AU2004276579A1 - Method and apparatus for producing molten iron - Google Patents
Method and apparatus for producing molten iron Download PDFInfo
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- AU2004276579A1 AU2004276579A1 AU2004276579A AU2004276579A AU2004276579A1 AU 2004276579 A1 AU2004276579 A1 AU 2004276579A1 AU 2004276579 A AU2004276579 A AU 2004276579A AU 2004276579 A AU2004276579 A AU 2004276579A AU 2004276579 A1 AU2004276579 A1 AU 2004276579A1
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- Australia
- Prior art keywords
- melting furnace
- iron
- molten iron
- producing molten
- gas
- Prior art date
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 165
- 229910052742 iron Inorganic materials 0.000 title claims description 81
- 238000000034 method Methods 0.000 title description 29
- 239000007789 gas Substances 0.000 claims description 107
- 238000002844 melting Methods 0.000 claims description 80
- 230000008018 melting Effects 0.000 claims description 80
- 230000009467 reduction Effects 0.000 claims description 46
- 239000000571 coke Substances 0.000 claims description 43
- 239000000446 fuel Substances 0.000 claims description 31
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 28
- 239000001301 oxygen Substances 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 238000002485 combustion reaction Methods 0.000 claims description 22
- 230000036961 partial effect Effects 0.000 claims description 15
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 239000003345 natural gas Substances 0.000 claims description 13
- 239000003245 coal Substances 0.000 claims description 12
- 230000002829 reductive effect Effects 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000013067 intermediate product Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002006 petroleum coke Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000005255 carburizing Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000001465 metallisation Methods 0.000 claims description 2
- 238000010248 power generation Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000001311 chemical methods and process Methods 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 230000008569 process Effects 0.000 description 22
- 239000000203 mixture Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 235000013980 iron oxide Nutrition 0.000 description 5
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 238000009628 steelmaking Methods 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 229910000805 Pig iron Inorganic materials 0.000 description 4
- 230000001174 ascending effect Effects 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000002860 competitive effect Effects 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 naphtha Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010747 number 6 fuel oil Substances 0.000 description 1
- QVGXLLKOCUKJST-BJUDXGSMSA-N oxygen-15 atom Chemical compound [15O] QVGXLLKOCUKJST-BJUDXGSMSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/02—Making spongy iron or liquid steel, by direct processes in shaft furnaces
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0006—Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state
- C21B13/0013—Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state introduction of iron oxide into a bath of molten iron containing a carbon reductant
- C21B13/002—Reduction of iron ores by passing through a heated column of carbon
-
- 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
-
- 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
- C21B2100/20—Increasing the gas reduction potential of recycled exhaust gases
- C21B2100/22—Increasing the gas reduction potential of recycled exhaust gases by reforming
-
- 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
- C21B2100/20—Increasing the gas reduction potential of recycled exhaust gases
- C21B2100/28—Increasing the gas reduction potential of recycled exhaust gases by separation
- C21B2100/282—Increasing the gas reduction potential of recycled exhaust gases by separation of carbon dioxide
-
- 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
- C21B2100/44—Removing particles, e.g. by scrubbing, dedusting
-
- 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
- C21B2100/64—Controlling the physical properties of the gas, e.g. pressure or temperature
-
- 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)
- Vertical, Hearth, Or Arc Furnaces (AREA)
- Manufacture Of Iron (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Furnace Details (AREA)
Description
WO 2005/031009 PCT/IB2004/003483 METHOD AND APPARATUS FOR PRODUCING MOLTEN IRON 5 RELATED APPLICATIONS/PATENTS & INCORPORATION BY REFERENCE A claim of priority is made to United States Provisional Application No. 60/507,160, filed September 30, 2003, and to U.S. utility application (serial number not yet known), filed September 29, 2004. 10 Each of the applications and patents cited in this text, as well as each document or reference cited in each of the applications and patents (including during the prosecution of each issued patent; "application cited documents"), and each of the PCT and foreign applications or patents corresponding to and/or claiming priority from any of these applications and patents, and each of the documents cited or referenced in each of the application cited documents, are hereby 15 expressly incorporated herein by reference. More generally, documents or references are cited in this text, either in a Reference List before the claims, or in the text itself; and, each of these documents or references ("herein-cited references"), as well as each document or reference cited in each of the herein-cited references (including any manufacturer's specifications, instructions, etc.), is hereby expressly incorporated herein by reference. 20 BACKGROUND OF THE INVENTION 1. Field of the invention The present invention relates to the field of producing iron material usable for steel making and other processes. Specifically, the present invention is directed to the combination of 25 direct reduction of iron-oxides in a moving bed reduction reactor, a melting furnace where the reduced iron material is converted into molten iron, and a reduction gas generator furnace.
I
WO 2005/031009 PCT/IB2004/003483 2. Description of the Related Art It has long been recognized that developing a process capable of producing molten iron from iron ores at a competitive cost, as compared to the most efficient blast furnaces, is desirable. Blast furnaces continue to be the preferred method of producing molten iron in the 5 steel industry due to their high productivity. Blast furnaces, however, require costly coke. This has several drawbacks, not the least of which is that coking coal is not found throughout the world. Thus, in many instances it must be imported at great cost to the iron producer. Further, the transformation of coal to coke requires a coking plant. Along with the cost associated with transforming coal into coke, coking plants are not considered environmentally friendly under 10 new pollution regulations in many countries. As a result, many producers are looking for alternative methods of producing iron that will essentially eliminate the need for a separate coking plant, and a process for producing iron that requires much less coke. A variety of techniques have been conceived for the production of molten iron that can be charged and refined in to steel in metallurgical furnaces. Two such examples are oxygen 15 converters and electric arc furnaces. These processes aim to optimize traditional blast-furnace type installation by substituting to some extent lower cost fuels for the traditional and more costly coke. But to date, these processes have failed to provide an operational plant capable of producing molten iron at competitive prices when compared with blast furnaces or with combined direct reduction and electric furnace facilities. 20 Examples of such proposals are U.S. Patent No. 4,001,008 to Stift and U.S. Patent No. 3,236,628 to L. Von Bogdandy. Stift discloses a method and apparatus for reducing iron ores in a shaft furnace, which is integrated to a melting furnace. Iron ores are introduced into the upper portion of the shaft without addition of coke and descend through the shaft in countercurrent to ascending reducing gases produced outside the furnace through partial combustion. 2 WO 2005/031009 PCT/IB2004/003483 Hot reducing gases and powdered carbon are introduced toward a molten iron bath in the melting portion of the furnace, Stift's process however requires additional heat to be provided to the hot gases besides the heat produced by the partial combustion, and the integration of the reduction shaft with the melting furnace does not allow for providing the optimal conditions for 5 the three main processes involved, namely: reduction of ores, melting of reduced ores and production of reducing gases. The Von Bogdandy process is similar in some respects also requiring additional heat for melting the reduced ores by providing electrical energy to the iron bath. U.S. Patents Nos. 4,504,043 and 4,564,389 to Yamaoka et al. describe a process and 10 apparatus for coal gasification and making pig iron. These patents disclose a melting furnace separate from the shaft reduction furnace, where the reducing gases are formed under conditions determined by the combustion of a fuel in the melting furnace. The melting furnace comprises a bed of coke filling most of the volume of the furnace. On top of the bed of coke a layer of reduced iron ore is laid which is melted by the heat of hot gases ascending through said bed of 15 coke. High temperature reducing gases are produced by partial combustion of a fuel, e.g. pulverized coal, heavy oil, natural gas, etc. with oxygen in a plurality of burners which extend through the walls of the melting furnace. The molten iron and slag are discharged from the lower portion of the melting furnace and the hot gases are withdrawn and utilized for reducing iron ores in a reduction shaft associated with the melting furnace, or for other purposes. 20 The process of Yamaoka has not been utilized in the steel industry because it presents several disadvantages. For example, since the oxidation reactions of the fuel take place inside the melting furnace, some of the reactants may react with the bed of coke and consume the coke. Coke consumption causes an increase in operation costs both because of cost and because 3 WO 2005/031009 PCT/IB2004/003483 replenishment of the consumed coke requires special openings or operations in the use of the melting furnace. US Patent No. 5,149,363 to Contrucci et al., discloses a process and a furnace for melting metal and smelting iron ores producing a molten iron material. This process has a shaft above a 5 melting furnace. The utilization of the energy of gases produced by combustion of pulverized coal, liquid or gaseous hydrocarbons with oxygen in the melting furnace is improved by supplying air or oxygen at different locations in the shaft whereby heat is produced by oxidation of such gases which is used for promoting iron reduction of carbon-containing self-reducing pellets. When this process is used for melting metallized material, for example, scrap or pig iron, 10 as in cupola furnaces, the coke consumption is significantly decreased because no coke is added to the burden, which thereby avoids any reaction of coke with the ascending reduction gases. However, this process does not separate the gas generation zone and equipment from the melting furnace. Another known melting-gasifier furnace effects partial combustion of coal in a chamber 15 coaxial to the melting furnace, whereby the gases produced impinge on the molten iron bath and then ascend counter-currently to iron containing particles descending through said furnace. This patent presents a separate chamber for partial combustion but presents a significant disadvantage because said chamber is located inside the melting furnace with considerable cost for special materials and design so that the structure withstands the high-temperature environment within 20 said furnace. Yet another process, which has been in operation for years, separates the reduction shaft furnace from the melting furnace but presents the disadvantage of forming a reaction chamber above the molten iron bath for combusting coal and producing heat and reducing gases which are utilized in the reduction furnace. Although this process is successful in not using coke, it 4 WO 2005/031009 PCT/IB2004/003483 however presents a great disadvantage of producing an excess of reducing gases that must be used for some other purposes, for example, electricity generation or for heating purposes. This process considered alone is not competitive and therefore its use has not spread as originally expected. 5 Accordingly, the present invention is directed to overcoming these and other shortcomings of the prior art. OBJECTS OF THE INVENTION It is therefore an object of the invention to provide an improved system for producing 10 molten iron useful for steel making and other metallurgical processes. It is another object of the invention to provide an improved system for producing molten iron with optimized operational conditions in three physically separated reaction zones or equipment, e.g. a reducing gas generation zone, a moving bed reduction zone and melting zone. It is a further object of the invention to provide an improved system for producing molten 15 iron adapted for its installation in conjunction with existing direct reduction plants, in order to substitute and efficiently utilize fuels having a lower cost that natural gas and therewith produce high quality pig-iron. It is still another object of the invention to provide an improved system for producing molten iron adapted for its installation in electric furnace steel-making facilities, in order to 20 charge molten metal to said electric furnaces and reduce electricity consumption as well as increasing their productivity. Other objects of the invention will be evident to the skilled in the art or will be pointed out in the specification below. 5 WO 2005/031009 PCT/IB2004/003483 SUMMARY OF THE INVENTION The objects of the invention will be generally achieved by providing a system for producing molten iron from iron ores in form of lumps or pellets, comprising three separated reaction zones or furnaces: (1) a direct reduction shaft furnace, (2) a melting furnace, and (3) a 5 reducing gas generation furnace; said system being characterized by: (a) producing a reduced intermediate product with a predetermined degree of metallization and carburization in said reduction furnace by reaction of said ores with a high-temperature reducing and carburizing gas; (b) charging said reduced intermediate product into said melting furnace upon a coke bed, whereby said reduced intermediate product is melted by contact with said high-temperature 10 reducing gas; and (c) producing a reducing gas in a reducing gas generation zone by partial combustion of a hydrocarbon fuel with an oxygen-containing gas and steam; and (d) transferring said reducing gas into said melting furnace preventing any free oxygen from contacting said coke bed in said melting furnace, whereby any combustion of said coke bed is minimized. 15 BRIEF DESCRIPTION OF THE DRAWINGS In this specification and the accompanying drawings, some preferred embodiments of the invention are shown and described, and various alternatives and modifications thereof have been suggested. It is to be understood that these are not intended to be exhaustive and that many other changes and modifications can be made within the scope of the invention. 20 The suggestions herein are selected and included for purposes of illustration in order that others skilled in the art will more fully understand the invention and the principles thereof and will thus be enabled to modify it in a variety of forms, each as may be best suited to the conditions of a particular use. 6 WO 2005/031009 PCT/IB2004/003483 In the following detailed description, reference will be made to the accompanying drawings, wherein: Figure 1 shows a schematic diagram of one embodiment of the present invention for producing the reducing gases and for distributing said gases in the melting furnace. 5 Figure 2 shows a schematic diagram of a second embodiment of the present invention for producing the reducing gases and for distributing said gases in the melting furnace. Figure 3 is a graph showing the preferred ratio of oxygen to natural gas for melting iron according to one embodiment of the present invention. Figure 4 is a schematic diagram of a further embodiment of the present invention for 10 producing the reduction gases and for distributing said gases in the melting furnace where DRI is produced remotely. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION The present invention will now be described with reference to the Figures. Referring to 15 Figure 1, a melting furnace 10 having a crucible section 12 and a charging shaft 14 is shown. A bed of coke 16 fills a major portion of the crucible section 12 providing a porous support for a bed 18 of metallic-iron-containing particles which descend through the shaft section 14 as said iron particles melt down. The high-temperature reducing gas 20 produced in a plurality of gas generating zones 22 passes through the coke bed 16 with a composition comprising in its major 20 part hydrogen and carbon monoxide, however, the mixture may contain some carbon dioxide and water, the classic by-products of combustion, and also some methane or other un-burnt fuel. The actual composition of the reducing gases 20 will depend on the type of fuel utilized and will be adjusted to a desired reducing potential value by reacting a fuel 24 and a free oxygen-containing gas 26. Flow rates of fuel and oxygen-gas are regulated by suitable control valves 33 and 35. 7 WO 2005/031009 PCT/IB2004/003483 Fuel 24 may be any hydrocarbon in solid, liquid or gaseous form. Natural gas may be utilized with advantages except for its unavailability in many places and its wide price fluctuation. Liquid hydrocarbons, such as naphtha, "bunker C" oil, and waste oils can be utilized, as well as coal ground to a suitable particle size so as to be handled as slurry with a 5 liquid hydrocarbon and fed to burners 30. Pure oxygen is preferred as oxidant for partially combusting the fuel, since the presence of nitrogen in the reducing gases will limit the amount of reducing gas, which may be recycled to the reduction reactor, but air and oxygen-enriched air in burners 44 can also be used for melting the reduced materials. 10 The reacting materials in burner 30 produce a high-temperature flame 20, between about 2,000 0 C and about 2,500 0 C. The gas-generating zones 22 are designed so that, preferably, the flame does not directly impinge in its refractory-lined walls. The gas-generating zones 22 are also designed so that the reaction volume allows for total consumption of the free-oxygen containing gas before such gases are introduced into the melting furnace and contact the coke 15 bed 16. To this end, said gas-generating zone has a length of at least about 0.6 m., preferably more than about 0.8 m. However, other lengths of the gas-generating zone will be apparent to those of skill in the art and are contemplated to be within the scope of the instant invention. The exact length is not by itself as important to the process of the present invention as combustion to a point of using all free oxygen and preventing contact of free-oxygen with the coke. 20 The goal of this length of the gas-generating zone 22 is to minimize the consumption of the coke and consequently the amount of coke, which must be replaced in the melting furnace, is minimized. This goal is largely achieved by ensuring that substantially all of the free oxygen is used in combustion prior to the reducing gases contacting the coke. By accomplishing this, there is nearly no oxygen remaining to oxidize or burn the coke. By preventing the coke from 8 WO 2005/031009 PCT/IB2004/003483 burning, a major cost from a potentially consumable material of the iron making process is minimized, thereby reducing the overall cost of the process. Thus through the use of other fuels, such as coal, oil, petcoke and the like, which are much less expensive, the efficiency and cost of iron making is substantially reduced. 5 The reduced-iron-containing material (DRI) 18 is melted and flows down through the coke bed 16 to the bottom portion of melting furnace 10 wherefrom it is extracted through discharge channel 32 into molds (not shown) in a manner known in the art. The melting furnace 10 is preferably operated under pressure, in the order of 1 to 10 kg/cm 2 , preferably from about 4 to 6 kg/cm 2 , so that the effluent gas 34 from outlet 36 may be 10 injected into the reducing gas circuit of reduction reactor 38, without need of any pumping means. The effluent gas is at a temperature of about 400 to 800 0 C. Iron-containing materials: DRI (sponge iron) 39, and other materials, for example, limestone 48, limestone and fluxes 50, coke 52 and DRI or scrap iron 53 are charged into melting furnace 10 through a bins-and-valve system comprising an atmospheric bin 40, a 15 pressurized bin 42 and seal valves 44 and 46. Materials are charged to bin 40 and transferred to bin 42 by opening valve 44 while valve 46 is closed and then closing valve 44, pressurizing bin 42 and opening valve 46, in a manner known in the industry. Coke is charged in the amount necessary to make-up coke bed 16 as some coke is incidentally gasified by the heat of gases 20. Iron briquettes, iron scrap and the like may also be charged to melting furnace 10 for melting. 20 Reduction reactor 38 comprises an upper reduction zone 54 and a lower discharge zone 56. Iron oxides in the form of lumps, pellets or mixtures thereof in suitable sizes, are charged into reduction zone 54 by any suitable means known in the art depending on the level of pressure under which the reactor is operated, for example a bins and valves means or a charging leg filled with an inert sealing gas. Iron oxides pellets descend by gravity through reduction zone 54 in 9 WO 2005/031009 PCT/IB2004/003483 contact with an ascending stream of reducing gases at a temperature between about 900 0 C and about 1100 0 C, whereby iron oxides are converted to metallic iron. After reduction, the DRI or sponge iron is charged into the melting furnace 10 as needed. It will be evident by those skilled in the art that a different type of reduction reactor, other 5 than the moving bed reactor 38, may also be utilized according to the invention, for example a fixed bed or a fluidized bed reactor. After reduction of the iron pellets, exhausted reducing gas 60 is withdrawn from reactor 38 and passes through heat exchanger 62 where water from source 64 is made into steam 65 that can be used in burners 24 or CO 2 removal system 78. The exhausted reducing gas 60 is then 10 cooled down in cooler 66 by, for example, contacting said gas with water. This process condenses any residual water content out of the exhausted reducing gas. A minor portion 68 of the cooled gas, regulated by control valve 70, is purged from the reduction circuit thus eliminating inert gases and simultaneously regulating the pressure of the system. The major portion 72 of the cooled gas is then pumped by compressor means 74 and is 15 fed to a CO 2 removal system 78 in order to remove carbon dioxide. This has the effect of regenerating the reducing potential of the gas. The CO2 removal system 78 may be of the absorption type where the gas is contacted with a liquid or of the adsorption type (pressure or volume swing adsorption). Recycled reducing gas 80, if necessary, is then combined with natural gas 82 from a suitable source 84 and heated in gas heater 90 to a temperature in the range 20 from about 750 0 C to about 950 0 C. Natural gas is also utilized, as required, in the burners of heater 90, combined with a portion 88 of reducing gas produced in melting furnace 10. Hot gas from heater 90 is combined in variable proportions with more natural gas 92 from a suitable source 94, a free-oxygen-containing gas 96 from source 98, which may be molecular oxygen or oxygen-enriched air, and effluent gasses 34 from the melting furnace 10. Free-oxygen injection 10 WO 2005/031009 PCT/IB2004/003483 produces a partial combustion of hydrocarbons in the hot gas 58 increasing its temperature in the range from about 1000 0 C to about I1150 0 C and is then fed to the reduction reactor 38 for producing the DRI or sponge iron 39. Fig. 2 depicts a further embodiment of the present invention, wherein like numbers 5 designate similar or equivalent elements described with reference to Figure 1. The apparatus depicted in Fig. 2 is used to produce molten iron or pig iron from iron ore. The apparatus includes a melting furnace 10, a reduction or shaft furnace 38, and a reduction gas-generating furnace 21. The melting furnace 10 includes a coke bed 16 on which reduced iron 18 or DRI or 10 sponge iron is deposited for melting. Iron is conveyed into the reduction furnace 38 by conventional means, and is therein reduced to form DRI. Heated gases are provided to the reduction chamber 38 to heat the iron ore, in part through the use of a reducing gas generator 21. The reducing gas generator 21 includes one or more burners 31 which burn hydrocarbon fuels including but not limited to coal, oil, petcoke, and the like. The burner 31 is connected to a 15 variety of piping systems 24, 26 that can include oxygen systems, fuel systems, steam systems, and others. Oxygen is used to effect a partial combustion of the hydrocarbons which are supplied by the fuel systems and steam may also be used to both atomize the fuel for combustion and to increase the temperature of the mixture before combustion. The partial burning of a fuel such as petcoke creates a high temperature, high-pressure reduction gas, which is injected into 20 the melting furnace 10 through a passage 23. The gas is typically above about 14000 C and has a reducing composition before it contacts the coke bed 16. These gases are distributed around the periphery of the crucible section 12 by a gas distribution plenum 25 formed in the refractory lining 27 and having nozzles (not shown) around said melting zone 12. In one embodiment, valves 33 and 35 regulate the flow rates of fuel 24 and oxygen-gas 26 respectively, in order to 11 WO 2005/031009 PCT/IB2004/003483 adjust the temperature and composition of the reducing gas produced. Gas generating chamber 21 is provided with a bottom outlet 100 and a shut-off valve 102 for withdrawing ashes, slag and impurities, which may accumulate therein. The hot gases rise through coke bed 16 melting the DRI deposited thereon in counter 5 current flow. The melted iron collects at the bottom of the melting furnace 10 and exits through connection 32 to molds or for use in further processing such as steel making. After passing through the DRI that has been charged into the melting furnace 10, the reduction gas is vented through a connection pipe 36 to the reduction furnace 38. In the reduction furnace the reduction gas is used to transform the iron ore into DRI for use in the 10 melting furnace. The reduction furnace 38 operates substantially the same as the reduction furnace described with relation to the embodiment shown in Fig. 1. Referring to Figure 3, the graph shows the preferred operating range of the ratio of volume of oxygen to volume of natural gas in the gas generating zones 22 or the gas generating furnace 21 so that the temperature of the gases reach such a level as to melt the DRI, and also 15 that the amount of heat produced is sufficient to melt the required amount of DRI and at the same time provide sufficient amounts of reducing gases (H2 + CO) for reducing the iron oxides in furnace 38 to DRI. It is known that the temperature and amount of heat will increase with an increase in the ratio of oxygen to natural gas, but this increase of oxidation will decrease the reducing quality of the reduction gas and therefore the amount of reducing agents available for 20 reduction. Applicants have found that the preferred range of the ratio of oxidant to fuel for operating a melting furnace must comply with the above-mentioned requirements for the process to be economically attractive. Although the concept of preferred range of oxygen to fuel ratio has been herein illustrated for natural gas it can be applied to other fuels. For natural gas the preferred range is from about 0.86 to about 1.04. 12 WO 2005/031009 PCT/IB2004/003483 Figure 4 depicts an embodiment of the present invention where the reduced-iron containing material is produced at a location remote from the molten-iron producing plant and charged into the melting furnace via DRI bin 39. This embodiment may be useful in an instance where a steel making plant buys DRI from DRI-merchant plants. As shown in Figure 4, the hot 5 reducing gases produced in the melting furnace 10 may then be utilized as fuel, synthesis gas or power generation after having been used in the melting furnace 10 and vented by connection pipe 36. Such an embodiment may also be useful in increasing the productivity of electric arc furnaces where molten iron is charged into an electric furnace thereby reducing melting time and electricity consumption. 10 In the schematic diagram Figure 4, of the present invention there is shown an application where the reducing gas effluent 34 from said melting furnace is recycled therein. Numerals in Figure 4 designate the same elements as in Figure 1. Reducing gases 34 effluent from melting furnace 10 are cooled and cleaned in heat exchanger 62 and cooler 66 and are then recycled through compressor means 74, passed through a CO 2 removal system 78 and then heated to a 15 temperature above about 800 0 C and then recycled to said melting furnace 10 in order to utilize them as much as possible for melting DRI. This gas recycle increases the efficiency of a melting furnace. It has thus been shown that the objects set forth above, among those made apparent from the preceding description, are efficiently attained and, because certain changes may be made in 20 carrying out the above method and in the construction(s) set forth without departing from the spirit and scope of the invention, it is intended that all matter contained in the above description and shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense. 13
Claims (17)
1. A system for producing molten iron from iron ores, comprising: (1) a direct reduction shaft furnace; (2) a melting zone in a melting furnace having a coke bed in its lower portion and a charging and preheating chamber in its upper portion; and (3) at least one reducing gas generation zone communicating with said melting zone, wherein said system: (a) produces a reduced intermediate product with a predetermined degree of metallization and carburization in said reduction furnace by reaction of said ores with a high-temperature reducing and carburizing gas; (b) charges said reduced intermediate product into said melting furnace upon said coke bed, whereby said reduced intermediate product is melted by contact with said high-temperature reducing gas; (c) produces a reducing gas in said reducing gas generation zone by partial combustion of a hydrocarbon fuel with an oxygen-containing gas; and (d) transfers said reducing gas into said melting furnace preventing any free oxygen from contacting said coke bed in said melting furnace.
2. The system for producing molten iron from iron ores according to claim 1, wherein said reducing gas is produced in a partial combustion chamber so that the hydrocarbon fuel, and oxygen-containing gas react an combust to substantially eliminate the presence of any free oxygen before contacting said coke bed. 14 WO 2005/031009 PCT/IB2004/003483
3. The system for producing molten iron from iron ores according to claim 2, wherein said hydrocarbon fuel is natural gas.
4. The system for producing molten iron from iron ores according to claim 3, wherein the ratio of the volumetric flow rate of the oxygen-containing gas to the flow rate of said natural gas is in the range from about 0.86 to about 1.04.
5. The system for producing molten iron from iron ores according to claim 2, wherein said hydrocarbon fuel is liquid.
6. A system for producing molten iron from iron ores according to claim 2, wherein said hydrocarbon fuel is pet-coke.
7. A system for producing molten iron from iron ores according to claim 2, wherein said hydrocarbon fuel is coal.
8. The system for producing molten iron from iron ores according to claim 1, wherein said system: (e) withdraws reacted reducing gas from said reduction furnace; (f) regenerates the reducing potential of said withdrawn reducing gas by cooling and removing at least a portion of its water content; (g) heats a portion of said regenerated withdrawn reducing gas to a temperature above 800 0 C; and (h) feeds said heated regenerated withdrawn reducing gas to the reduction furnace.
9. The system for producing molten iron from iron ores according to claim 1, wherein said reducing gas is produced in a single partial combustion chamber and fed to said melting furnace through a plurality of inlet ports formed and located in the refractory lining of said melting furnace. 15 WO 2005/031009 PCT/IB2004/003483
10. The system for producing molten iron from iron ores according to claim 1, wherein said reducing gas being is produced in a plurality of partial combustion chambers connecting to said melting furnace through a plurality of inlet ports formed through the wall of said melting furnace.
11. The system for producing molten iron from ores according to claim 1, wherein said inlet ports are located in said melting furnace so that the high-temperature reducing gas is fed to contact said coke and ascend through a portion of said coke bed and through said preheating chamber of said melting furnace.
12. The system for producing molten iron according to claim 10, wherein said iron containing material is DRI produced in a location remote from said melting furnace.
13. The system for producing molten iron according to claim 11, wherein said reducing gas effluent from said melting furnace is further used as fuel, power generation or synthesis gas in other chemical processes.
14. The system for producing molten iron according to claims 8, wherein the length of said partial combustion chamber is at least about 0.6 m.
15. The system for producing molten iron according to claims 8, wherein the length of said partial combustion chamber is at least about 0.8 m.
16. The system for producing molten iron according to claim 1, wherein said melting furnace is located at a remote distance from said direct reduction shaft furnace, wherein said system: (a) withdraws effluent gases from said melting furnace; (b) cools and cleans said effluent gases; (c) separates CO 2 from said cooled effluent gases; (d) heats said cooled effluent gases to a temperature above about 600 0 C; and 16 WO 2005/031009 PCT/IB2004/003483 (e) recycles said heated reducing gases to said melting furnace.
17. The system for producing molten iron according to claim 15, wherein a portion of said cooled and cleaned effluent gases from said melting furnace are utilized as fuel for heating said recycled gases. 17
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US50716003P | 2003-09-30 | 2003-09-30 | |
| US60/507,160 | 2003-09-30 | ||
| US10/953,735 US20050151307A1 (en) | 2003-09-30 | 2004-09-29 | Method and apparatus for producing molten iron |
| US10/953,735 | 2004-09-29 | ||
| PCT/IB2004/003483 WO2005031009A2 (en) | 2003-09-30 | 2004-09-30 | Method and apparatus for producing molten iron |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU2004276579A1 true AU2004276579A1 (en) | 2005-04-07 |
Family
ID=34396341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2004276579A Abandoned AU2004276579A1 (en) | 2003-09-30 | 2004-09-30 | Method and apparatus for producing molten iron |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20050151307A1 (en) |
| EP (1) | EP1670958A2 (en) |
| AU (1) | AU2004276579A1 (en) |
| BR (1) | BRPI0414951A (en) |
| RU (1) | RU2006114771A (en) |
| WO (1) | WO2005031009A2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995402B (en) * | 2006-01-06 | 2011-11-16 | 伊尔技术有限公司 | Method for directly reducing iron oxide to metallic iron by using coke oven gas and the like |
| RU2533991C2 (en) * | 2009-06-10 | 2014-11-27 | Кеки Хормусджи ГХАРДА | Method for obtaining cast-iron, semi-finished steel products and reducing gas, and unit for its implementation |
| US9797023B2 (en) * | 2013-12-20 | 2017-10-24 | Grede Llc | Shaft furnace and method of operating same |
| EP2905345A1 (en) * | 2014-02-10 | 2015-08-12 | Primetals Technologies Austria GmbH | Pneumatic ore charging |
| EP3269830A4 (en) * | 2015-03-13 | 2018-08-08 | Tleugabulov, Suleiman | Method for the reduction smelting of steel and apparatus for carrying out said method |
| US12000011B2 (en) | 2021-06-22 | 2024-06-04 | Midrex Technologies, Inc. | System and method for the production of hot briquetted iron (HBI) containing flux and/or carbonaceous material at a direct reduction plant |
| AU2024218189A1 (en) * | 2023-02-08 | 2025-08-28 | Hatch Ltd. | System and method for feeding an electric furnace |
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| US2889219A (en) * | 1956-12-28 | 1959-06-02 | Inland Steel Co | Control method and apparatus for iron ore reduction process |
| US2928730A (en) * | 1957-01-15 | 1960-03-15 | Inland Steel Co | Iron ore reduction process |
| US2919983A (en) * | 1958-05-22 | 1960-01-05 | Inland Steel Co | Iron ore reduction process |
| GB988579A (en) * | 1960-09-14 | 1965-04-07 | Huettenwerk Oberhausen Ag | Improvements in and relating to the production of liquid pig iron from ore |
| US3282677A (en) * | 1963-04-30 | 1966-11-01 | Futakuchi | Method of manufacturing iron by low temperature reduction with use of methane gas |
| IT1038230B (en) * | 1974-05-22 | 1979-11-20 | Krupp Gmbh | PROCEDURE FOR THE PRODUCTION OF STEEL |
| US4001008A (en) * | 1974-08-06 | 1977-01-04 | Vereinigte Osterreichische Eisen- Und Stahlwerke-Alpine Montan Aktiengesellschaft | Method and apparatus for the reduction of ores, especially iron ores |
| US4316739A (en) * | 1979-07-16 | 1982-02-23 | Midrex Corporation | Method for producing molten iron |
| US4248626A (en) * | 1979-07-16 | 1981-02-03 | Midrex Corporation | Method for producing molten iron from iron oxide with coal and oxygen |
| US4246024A (en) * | 1979-10-31 | 1981-01-20 | Grupo Industrial Alfa, S.A. | Method for the gaseous reduction of metal ores using reducing gas produced by gasification of solid or liquid fossil fuels |
| SE457265B (en) * | 1981-06-10 | 1988-12-12 | Sumitomo Metal Ind | PROCEDURE AND ESTABLISHMENT FOR PREPARATION OF THANKS |
| DE3437913C2 (en) * | 1984-10-12 | 1987-05-07 | Korf Engineering GmbH, 4000 Düsseldorf | Process and apparatus for producing sponge iron and/or liquid pig iron |
| US4571259A (en) * | 1985-01-18 | 1986-02-18 | Westinghouse Electric Corp. | Apparatus and process for reduction of metal oxides |
| DE3503493A1 (en) * | 1985-01-31 | 1986-08-14 | Korf Engineering GmbH, 4000 Düsseldorf | METHOD FOR THE PRODUCTION OF RAW IRON |
| US4664389A (en) * | 1985-10-08 | 1987-05-12 | Barclay Precision Toys Inc. | Toy car and method of utilzing same |
| BR8605001A (en) * | 1986-10-13 | 1988-05-31 | Setepla Tecnometal Engenharia | EQUIPMENT FOR THE PRODUCTION OF FERROUS METALS OR NOT FROM SELF-REDUCING AND SELF-REDUCING ORES OR AGLOMERATES OR NOT FROM |
| DE3644775A1 (en) * | 1986-12-23 | 1988-07-14 | Korf Engineering Gmbh | METHOD FOR THE PRODUCTION OF RAW IRON |
| EP0304413B1 (en) * | 1987-08-21 | 1993-03-10 | VOEST-ALPINE STAHL Donawitz GmbH (HRB Nr. 502) | Method for melting scrap, sponge iron and/or solid pig iron or the like |
| AT390622B (en) * | 1988-10-25 | 1990-06-11 | Voest Alpine Ind Anlagen | METHOD AND INSTALLATION FOR THE PRODUCTION OF LIQUID PIG IRON |
| DE4037977A1 (en) * | 1990-11-29 | 1992-06-11 | Voest Alpine Ind Anlagen | METHOD FOR THE PRODUCTION OF RAW IRON OR IRON SPONGE |
| US5338336A (en) * | 1993-06-30 | 1994-08-16 | Bechtel Group, Inc. | Method of processing electric arc furnace dust and providing fuel for an iron making process |
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| AT404735B (en) * | 1992-10-22 | 1999-02-25 | Voest Alpine Ind Anlagen | METHOD AND INSTALLATION FOR THE PRODUCTION OF LIQUID PIPE IRON OR LIQUID STEEL PRE-PRODUCTS |
| DE4240197C2 (en) * | 1992-11-30 | 1996-04-18 | Vuletic Bogdan Dipl Ing | Process for the production of pig iron from iron ore and device for the thermal and / or chemical treatment of a readily disintegrating material or for the production of pig iron by means of this process |
| US5413622A (en) * | 1993-12-16 | 1995-05-09 | Bechtel Group, Inc. | Method of making hot metals with totally recycled gas |
| TW303389B (en) * | 1994-10-17 | 1997-04-21 | V0Est Alpine Industrieanlagenbau Gmbh | |
| AT405187B (en) * | 1994-12-01 | 1999-06-25 | Voest Alpine Ind Anlagen | METHOD FOR THE PRODUCTION OF IRON SPONGE AND SYSTEM FOR IMPLEMENTING THE METHOD |
| AT406482B (en) * | 1995-07-19 | 2000-05-25 | Voest Alpine Ind Anlagen | METHOD FOR THE PRODUCTION OF LIQUID PIPE IRON OR STEEL PRE-PRODUCTS AND SYSTEM FOR IMPLEMENTING THE METHOD |
| AT406483B (en) * | 1995-07-19 | 2000-05-25 | Voest Alpine Ind Anlagen | METHOD FOR THE PRODUCTION OF LIQUID PIPE IRON OR STEEL PRE-PRODUCTS AND SYSTEM FOR IMPLEMENTING THE METHOD |
| AUPN639995A0 (en) * | 1995-11-03 | 1995-11-30 | Technological Resources Pty Limited | A method and an apparatus for producing metals and metal alloys |
| DE69720606T2 (en) * | 1996-01-26 | 2004-03-04 | Nippon Steel Corp. | METHOD FOR OPERATING A SHAFT |
| AT403929B (en) * | 1996-07-10 | 1998-06-25 | Voest Alpine Ind Anlagen | METHOD FOR GENERATING A REDUCING GAS FOR THE REDUCTION OF METAL ORE, AND SYSTEM FOR IMPLEMENTING THE METHOD |
| AUPO276496A0 (en) * | 1996-10-07 | 1996-10-31 | Technological Resources Pty Limited | A method and an apparatus for producing metals and metal alloys |
| AT404138B (en) * | 1996-10-08 | 1998-08-25 | Voest Alpine Ind Anlagen | METHOD FOR PRODUCING LIQUID PIPE IRON OR STEEL PRE-PRODUCTS AND SYSTEM FOR IMPLEMENTING THE METHOD |
| AT404362B (en) * | 1996-12-17 | 1998-11-25 | Voest Alpine Ind Anlagen | METHOD AND MELTING CARBURETOR FOR PRODUCING LIQUID METAL |
-
2004
- 2004-09-29 US US10/953,735 patent/US20050151307A1/en not_active Abandoned
- 2004-09-30 WO PCT/IB2004/003483 patent/WO2005031009A2/en not_active Ceased
- 2004-09-30 EP EP04769713A patent/EP1670958A2/en not_active Withdrawn
- 2004-09-30 AU AU2004276579A patent/AU2004276579A1/en not_active Abandoned
- 2004-09-30 RU RU2006114771/02A patent/RU2006114771A/en unknown
- 2004-09-30 BR BRPI0414951-3A patent/BRPI0414951A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005031009A2 (en) | 2005-04-07 |
| BRPI0414951A (en) | 2006-11-07 |
| RU2006114771A (en) | 2007-11-10 |
| EP1670958A2 (en) | 2006-06-21 |
| US20050151307A1 (en) | 2005-07-14 |
| WO2005031009A3 (en) | 2006-04-13 |
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