO PCT/US2007/021254 patent/WO2008051356A2/en active Application Filing
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WO1989004379A1 (en) * | 1987-11-13 | 1989-05-18 | Wollongong Uniadvice Limited | Microwave irradiation of mineral ores and concentrates |
US6277168B1 (en) * | 2000-02-14 | 2001-08-21 | Xiaodi Huang | Method for direct metal making by microwave energy |
US20040060387A1 (en) * | 2000-12-04 | 2004-04-01 | Jeffrey Tanner-Jones | Plasma reduction processing of materials |
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WO2005118480A1 (en) * | 2004-06-01 | 2005-12-15 | Atraverda Limited | Reduced moisture chemical reactions |
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WO2008051356A2 (en) | 2008-05-02 |
WO2008051356A3 (en) | 2009-03-05 |
EP2089549A4 (en) | 2011-03-02 |
BRPI0717798A2 (en) | 2014-06-17 |
AU2007309609A1 (en) | 2008-05-02 |
EP2089549A2 (en) | 2009-08-19 |
CN101548024B (en) | 2013-11-20 |
CN101548024A (en) | 2009-09-30 |
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