EP2690181A1 - Verfahren und System zur Herstellung von Eisenklumpen - Google Patents

Verfahren und System zur Herstellung von Eisenklumpen Download PDF

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Publication number
EP2690181A1
EP2690181A1 EP13005096.6A EP13005096A EP2690181A1 EP 2690181 A1 EP2690181 A1 EP 2690181A1 EP 13005096 A EP13005096 A EP 13005096A EP 2690181 A1 EP2690181 A1 EP 2690181A1
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EP
European Patent Office
Prior art keywords
metallic iron
nuggets
slag
iron nuggets
reducible mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13005096.6A
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English (en)
French (fr)
Inventor
Iwao Iwasaki
Andrew J. Lindgren
Richard F. Kiesel
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Nu-Iron Technology Inc
Nu Iron Technology LLC
Original Assignee
Nu-Iron Technology Inc
Nu Iron Technology LLC
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Filing date
Publication date
Application filed by Nu-Iron Technology Inc, Nu Iron Technology LLC filed Critical Nu-Iron Technology Inc
Publication of EP2690181A1 publication Critical patent/EP2690181A1/de
Withdrawn legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/008—Use of special additives or fluxing agents
    • 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

Definitions

  • the present invention was made with support by the Economic Development Administration, Grant No. 06-69-04501, and the Department of Energy, Sponsor Award DE-FG36-05GO15185.
  • the United States government may have certain rights in the invention.
  • the present invention relates to the reduction iron bearing material, such as iron ore, to metallic iron.
  • the conventional reduction processes for production of direct reduced iron involve heating beneficiated iron ores to below the melting point of iron, below 1200 °C (2372 °F), either by gas-based processes or coal-based processes.
  • direct reduction of iron oxide e.g., iron ores or iron oxide pellets
  • a reducing gas e.g., reformed natural gas
  • Methods of making DRI have employed the use of materials that include carbon such as coal and coke as a reducing agent.
  • a typical composition of DRI is 90 to 95% metallization and 2-4% gangue, but has shortcomings for steelmaking processes as a replacement of scrap because its oxygen and gangue content increases energy usage, increase slag volume, and necessitates the addition of costly reagents.
  • Natural gas-based direct reduced iron accounts for over 90% of the world's production of DRI. Coal-based processes are generally used in producing the remaining DRI production. However, in many geographical regions, the use of coal may be more desirable because coal prices may be more stable than natural gas prices. Further, many geographical regions are far away from steel mills that use the processed product. Therefore, shipment of iron units in the form of iron nuggets produced by a coal-based direct reduction process may be more desirable than use of a smelting reduction process.
  • fusion reduction Another reduction process in gas-based or coal-based directly reducing iron bearing material to metallic nuggets is often referred to as fusion reduction.
  • fusion reduction processes generally involve the following processing steps: feed preparation, drying, preheating, reduction, fusion/melting, cooling, product discharge, and metallic iron/slag product separation. These processes result in direct reduction of iron bearing material to metallic iron nuggets and slag.
  • Metallic iron nuggets produced by these direct reduction processes are characterized by high grade reduction, nearing 100% metal (e.g., about 96% to about 97% metallic Fe). 1
  • these metallic iron nuggets have low oxygen content because they are metallic iron and have little or no porosity. These metallic iron nuggets are also low in gangue because silicon dioxide has been removed as slag. Such metallic iron nuggets are desirable in many circumstances such as use in place of scrap in electric arc furnaces. These metallic iron nuggets can be also produced from beneficiated taconite iron ore, which may contain 30% oxygen and 5% gangue. As a result, with such metallic iron nuggets, there is less weight to transport than with beneficiated taconite pellets and DRI, as well as a lower rate of oxidation and a lower porosity than DRI. In addition, generally, such metallic iron nuggets are just as easy to handle as taconite pellets and DRI.
  • a rotary hearth furnace has been used as a furnace for coal-based direct reduction.
  • the rotary hearth furnace has an annular hearth partitioned into a preheating zone, a reduction zone, a fusion zone, and a cooling zone, between the supply location and the discharge location of the furnace.
  • the annular hearth is supported in the 1 Percents (%) herein are percents by weight unless otherwise stated. furnace to move rotationally.
  • raw reducible material comprising a mixture of iron ore and reducing material is charged onto the annular hearth and provided to the preheat zone.
  • the iron ore mixture on the hearth is moved to the reduction zone where the iron ore is reduced in the presence of the reducing material and fused into metallic iron nuggets, using one or more heat sources (e.g., gas burners).
  • the reduced and fused product after completion of the reduction process, is cooled in the cooling zone on the rotating hearth, preventing oxidation and facilitating discharge from the furnace.
  • One exemplary metallic iron nugget direct reduction process for producing metallic iron nuggets is referred to as ITmk3 ® by Kobe Steel.
  • ITmk3 ® One exemplary metallic iron nugget direct reduction process for producing metallic iron nuggets.
  • ITmk3 ® One exemplary metallic iron nugget direct reduction process for producing metallic iron nuggets.
  • dried balls formed using iron ore, coal, and a binder are fed to a rotary hearth furnace.
  • the iron ore concentrate is reduced and fuses when the temperature reaches between 1450 °C to 1500 °C.
  • the resulting products are cooled and then discharged.
  • the intermediate products generally are shell-shaped, pellet-sized metallic iron nuggets with slag inside, from which the metallic iron can be separated.
  • Both of these direct reduction processes for producing metallic iron nuggets have involved mixing of iron-bearing materials and a carbonaceous reductant (e.g., pulverized coal).
  • a carbonaceous reductant e.g., pulverized coal.
  • iron ore/carbon mixture is fed to a hearth furnace (e.g., a rotary hearth furnace) and heated to a reported temperature of 1450 °C to approximately 1500 °C, to form metallic iron nuggets and slag.
  • Metallic iron and slag can then be separated, for example, with use of mild mechanical action and magnetic separation techniques.
  • a particular problem with the metallic iron nuggets formed by these previous direct reduction processes was the sulfur content of the nuggets.
  • Sulfur is a major impurity in direct reduced metallic iron nuggets.
  • carbonaceous reductants utilized in direct reduction processes of iron ore have generally resulted in metallic iron nuggets with at least 0.1% or more by weight sulfur. This high level of sulfur has made the metallic iron nuggets made by direct reduction undesirable in many steelmaking processes, and particularly in the electric arc furnace processes.
  • the present invention provides the following items 1 to 107:
  • a method and system are disclosed that provide for various advantages in the reduction processes in the production of metallic iron nuggets.
  • the method and system results in a marked higher percent of the sulfur in the slag without the use of large amounts of Mg compounds, and a marked lower percent of the sulfur in the metallic iron nuggets.
  • a novel intermediate metallic nugget/slag product having a ratio of percent weight sulfur in the slag to sulfur in the metallic nugget of at least 12, at least 15 or at least 30, without large amounts of MgO within the slag, which may result in nuggets with less than 0.05% sulfur content.
  • a novel metallic nugget having a sulfur content less than 0.03% by weight may also be produced by the disclosed process.
  • a method for use in production of metallic iron nuggets comprises providing a hearth refractory material, providing a hearth material layer comprising at least carbonaceous material on the refractory material, providing a layer of reducible mixture comprised of at least reducing material and reducible iron bearing material arranged in a plurality of discrete portions over at least a portion of the hearth material layer, providing a layer of coarse carbonaceous material over at least a portion of the discrete portions of reducible mixture, and heating the reducible mixture to form one or more discrete portions into an intermediate product of metallic iron nuggets and slag, and after separation, metallic iron nuggets.
  • the step of heating the reducible mixture may form singular metallic iron nuggets with separate slag portions from a majority of the discrete portions.
  • the overlayer is generally provided prior to heating, but may be provided after devolatilization of carbonaceous material occurs and before completion of solid state reduction.
  • the coarse carbonaceous material of the overlayer has an average particle size greater than an average particle size of the hearth layer.
  • the overlayer of coarse carbonaceous material may include discrete particles having a size greater than about 20 mesh or greater than about 6 mesh, and in some embodiments, the overlayer of coarse carbonaceous material may have discrete particles with a size between about 20 mesh or about 6 mesh and about 1 ⁇ 2 inch (12.7mm).
  • the coarse carbonaceous material may be coke, non-caking coal, char, or a combination of one or more of these.
  • the overlayer of coarse carbonaceous material may have discrete particles with a size between about 3/8 inch (9.7 mm) and about 1 ⁇ 2 inch (12.7 mm) or between about 3 mesh (6.7 mm) and about 3/8 inch (9.7 mm).
  • the discrete particles of the hearth layer may have a particle size less than 4 mesh, and in some embodiments a particle size between 100 and 20 mesh or 6 mesh. Particle sizes less than 100 mesh should be avoided because these particles sizes tend to have more ash content.
  • the thickness and particle size of the carbonaceous and other material in the hearth layer should be selected so that the hearth layer protects the hearth refractory from slag and molten metal formed during reduction of the reducible mixture, while avoiding production of excess ash.
  • the hearth layer may have a particle size between a range of -6 to -20 mesh to a range of +65 to +150 mesh.
  • the carbonaceous material in the reducible mixture is also different in particle size from those of the coarse overlayer, but for the different considerations.
  • a consideration is the surface area for rapid reaction of the carbonaceous material with the reducible iron bearing material in commercial production.
  • Less than 65 mesh or less than 100 mesh particle size of carbonaceous material in the reducible mixture is effective for efficient reduction of the iron oxide to produce metallic iron nuggets.
  • the overlayer of coarse carbonaceous material may provide between 50% and 100% coverage of the discrete portions of reducible mixture and may be about 1 ⁇ 2 inch (12.7mm) in thickness. Further, in some embodiments of the method, the coverage of the overlayer of coarse carbonaceous material may be between about 0.5 lb/ft 2 (2.44 kg/m 2 ) and about 1 lb/ft 2 (4.88 kg/m 2 ) of coarse carbonaceous material, or between about 0.75 lb/ft 2 (3.66 kg/m 2 ) and about 1 lb/ft 2 (4.88 kg/m 2 ) of coarse carbonaceous material over the reducible mixture.
  • the step of providing a reducible mixture over at least a portion of the hearth material layer may comprise forming at least a portion of the reducible mixture with a predetermined quantity of reducing material between about 70 percent and about 90 percent of said stoichiometric amount of reducing material necessary for complete metallization.
  • Said stoichiometric amount may be between about 75 percent and about 85 percent of said stoichiometric amount of reducing material for complete metallization, or about 80 percent of said stoichiometric amount of reducing material for complete metallization.
  • the stoichiometric amount of reducing material is the calculated amount of carbonaceous material needed for complete metallization of iron in the formation of metallic iron nuggets from a predetermined quantity of reducible iron bearing material.
  • the discrete portions may be formed in situ as mounds, or alternatively, preformed as briquettes, balls, extrudates, or other shapes as needed.
  • the discrete portions of reducible mixture may be at least partially surrounded with nugget separation fill material comprising at least carbonaceous material.
  • the fill material may be placed by depositing the carbonaceous material after the discrete portions are formed, or by dropping or pushing preformed discrete portions into the hearth layer.
  • the nugget separation fill material may also have an average particle size less than the average particle size of the coarse carbonaceous material of the overlayer.
  • the step of providing an overlayer of coarse carbonaceous material may comprise at least partially surrounding the discrete portions of reducible mixture with coarse carbonaceous material. In some embodiments, this may be accomplished by placing the coarse carbonaceous material over the discrete portions of reducible mixture and allowing some of the coarse carbonaceous material to go between the discrete portions of reducible mixture.
  • the step of heating the layer of reducible mixture includes heating the layer of reducible mixture at a temperature of less than about 1425 °C. Also, the step of thermally heating the layer of reducible mixture may include heating the layer of reducible mixture at a temperature of less than about 1400 °C or less than 1375 °C.
  • Also disclosed is a method for use in production of metallic iron nuggets that comprises providing a hearth refractory material, providing a hearth material layer comprising at least carbonaceous material on the refractory material, providing a layer of reducible mixture comprised of at least reducing material and reducible iron bearing material arranged in a plurality of discrete portions over at least a portion of the hearth material layer, providing a layer of turbulent gas flow disrupting material over at least a portion of the discrete portions of reducible mixture, and heating the reducible mixture to form one or more discrete portions into an intermediate product of metallic iron nuggets and slag, and after separation, metallic iron nuggets.
  • the step of providing an overlayer of turbulent gas flow disrupting material may include providing coarse carbonaceous material.
  • the overlayer of turbulent gas flow disrupting material may include providing between about 0.5 lb/ft 2 (2.44 kg/m 2 ) and about 1 lb/ft 2 (4.88 kg/m 2) of coarse carbonaceous material, or between about 0.75 lb/ft 2 (3.66 kg/m 2 ) and about 1 lb/ft 2 (4.88 kg/m 2) of coarse carbonaceous material.
  • an intermediate product comprising metallic iron nuggets and slag having less than 5 % MgO and having a ratio of percent by weight sulfur in the slag to sulfur in the metallic nuggets of at least 12, at least 15, or at least 30, which may produce nuggets of less than 0.05% sulfur.
  • a metallic iron nugget composition having a sulfur content less than 0.03% by weight is disclosed.
  • the metallic nugget/slag product and metallic iron nuggets may be produced by the method steps that comprise providing a hearth refractory material, providing a hearth material layer comprised of at least carbonaceous material on the refractory material, providing a layer of reducible mixture comprising at least reducing material and reducible iron bearing material arranged in a plurality of discrete portions over at least a portion of the hearth material layer, optionally at least partially surrounding the discrete portions of reducible mixture with nugget separation fill material comprising at least carbonaceous material, providing a layer of coarse carbonaceous material over at least a portion of the discrete portions of reducible mixture, and heating the reducible mixture to form the one or more discrete portions into the intermediate product of metallic iron nuggets and slag of said sulfur slag/nugget ratio, and after separation, metallic iron nuggets.
  • the slag formed may have an iron content of less than about 1%, less than about 0.25%, or essentially less than 0.1%.
  • the carbonaceous material of the hearth layer, the coarse overlayer, and the layer of reducible mixture may contain an amount of sulfur in a range from about 0.2% to about 1.5%, and more typically, in the range of 0.5% to 0.8%.
  • the reducible mixture may also contain an amount of additives in a range from about 1% to about 10%.
  • the reducible mixture may further include an additive selected from the group consisting of SiO 2 , CaF 2 , Na 2 CO 3 , aluminum smelter slag, cryolite, fluorspar and soda ash.
  • the additives may be separately added to the reducible mixture in its making, or may be naturally part of the reducible iron bearing material and/or the carbonaceous material used in making the reducible mixture.
  • 2% of the content of the reducible mixture may be additives, but may range between about 1% and about 7% by weight.
  • Compounds containing Mg, such as dolomite, should be avoided, and in any event compounds containing Mg are not added in quantities such that greater than 3%, or greater than 4%, or greater than 5% MgO results in the slag.
  • FIG. 1 shows a block diagram of one or more general embodiments of a metallic iron nugget process
  • FIG. 2 is a generalized block diagram of a furnace system for implementing a metallic iron nugget process such as that shown generally in FIG. 1 ;
  • FIG. 3 is a diagram of a linear hearth furnace that may be used to carry out one or more processes described herein, and produce one or more products described herein;
  • FIG. 4 shows a pallet or tray with an arrangement of different feed mixtures therein for use in describing one or more tests employing a linear hearth furnace such as that shown in FIG. 3 ;
  • FIG. 5 shows a table giving chemical compositions of one or more additives that may be used in one or more embodiments of the metallic iron nugget process described generally in FIG. 1 , and/or for use in other processes that form metallic iron nuggets;
  • FIGS. 6A and 6B are generally top views showing stages of one embodiment of a metallic iron nugget process as shown generally in FIG. 1 ;
  • FIG. 6C is a generalized cross-section view of a hearth and the layers thereon;
  • FIGS. 7A-7D show illustrations of the effect of time on metallic nugget formation in a metallic iron nugget process as shown generally in FIG. 1 ;
  • FIG. 8 shows a block diagram of one exemplary embodiment of a reducible mixture provision method for use in a metallic iron nugget process as shown generally in FIG. 1 , and/or for use in other processes that form metallic iron nuggets.
  • FIG. 9 shows a CaO-SiO 2 -Al 2 O 3 phase diagram
  • FIGS. 10-12 show tables for use in describing the effect of adding calcium fluoride or fluorspar to a reducible mixture in a metallic iron nugget process such as that shown generally in FIG. 1 , and/or for use in other processes that form metallic iron nuggets;
  • FIGS. 13 , 14 and 15 show a table, an illustration, and another table, respectively, for use in showing the effect of Na 2 CO 3 and CaF 2 additives to a reducible mixture with respect to control of sulfur levels in one or more exemplary embodiments of a metallic iron nugget process such as that shown generally in FIG. 1 , and/or for use in other processes that form metallic iron nuggets;
  • FIG. 16 is a graph showing concentrations of CO in various zones of a linear hearth furnace such as that shown in FIG. 3 for use in describing one or more tests employing such a furnace;
  • FIG. 17 is a table showing the effect of slag composition on a reduction process for use in describing one or more tests employing a linear hearth furnace shown in FIG. 3 ;
  • FIGS. 18A and 18B show a pallet with an arrangement of different feed mixtures therein for use in describing one or more tests employing a linear hearth furnace such as that shown in FIG. 3 , and the resulting product from a typical test;
  • FIG. 19 is a table showing analytical results of iron nuggets and slag for use in describing one or more tests employing a linear hearth furnace shown in FIG. 3 ;
  • FIGS. 20 and 21 show the effect of use of various coal addition levels on one or more exemplary embodiments of a metallic iron nugget process as shown generally in FIG. 1 , and/or for use in other processes that form metallic iron nuggets;
  • FIG. 22 is a table showing analytical results of iron nuggets and slag for use in describing one or more tests employing a linear hearth furnace as shown in FIG. 3 ;
  • FIGS. 23 and 24 show a pallet with an arrangement of different feed mixtures covered with different amounts of a coarse coke overlayer therein for use in describing one or more tests employing a linear hearth furnace as shown in FIG. 3 , and the resulting product from a typical test;
  • FIGS. 25 and 26 show the separation of products produced from the different areas shown in FIG. 24 ;
  • FIG. 27 table showing analytical results of weight distribution of iron nuggets, micro-nuggets, +20 mesh magnetic fraction and slag as shown in FIG. 24 for use in describing one or more tests employing a linear hearth furnace as shown in FIG. 3 ;
  • FIG. 28 shows the separation of products from the different areas shown in FIG. 27 ;
  • FIG. 29 table showing analytical results of weight distribution of iron nuggets, micro-nuggets, +20 mesh magnetic fraction and slag for use in describing one or more tests employing a linear hearth furnace shown in FIG. 3 ;
  • FIG. 30 is a table showing analytical results of iron nuggets and slag for use in describing one or more tests employing a linear hearth furnace shown in FIG. 3 ;
  • FIGS. 31-33 show a tray with an arrangement of briquettes containing different levels of feed mixtures with the use of different levels of coarse coke overlayer therein for use in describing one or more tests employing a linear hearth furnace as shown in FIG. 3 , and the resulting product from a typical test;
  • FIGS. 34-36 show a tray with an arrangement different levels of feed mixtures with the use of different levels of coarse coke overlayer therein for use in describing one or more tests employing a linear hearth furnace as shown in FIG. 3 , and the resulting products from a typical test;
  • FIG. 37 shows the separation of products from different areas from that shown in FIG. 36 ;
  • FIG. 38 shows the resulting product after heating a pallet with an arrangement of feed mixtures with the use of different levels of coarse coke overlayer therein for use in describing one or more tests employing a linear hearth furnace as shown in FIG. 3 ;
  • FIG. 39 shows the separation of products from different areas shown in FIG. 44;
  • FIG. 40 shows the resulting product after heating a tray with an arrangement different levels of feed mixtures with the use of different levels of coarse coke overlayer therein for use in describing one or more tests employing a linear hearth furnace as shown in FIG. 3 ;
  • FIG. 41 shows the separation of products from different areas shown in FIG. 40 ;
  • FIG. 42 shows a plot of the ratio of percent sulfur in the slag over percent sulfur in the metallic iron nuggets for tests with and without the addition of the coarse overlayer.
  • FIGS. 1-3 Certain embodiments of a process for the production of metallic iron nuggets are described with reference to FIGS. 1-3 . Various other embodiments of the process for the production of metallic iron nuggets and examples supporting such various embodiments are also described with reference to the other Figures as described below.
  • the method and system for producing metallic iron nuggets as will be described in further detail by way of example, together with one or more of the resulting benefits and features.
  • the disclosed process permits the control of the amount of sulfur to produce a novel intermediate slag/metallic nugget product, and with separation, novel metallic iron nuggets.
  • FIG. 1 shows a block diagram of one or more generalized illustrative embodiments of a metallic iron nugget process 10.
  • the metallic iron nugget process 10 shown in the block diagram shall be described with further reference to a more detailed embodiment shown in FIG. 3 .
  • One skilled in the art will recognize that one or more of the process steps described with reference to the metallic iron nugget process 10 may be optional.
  • blocks 20, and 26 are labeled as being optionally provided.
  • the metallic iron nugget process 10 is an illustrative embodiment, and that the present invention is not limited to any specific process embodiments described herein, but rather as described in the accompanying claims.
  • a hearth 42 is provided as shown in FIG. 6C .
  • the hearth 42 may be any moving hearth suitable for use with a furnace system 30 (e.g., such as that shown generally in FIG. 2 ) operable for use in carrying out the metallic iron nugget process 10, or another metallic nugget processes that incorporate one or more features described herein.
  • hearth 42 includes a refractory material upon which reducible material to be processed (e.g., feed material) is received.
  • Hearth 42 may be a hearth suitable for use in a rotary hearth furnace, a linear hearth furnace (e.g., as shown in FIG. 3 ), or any other furnace system operable for implementation for direct reduction of metallic iron nuggets.
  • the refractory material may be, for example, refractory board, refractory brick, ceramic brick, or a castable refractory.
  • the hearth may include a supporting substructure that carries a refractory material (e.g., a refractory lined hearth) forming hearth 42.
  • the supporting substructure may be formed from one or more different materials, such as, for example, stainless steel, carbon steel, or other metals, alloys, or combinations thereof that have the required high temperature characteristics for furnace processing.
  • a hearth material layer 44 is provided on hearth 42.
  • the hearth material layer 44 includes at least carbonaceous material.
  • carbonaceous material refers to any carbon-containing material suitable for use as a reductant with the iron-bearing material.
  • the hearth material layer 44 includes anthracite, coke, char, or mixtures thereof.
  • anthracite coal, low volatile bituminous coal, medium volatile bituminous coal, high volatile bituminous coal, sub-bituminous coal, coke, graphite, or other sub-bituminous char materials may be used for the hearth layer 44.
  • Some low, medium, and high volatile bituminous coals may not be suitable for use as hearth layers by themselves, but may be used as make-up materials to pulverized bituminous char.
  • coke materials such as coke breeze may be used.
  • the carbonaceous material of the hearth layer may contain an amount of sulfur in a range from about 0.2% to about 1.5%, and more typically, in the range of 0.5% to 0.8%.
  • the hearth material layer 44 is of a thickness sufficient to prevent slag from penetrating the hearth material layer 44 and contacting refractory material of hearth 42.
  • the carbonaceous material may be ground or pulverized to an extent such that it is fine enough to prevent the slag from such penetration, but typically not so fine as to create excess ash.
  • contact of slag with the hearth 42 during the metallic iron nugget process 10 produces undesirable damage to the refractory material of hearth 42.
  • a suitable particle size for the hearth layer is less than 4 mesh 2 and desirably between 4 and 100 mesh, with a reasonable hearth layer thickness of about 1 ⁇ 2 inch or more, is effective protection for the hearth 42 from penetration of the slag and metallic iron during processing.
  • Carbonaceous material less than 100 mesh is generally high in ash and also may result in entrained dust that is difficult to handle in commercial operations. 2
  • the mesh size of the discrete particles is measured by Tyler Mesh Size for the measurements given herein.
  • a layer of reducible mixture 46 is provided on the underlying hearth material layer 44.
  • the layer of reducible mixture includes at least a reducible iron-bearing material and reducing material for the production of iron metal nuggets.
  • iron-bearing material includes any material capable of being formed into metallic iron nuggets via a metallic iron nugget process 10 as described with reference to FIG. 1 .
  • the iron-bearing material may include iron oxide material, iron ore concentrate, taconite pellets, recyclable iron-bearing material, pellet plant wastes and pellet screened fines. Further, such pellet plant wastes and pellet screened fines may include a substantial quantity of hematite.
  • iron-bearing material may include magnetite concentrates, oxidized iron ores, steel plant wastes (e.g., blast furnace dust, basic oxygen furnace (BOF) dust and mill scale), red mud from bauxite processing, titanium-bearing iron sands and ilmenites, manganiferous iron ores, alumina plant wastes, or nickel-bearing oxidic iron ores. Also, less expensive iron ores high in silica may be used. Other reducible iron bearing materials may also be used for making the reducible mixture for producing metallic iron nuggets used in the processes described herein to produce metallic iron nuggets.
  • nickel-bearing laterites and garnierite ores for ferronickel nuggets or titanium bearing iron oxides such as ilmenite that can be made into metallic titanium iron nuggets (while producing a titania rich slag), or iron rich oxides which contain manganese oxides can be used to produce manganese iron nuggets.
  • such iron-bearing material may be ground to less than 65 mesh (i.e., -65 mesh) or less than 100 mesh (i.e., -100 mesh) in size for processing according to the disclosed processes.
  • the various examples presented herein use iron-bearing material ground to 100 mesh and less unless otherwise specified.
  • larger size particles of iron-bearing material may also be used.
  • pellet screened fines and pellet plant wastes are generally approximately 3 mesh (about 0.25 inches, about 6.7 mm) in average size.
  • Such material may be used directly, or may be ground to -65 or -100 mesh (0.21 mm to 0.15 mm) to provide larger surface contact of carbonaceous reductant with the iron bearing material during processing.
  • the reduction process is generally more effective to efficiently produce metallic iron nuggets with increased surface area with more finely divided material.
  • the carbonaceous material for the reducible mixture may be ground to 100 mesh or less in size for processing. In another embodiment, such carbonaceous material is provided in the range of -65 mesh to -100 mesh. However, carbonaceous material in the range of -200 mesh to -8 mesh (0.074 mm to 2.4 mm) may also be used.
  • coarser carbonaceous material e.g., coal
  • Finer ground carbonaceous material may be more effective in the reducible mixture. Even larger size carbonaceous material may also be used.
  • carbonaceous material of less than about 6 to 7 mesh e.g., about 0.13 inch to about 0.11 inch, about 3.3 mm to 2.8 mm
  • Such larger size material may be used directly, or may be ground to -65 or -100 mesh for better contact and more efficiently react with the iron-bearing reducible material during processing.
  • the various examples presented herein use carbonaceous material ground to -100 mesh unless otherwise specified. When other additives are also added to the reducible mixture, such additives may also ground to -100 mesh or less in size.
  • Various carbonaceous materials may be used in providing the reducible mixture of reducing material and reducible iron-bearing material.
  • eastern anthracite and bituminous non-caking coals may be used as the carbonaceous reductant in at least one embodiment.
  • western sub-bituminous non-caking coal offers an attractive alternative, as such coals are more readily accessible with the rail transportation systems already in place, plus they are generally lower in cost and lower in sulfur levels.
  • western sub-bituminous coals may be used in one or more processes as described herein.
  • an alternative to the direct use of sub-bituminous coals may be to carbonize it, e.g., at 900 °C, prior to its use.
  • the carbonaceous material in the reducible mixture may contain an amount of sulfur in a range from about 0.2% to about 1.5%, and more typically, in the range of 0.5% to 0.8%.
  • the amount of reducing material in the mixture of reducing material and reducible iron bearing material will depend on the stoichiometric quantity necessary for complete metallization of the iron in the reducing reaction in the furnace process. As described further below, such a quantity may vary depending on the furnace used and the furnace atmosphere in which the reducing reaction takes place. In one or more embodiments, the quantity of reducing material necessary to carry out the reduction of the iron-bearing material is between about 70 percent and 90 percent of the stoichiometric quantity of reducing material theoretically necessary for carrying out the reduction to completely metallize the iron.
  • Such carbonaceous material may be used at different stoichiometric levels (e.g., 70 percent, 80 percent or 90 percent) of the stoichiometric amount necessary for reduction of the iron-bearing material.
  • the mounds of reducible material have a density of about 1.8-1.9
  • balls have a density of about 2.1
  • briquettes or extrudates have a density of about 2.1. This feature of the invention is described in more detail below.
  • the reducible mixture 46 may have a thickness of more than 0.25 inches (6.35 mm) and less than 2.0 inches (50.8 mm). In some embodiments, the reducible mixture 46 may have a thickness of less than 1 inch (25.4 mm) and more than 0.5 inches (12.7 mm). In other embodiments, the reducible mixture 46 may have a thickness of about 0.5 inches or less (12.7 mm or less). The thickness of the reducible mixture is generally limited and/or dependent upon the effective heat penetration therein. Increased surface area of iron bearing material and carbonaceous material in the reducible mixture allows for improved heat transfer and reduction activity.
  • additives may optionally be provided to the reducible mixture, for one or more purposes, in addition to the reducing material (e.g., coal or char) and reducible iron-bearing material (e.g., iron oxide material or iron ore).
  • reducing material e.g., coal or char
  • reducible iron-bearing material e.g., iron oxide material or iron ore
  • additives may be provided (i) for controlling slag basicity, (ii) for binders to provide binder functionality (e.g., lime can act as a weak binder in a micro-agglomerate configuration when wetted), (iii) for controlling the slag fusion temperature, (iv) to reduce the formation of micro-nuggets, and/or (v) for further controlling the content of sulfur in resultant iron nuggets formed by the metallic iron nugget process 10.
  • the table of FIG. 5 shows the chemical compositions of various additives to the reducible mixture 46.
  • additives such as Al(OH) 3 , bauxite, bentonite, Ca(OH) 2 , lime hydrate, limestone, and Portland cement.
  • Other additives may also be used such as CaF 2 , Na 2 CO 3 , fluorspar, soda ash, aluminum smelter slag, cryolite, and SiO 2.
  • One or more of such additives, separately or in combination, may provide for beneficial results when used in the metallic iron nugget process 10. These additives and their impact particularly in reducing sulfur levels in the metallic iron nuggets is explained in more detail below.
  • Some of the illustrated additives contain trace amounts of Mg, as shown. Mg, in compounds such as dolomite, should be avoided and in any event is not used in quantities that will produce 5% mass or more MgO in the resulting slag.
  • the reducible mixture 46 is then formed into discrete portions (compacts) either in situ as explained in detail in application U.S. Serial No. 11/296,198, filed December 7, 2005 , incorporated by reference, or preformed into briquettes or extrudates for use in the disclosed process of forming metallic iron nuggets.
  • Compacts refer to any compacted reducible mixture or other feed material that has pressure applied thereto to form in situ desired discrete portions on the hearth layer. For example, compaction or pressure to form discrete portions as mounds in situ on the hearth layer or to provide one or more discrete portions of different profiles in a layer of reducible material.
  • Discrete portions or compacts may also be preformed compacted balls or shaped reducible mixtures such as briquettes or extrudates, which are preformed using compaction or pressure. It should also be noted that different pressurization during formation of the compacts may result in different processing characteristics as desired for the particular embodiment of the present process.
  • a channel definition tool 35 may then be used to create a plurality of channel openings 50 that extend at least partially through the layer of the reducible mixture to define the plurality of nugget forming discrete portions 59 of reducible material for forming the metallic iron nuggets.
  • the channel definition tool 35 may be any suitable apparatus (e.g., channel cutting device, mound forming press, etc.) for creating the channel openings 50 in the layer of reducible mixture (e.g., forming the discrete portions 59, pressing the reducible mixture, cutting the openings, etc.).
  • the channel definition tool 35 may include one or more molds, cutting tools, shaping tools, drums, cylinders, bars, and the like.
  • the disclosed process for forming metallic iron nuggets is not limited to any specific apparatus for creating the channel openings 50 in the formation of the discrete portions 59 of nugget forming reducible material.
  • the nugget separation fill material 58 includes at least carbonaceous material.
  • the carbonaceous material includes pulverized coke, pulverized char, pulverized anthracite, or mixtures thereof.
  • at least a portion of the discrete portions of reducible mixture are dropped onto or pushed into a portion of the hearth material layer to form the nugget separation fill material 58.
  • the reducible mixture may be formed into briquettes or extrudates for use in the process of the producing metallic iron nuggets.
  • the size of the particles of carbonaceous material provided to surround the discrete portions 59, whether formed in situ or preformed may be the same size as the particles used for the hearth layer.
  • Such pulverized material used to fill the areas surrounding the discrete portions of reducible mixture may be ground to -4 or -6 mesh (4.7 mm or 3.3 mm) in size for processing according to the disclosed process.
  • such pulverized material used to fill the areas surrounding the discrete portions of reducible material is -20 mesh (0.83 mm).
  • Finer pulverized material of -100 mesh (0.15 mm) also may be used for the fill surrounding the discrete portions, but a balance should be found to avoid an increase in the amount of micro-nugget formation. Larger size materials may also be used. For example, carbonaceous material of about 1/4 inch (6 mm) in average size may be used for the fill surrounding the discrete portions.
  • a layer containing coarse carbonaceous material 49 is provided over at least some of the discrete portions of the reducible mixture.
  • the coarse carbonaceous material of the overlayer has an average particle size greater than an average particle size of the hearth layer.
  • the overlayer of coarse carbonaceous material may include discrete particles having a size greater than about 4 mesh or about 6 mesh and in some embodiments, the overlayer of coarse carbonaceous material may have discrete particles with a size between about 4 mesh or 6 mesh and about 1 ⁇ 2 inch (about 12.7 mm).
  • the coarse carbonaceous material may be coke, coal, char, or a combination of one or more of these.
  • a reducing furnace 34 (shown in FIG. 2 ) is provided to thermally directly reduce the layer of reducible mixture 46 to produce one or more metallic iron nuggets 63 in one or more of the plurality of discrete portions 59.
  • the reducing furnace 34 may include any suitable furnace regions or zones for providing the appropriate conditions (e.g., drying/heating, reducing, fusion and cooling zones) for processing the reducible mixture 46 of the discrete portions 59 to form one or more metallic iron nuggets 63.
  • a linear hearth furnace, or any other furnace capable of performing the thermal treatment (block 24 of FIG. 1 ) of the reducible mixture 46 may be used.
  • resultant slag 60 on hearth material layer 44 is shown with the one or more metallic iron nuggets 63. That is, slag beads on hearth material layer 44 are separated from the iron nuggets 63, or attached thereto.
  • the metallic iron nuggets 63 and slag 60 e.g., attached slag beads
  • the discharged metallic nuggets are then separated from the slag 60 (block 29).
  • metallic iron nuggets formed by the process described with reference to FIG. 1 is shown.
  • Resultant slag 60 on hearth material layer 44 is shown with the one or more metallic iron nuggets 63.
  • Slag beads on hearth material layer 44 are shown separated from the iron nuggets 63, and attached thereto.
  • the metallic nuggets 63 and attached slag 60 are discharged from hearth 42, and the discharged metallic nuggets are then separated from the slag 60 (block 29).
  • the compacts positioned on the hearth layer may have the areas surrounding the discrete portions 59 of reducible material filled at least partially with nugget separation fill material (e.g., carbonaceous material) (block 26) as described herein.
  • nugget separation fill material e.g., carbonaceous material
  • substantially similar-sized metallic iron nuggets 63 may be almost always, if not always, uniformly formed in each discrete portion 59, which the areas surrounding the discrete portions of reducible material assist in defining.
  • the overlayer 49 of coarse carbonaceous material may contain an amount of sulfur in a range from about 0.2% to about 1.5%, and more typically, in the range of 0.5% to 0.8%.
  • Metallic iron nugget processes that differ from that described with reference to FIG. 1 (e.g., the ITmk3 process, the Hi-QIP process) also can be adapted to practice the process described herein and to produce the novel intermediate slag/nugget product with high sulfur partitioning into the slag.
  • the same reducing material and same iron bearing materials may be used (i.e., type of composition), but the form of the reducible mixture on the hearth may be different.
  • the form that the reducible mixture takes may be preformed green balls using a binder, or may be filled dimples in a pulverized carbonaceous hearth layer, rather than briquettes or other type of compacts to form the discrete portions.
  • the process may be used to form novel intermediate products with ratios of sulfur in slag to sulfur in nuggets of greater than 12, or 15 or 30, and novel metallic iron nuggets with less than 0.03% sulfur, and not just with the process described above with reference to FIG. 1 .
  • depressions are formed in a portion of the hearth material layer followed by the placement of the reducible mixture into the depressions.
  • the metallic iron nugget process 10 may be carried out by a furnace system 30 as shown generally in FIG. 2 .
  • the furnace system 30 generally includes a charging apparatus 36 operable to provide a layer of reducible mixture 46 on at least a portion of hearth material layer 44.
  • the charging apparatus may include any apparatus suitable for providing a reducible mixture 46 onto a hearth material layer 44.
  • a controllable feed chute, a leveling device, and a feed direction apparatus may be used to place such reducible mixture on the hearth 42.
  • the furnace system 30 further may include a nugget separation fill apparatus 37 operable to at least partially fill the areas surrounding the discrete portions 59 of reducible mixture with nugget separation fill material 58.
  • a nugget separation fill apparatus 37 operable to at least partially fill the areas surrounding the discrete portions 59 of reducible mixture with nugget separation fill material 58.
  • Any suitable fill apparatus 37 for providing such nugget separation fill material 58 into the areas surrounding the discrete portions of reducible mixture may be used for manual or automatic operation thereof.
  • Apparatus 37 can also be used to provide the coarse carbonaceous overlayer 49 over the discrete portions 59, which may also partially fill the areas surrounding the discrete portions 59.
  • the furnace system 30 includes a discharge apparatus 38 used to remove the metallic iron nuggets 63 and the slag 60 formed during processing by the furnace system 30 and discharge such components (e.g., metallic iron nuggets 63 and slag 60) from the system 30 after the metallic iron nuggets are cooled and solidified.
  • the discharge apparatus 38 may include any number of various discharge techniques including gravity-type discharge (e.g., tilting of a tray including the nuggets and slag) or techniques using a screw discharge device or a rake discharge device.
  • any number of different types of discharge apparatus 38 may be suitable for providing such discharge of the nuggets 63 (e.g., iron nugget 63 and slag bead 60 aggregates). Further, a separation apparatus may then be used to separate the metallic iron nuggets 63 from the slag beads 60. Any method of breaking and separating the iron nugget and slag bead aggregates may be used, e.g., tumbling in a drum, screening, or a hammer mill. However, any suitable separation apparatus may be used (e.g., a magnetic separation apparatus).
  • One or more different reducing furnaces may be used according to the disclosed processes depending on the particular application of the disclosed processes.
  • laboratory furnaces were used to perform the thermal treatment.
  • scaling to mass production level can be performed and the present processes contemplate such scaling.
  • various types of apparatus described herein may be used in larger scale processes, or production equipment necessary to perform such processes at a larger scale may be used.
  • a linear hearth furnace such as that described in U.S. Provisional Patent Application No. 60/558,197 , entitled “Linear hearth furnace system and methods," filed 31 March 2004, published as US 2005/0229748A1 , may also be used.
  • a summary of the linear hearth furnace described therein is as follows.
  • One exemplary embodiment of such a linear hearth furnace is shown generally in FIG. 3 and, may be, a forty-foot long walking beam iron reduction furnace 712 including three heating zones 728, 730, 731 separated by internal baffle walls 746, and also including a final cooling section 734.
  • various tests were also run using this linear hearth furnace and results thereof are described with reference to the Figures.
  • Zone 728 is described as an initial heating and reduction zone. This zone may operate on two natural gas-fired 450,000 BTU (113,398 Kcal) burners 738 capable of achieving temperatures of 1093 °C. The burners are typically operated sub-stoichiometrically to minimize oxygen levels.
  • BTU 113,398 Kcal
  • Zone 730 is described as the reduction zone. This zone may operate on two natural gas-fired 450,000 BTU (113,398 Kcal) burners 738 capable to achieve 1316 °C. The reduction of the feed mixture occurs in this zone 730.
  • Zone 731 is described as the melting/fusion zone. This zone may operate on two natural gas-fired 1,000,000 BTU (251,995 Kcal) burners 738 capable to sustain this zone at 1426 °C. The function of this zone is to complete the reduction, fusing the iron into metallic iron nodules or "nuggets". In the event that this furnace is being used to make direct reduced iron or sponge iron, the temperatures in this zone would be reduced where complete reduction would be promoted without melting or fusion.
  • the walking beam 724 transports trays 715 to the opposite end 722 of the furnace where they are discharged onto a similar platform (roller ball plate) elevator 754.
  • a safety mechanism has been installed to monitor the position of the hot trays at the discharge of the furnace. Discharge rollers drive the trays onto the platform elevator where they can be removed or re-inserted back into the furnace. The discharge rollers will not function unless trays are in position for discharge, platform elevator is in the "up" position, and the walking beams have been lowered to prevent hot trays from accidental discharge.
  • Tiered conveyor rollers are located at the discharge of the furnace to remove and store sample pallets until cool.
  • a controller 718 coupled to walking beam mechanism 724 controls the furnace through a PC interface.
  • the exhaust gas system 747 is connected to an exhaust fan 753 with a variable flue damper controlled by the furnace PLC. Because the exhaust fan 753 is oversized for this application, a manually controlled in-line damper or pressure control 755 is used to reduce the capacity of the exhaust fan 753 to improve zone pressure control. As a safety precaution, a barometric leg into a level controlled water tank is installed between the common header and exhaust fan to absorb any sudden pressure changes. Exhaust gases are discharged from the fan 753 to a forty-foot exhaust stack 757.
  • the exhaust ducts are refractory lined to the exterior walls of the furnace where they transition to high temperature stainless steel, fitted with water spray nozzles 749, used to cool the waste gases.
  • the sample trays or pallets 715 (as shown in FIG. 4 ) have 30 inch square (762 mm square) refractory lined pans with a flat bottom to be conveyed through the furnace by the walking beam mechanism 724.
  • the trays framework may be made from a 303 stainless steel alloy or carbon steel. They may be lined with high temperature refractory brick or ceramic fiberboard with sidewalls to contain the feed mixture.
  • furnace systems are given to further illustrate the nugget formation process 10, and has provided certain aspects in testing and the results reported herein.
  • any suitable furnace system capable of carrying out one or more embodiments of a metallic iron nugget formation process described herein may be used.
  • each of the one or more metallic iron nuggets includes a maximum cross-section.
  • One or more of the metallic iron nuggets includes a maximum length across the maximum cross-section that is greater than about 0.25 inch (about 6.35 mm) and less than about 4.0 inch (about 101.6 mm).
  • a maximum length across the maximum cross-section is greater than about 0.5 inch (about 12.7 mm) and less than about 1.5 inch (about 38.1 mm). Note that these iron nuggets were produced without the use of a coarse carbonaceous overlayer.
  • carbonaceous reducing materials are typically added to the reducible mixture in an amount greater than the theoretical stoichiometric amount required to complete reduction the iron oxides. This is done to promote carburizing of metallic iron in order to lower the melting point and the reduction temperature of the reducible mixture to metallic iron.
  • the amount of carbonaceous reductant in the balls includes an amount required for reducing iron oxide plus an amount required for carburizing metallic iron and for loss associated with oxidation.
  • the reducible mixture includes a predetermined quantity of reducing material (e.g., carbonaceous reductant) between about 70 percent and about 90 percent of the stoichiometric amount necessary for complete metallization thereof.
  • reducing material e.g., carbonaceous reductant
  • FIGS. 20-21 the addition of about 70% to about 90% of the theoretical amount minimized the formation of micro-nuggets.
  • Carbon needed for further reduction and carbonizing molten metal came from, for example, CO in the furnace atmosphere from oxidization of the carbonaceous material of the coarse carbonaceous overlying layer 49 and underlying carbonaceous hearth material layer 44.
  • the sub-stoichiometric carbon levels in the reducible mixtures are believed to assist in controlling the nucleation sites and inhibiting formation of small metallic nuggets that do not consolidate in larger nuggets.
  • the stoichiometric requirements in carbon for complete reduction of the iron in the metallic nuggets are satisfied from the carbon in the hearth layer, the nugget separation fill and/or the overlayer. These sources are believed to also provide the additional carbon needed for dissolved carbon in the iron phase of the metallic iron nuggets.
  • the availability of carbon from the hearth layer, nugget separation fill and overlayer for solubilization into the reduced iron lowers its melting point, and in turn reduces the processing temperature needed for metal/slag separation.
  • Use of compacts may alleviate any need to use nugget separation material as described with reference to FIG. 1 .
  • control of pressure, temperature and gas diffusion in a briquette, extrudates, or other type of preformed compact may provide such benefits.
  • control of the amount of reducing material in the reducible mixture based on the stoichiometric amount theoretically necessary to complete the metallization process applies not only to the methods described with reference to FIG. 1 , but also to other direct reduction processes for forming metallic nuggets.
  • the coarse overlayer together with the underlying hearth layer described herein reduces the formation of micronuggets formed in the reduction process.
  • the reducible mixture 46 for use in the metallic iron nugget process 10 may include one or more additives in combination with the reducing material and the reducible iron-bearing material (e.g., reducible iron oxide material).
  • One such method 200 for providing the reducible mixture 46 with optional additives as shown in the block diagram of FIG. 8 A mixture of at least reducing material of carbonaceous material such as coal, coke or charcoal and reducible iron oxide material are provided (block 202).
  • calcium oxide or one or more compounds capable of producing calcium oxide upon thermal decomposition thereof may be added to the reducible mixture.
  • sodium oxide or one or more compounds producing sodium oxide upon thermal decomposition may be provided (block 206), in combination with the other components of the reducible mixture.
  • one or more fluxing agents may optionally may be provided for use in the reducible mixture (block 208).
  • the fluxing agents that may be provided for use with the reducible mixture (block 208) may include any suitable fluxing agent.
  • an agent that assists in the fusion process by lowering the fusion temperature of the reducible mixture or increases the fluidity of the reducible mixture may be included.
  • the additives may be naturally part of the reducible iron bearing material used as a source for the iron oxide, and typically may be 2% of the content of the reducible iron bearing material but may range from about 1% to about 7% by weight.
  • calcium fluoride (CaF 2 ) or fluorspar may be used as the fluxing agent.
  • fluorspar e.g., a mineral form of CaF 2
  • SiO 2 , borax, NaF, soda ash (Na 2 CO 3 ), or aluminum smelting industry slag or cryolite may be used as the fluxing agent.
  • fluorspar about 0.5% to about 4% by weight of the reducible mixture may be fluorspar.
  • Fluorspar for example, as well as one or more other fluxing agents, lowers the fusion temperature of the slag phase during formation of the metallic iron nuggets, and at the same time reduces the generation of micro-nuggets. Fluorspar has been found to lower not only the nugget formation temperature, but also to be uniquely effective in decreasing the amount of micro-nuggets generated. It is believed that the lower temperature slag allows for removal of slag from the reducing iron and formation of the metallic iron nuggets.
  • the level of lime or one or more other compounds capable of producing calcium oxide may also be increased beyond a composition (L), as shown on the CaO-SiO 2 -Al 2 O 3 phase diagram of FIG. 9 that indicates the slag compositions of (A), (L), (L 1 ), and (L 2 ).
  • Composition (L) is located in the low fusion temperature trough in the CaO-SiO 2 -Al 2 O 3 phase diagram.
  • the slag compositions are abbreviated by indicating the amounts of additional lime used in percent as a suffix, for example, (L 1 ) and (L 2 ) indicate lime addition of 1% and 2%, respectively, over that of Composition (L).
  • the amount of chemical CaF 2 (abbreviated to CF) added in percent was also indicated as a suffix, for example, (L 0.5 CF 0.25 ), which represents that 0.25% by weight of CaF 2 was added to a feed mixture with Slag Composition of (L 0.5 ).
  • fluorspar is reported to be a not particularly effective desulfurizer in steelmaking slag
  • sulfur in iron nuggets was found to be lowered more effectively at Slag Compositions (L 1.5 ) and (L 2 ) than at (L 1 ). Therefore, the use of fluorspar not only lowered the operating temperature and further lowered the sulfur in iron nuggets, but has also been found to have the unexpected benefit of minimizing the generation of micro-nuggets in the metallic iron nuggets. It is believed that the melting temperature for the slag components is lower when fluorspar is employed. An increased amount of liquid slag is thus available to interact with the sulfur in the iron nugget and extract the sulfur into the slag. If lime is present as an additive, the slag volume is increased and the fluorspar is more effective in increasing sulfur levels in the slag and decreasing sulfur levels in the metallic iron nuggets.
  • calcium oxide, and/or one or more compounds capable of producing calcium oxide upon thermal decomposition may also be used (block 204).
  • lime may be used as an additive to the reducible mixture.
  • Increased use of lime decreased sulfur in iron nuggets from 0.084% to 0.05%.
  • Increased use of lime requires increasingly higher reduction temperatures and longer time at reduction temperature for forming fully fused metallic iron nuggets.
  • a substantial amount of lime is not desirable, as higher temperatures also result in less economical production of metallic iron nuggets, and reduces yields with increased formation of micronuggets.
  • further decreases in sulfur content may be accomplished by use of the coarse overlayer of carbonaceous material as explained more fully herein.
  • sodium oxide, and/or one or more compounds capable of producing sodium oxide upon thermal decomposition may be used in addition to lime (block 206) to lower sulfur in the formed metallic iron nuggets.
  • Soda ash, Na 2 CO 3 , NaHCO 3 , NaOH, borax, NaF and/or aluminum smelting industry slag may be used to lower sulfur in the metallic iron nuggets (e.g., used in the reducible mixture).
  • the sulfur levels in the metallic nuggets by use of these additives has been found to range from 0.083% to 0.018% by weight.
  • the table of FIG. 15 shows the effect of temperature on analytical results of iron nuggets formed from reducible feed mixtures.
  • the reducible feed mixture included a 5.7% SiO 2, magnetic concentrate, a Slag Composition (L 1.5 FS 1 SC 1 ), and medium-volatile bituminous coal at 80% of the stoichiometric requirement for metallization.
  • the reducible feed mixture was heated in the tube furnace at the listed temperatures for 7 minutes in a N 2 -CO atmosphere.
  • sulfur in the iron nuggets decreased markedly with decreasing temperature from 0.029% S at 1400°C to 0.013% S at 1325°C.
  • a furnace atmosphere with a minimum of 75% CO and a maximum of 25% CO 2 may be useful in producing metallic iron nuggets with less than 0.05% sulfur.
  • FIG. 10 shows the effect of fluorspar addition on analytical results of iron nuggets formed from feed mixtures that included a 5.7% SiO 2 magnetic concentrate, medium-volatile bituminous coal at 80% of the stoichiometric requirement for metallization and slag composition (L 1 ), (L 1.5 ), and (L 2 ).
  • the samples in a 2-segment pattern in boats were heated at 1400 °C for 7 minutes in a N 2 -CO atmosphere.
  • the table of FIG. 13 shows the effect of Na 2 CO 3 and CaF 2 additions on sulfur analysis of iron nuggets at different levels of lime addition, the iron nuggets formed from feed mixtures that included a 5.7% SiO 2 magnetic concentrate, medium-volatile bituminous coal at 80% of the stoichiometric requirement for metallization, and slag composition (L m CF 1 or L m FS 1 ).
  • the feed mixtures were heated in the tube furnace at 1400 °C for 7 minutes in a N 2 -CO atmosphere.
  • FIG. 10 shows that with increasing fluorspar addition, sulfur in iron nuggets was lowered more effectively at Slag Compositions (L 1.5 ) and (L 2 ) than at (L 1 ).
  • Slag Compositions (L 1.5 ) and (L 2 ) iron nuggets analyzed including 0.058% by weight sulfur and 0.050% by weight sulfur, respectively, while sulfur decreased steadily to as low as 0.013% and 0.009% by weight, respectively, at fluorspar addition of 4%. Therefore, the use of fluorspar not only lowered the operating temperature and the sulfur in iron nuggets, but also showed an unexpected benefit of minimizing the generation of micro-nuggets as shown in FIGS. 11 and 12 .
  • Analytical results of iron nuggets and slags of linear hearth furnace Tests 14 and 17 are given in FIG. 17 , along with such results for another Test 15.
  • linear hearth furnace Test 15 a tray having an arrangement of feed mixtures in domes was used, such as generally shown in FIG. 18A to provide the nuggets shown in FIG. 18B .
  • the feed mixture of Test 15 included medium-volatile bituminous coal at 115% and 110% of the stoichiometric amount and at Slag Compositions (L 1.5 FS 1 ), placed on a layer of -10 mesh coke. No overlayer of coarse carbonaceous material was used during these tests.
  • sulfur in the iron nuggets ranged 0.152 to 0.266%, or several times to even an order of magnitude higher than those in iron nuggets formed in the laboratory tube and box furnaces with the same feed mixtures as shown and described previously with reference to FIG. 10 .
  • the slags were analyzed to confirm that they were indeed high in lime. Though the CaO/SiO 2 ratios ranged from 1.48 to 1.71, it was noted that the slags were high in FeO ranging from 6.0 to 6.7%.
  • the FeO analyses of slags in the laboratory tube and box furnaces under identical slag compositions analyzed less than 1% FeO.
  • FIG. 19 analytical results of iron nuggets and slag of linear hearth furnace Tests 14, 15, and 17, along with additional Tests 21 and 22 are shown. Carbon and sulfur in iron nuggets and iron, FeO and sulfur in slags for such Tests are summarized.
  • linear hearth furnace Tests 21 and 22 a pallet having an arrangement of different feed mixtures in 6-segment domes was used, such as generally shown in FIG. 18A .
  • the feed mixture included medium-volatile bituminous coal in the indicated percentages of the stoichiometric amount as shown in FIG. 19 and at the indicated Slag Compositions as shown in FIG. 19 , placed on a -10 mesh coke layer.
  • the temperature in Zone 3 was 25 °F (13.9 °C) higher at 2625 °F (1441 °C) in Tests 21 and 22.
  • novel metallic iron nuggets with less than 0.05% sulfur can be produced with the addition of additives to the reducible mixture.
  • additives add to the expense of producing the metallic iron nuggets of the disclosed process.
  • the tests were run using a 40-ft. long (12.19 m), natural gas-fired linear hearth furnace including three heating zones and a cooling section like that described with reference to FIG. 3 .
  • the heating schedule of feed samples in the furnace was modified to eliminate the baffle between the reduction zone (Zone 2) and the fusion or high temperature zone (Zone 3). No Mg was deliberately added beyond trace amounts or impurities found in the materials used. Hydrated lime or limestone may be added to adjust the C/S ((CaO)/(SiO 2 )) ratio to the range of 1.40 to 1.60, or to 1.43 to 1.48.
  • Sample trays 223 (or pallets) as illustrated in FIG. 4 were used in the tests.
  • the trays were made from a 30 inch square carbon steel framework and were lined with high temperature fiber board (with sidewalls) to contain samples (i.e., the reducible mixture and products resulting after completion of reduction processing.
  • the trays 223 were conveyed through the furnace by a hydraulically driven walking beam system as described with reference to FIG. 3 .
  • the arrow 229 in FIG. 4 indicates the direction of tray movement through the furnace.
  • a 1 ⁇ 2" (12.7 mm) layer of anthracite char of particle size between 6 and 100 mesh was used in each of the tests described below in this section, unless otherwise stated.
  • the sample tray 223 traveled through Zone 1 at 1800 °F (982 °C) for 3 minutes without stopping, then through Zone 2 at 2400 °F (1316 °C) by moving one stroke of 5.5" (140 mm) every 16 seconds for a total time of 5 minutes. Then, the tray was moved to the center of Zone 3 (in 55 seconds) for a total time of 10 minutes. The tray was held in Zone 3 at 2600 °F (1427 °C) for long enough time to visually ascertain fusion of the mounds or briquettes, and then moved into the cooling zone without stoppage. The tray was held in the cooling zone for 20 minutes and then discharged.
  • Test LHF 22 are mounds with coarse coke overlayer.
  • the feed mixtures were covered with coarse coke overlayers of 1.0, 0.5 and 0.25 lb/ft 2 (100, 50 and 25% coverage, respectively, 4.88, 2.44 and 1.22 kg/m 2 respectively) of between 1/4" (6.35 mm) and 1/2" (12.7 mm) particle size.
  • a sheet of paper was placed over the feed mixtures to prevent accidental mixing with coarse coke when the coke was distributed over the feed mixtures.
  • the tray was held at 1400 °C (2552 °F) for 24 minutes in Zone 3.
  • FIG. 24 The products are shown in FIG. 24 . Most of the outermost rows and columns were not fused because coarse coke particles of the overlayer rolled off around the periphery, and the mounds were exposed to the furnace gas and oxidized. Therefore, the outermost pieces were excluded from the samples from each section for weight measurements and chemical analyses. The products in each section, excluding these outermost pieces, are shown in FIGS. 25 and 26 .
  • FIG. 25 shows the products from the reducible feed mixtures with 85, 90 and 95% stoichiometric coal, overlayered with coarse coke at 1.0 lb/ft 2 (100% coverage, 4.88 kg/m 2 ), gathered from Row (a) in FIG. 23 .
  • the weights of products are shown in FIG. 27 , and the analytical results of the iron nuggets and slag in FIG. 22 .
  • the amount of micro-nuggets at 85% stoichiometric coal was 1.4% and increased to 3.3% as the amount of added coal increased to 95% of the stoichiometric amount.
  • the metallic iron nuggets analyzed about 0.02% S. This level of sulfur is below the desired level of less than 0.05%. Further optimization as to size consist, coverage density, proximate analyses of reductant coal as well as hearth layer materials, and optimum temperature as well as time at temperature in lowering the sulfur in the iron nuggets, become of interest. Fe and FeO in slag analyzed notably lower than 0.2 and 0.3%, respectively, and the sulfur in the slag analyzed at about 1%.
  • FIG. 28 shows the products from the reducible feed mixtures with 85, 90 and 95% stoichiometric coal, overlayered with coarse coke at 0.5 lb/ft 2 (50% coverage, 2.44 kg/m 2 ), gathered from Row (b) in FIG. 23 . It was determined that the coarse coke coverage of 0.5 lb/ft 2 (50% coverage) produced iron nuggets just as effectively at 90% of the stoichiometric coal. The weight distributions of products, shown in FIG. 27 , indicate again that the amounts of micro-nuggets increased from 0.8% with 85% stoichiometric coal to 2.9% with 95% stoichiometric coal. Hence, the lower stoichiometric amount of coal was found to reduce the amount of micro-nugget generation.
  • Shown in FIG. 28 are the products from the reducible feed mixtures with 85, 90 and 95% stoichiometric coal, overlayered with coarse coke at 0.25 lb/ft 2 (25% coverage, 1.22 kg/m 2 ), gathered from Row (c) in FIG. 23 .
  • all sections resulted in large amounts of square pieces, indicating that the coarse coke overlayer of 0.25 lb/ft 2 (25% coverage, 1.22 kg/m 2 ) was not sufficient. With these large amounts of insufficiently fused iron nugget-slag mixtures, no weight distributions were recorded.
  • Test LHF 26 are dry briquettes with a coarse coke overlayer.
  • two columns of dry briquettes at 80% and 110% stoichiometric amount of coal without a binder were arranged as shown in FIG. 31 .
  • the briquettes were provided with a coarse coke overlayer between 1/4" (6.35 mm) and 1/2" (12.7 mm) particle size at 1.0 and 0.75 lb/ft 2 (4.88 and 3.66 kg/m 2 ) in Rows (a) and (b), respectively.
  • a sheet of paper was placed over the feed mixtures to prevent accidental mixing with coarse coke when the coke was distributed over the reducible feed mixture.
  • the coke-overlayered feed is shown in FIG. 32 .
  • the tray was held at 2552 °F (1400 °C) for 20 minutes in Zone 3.
  • the products of the briquettes were 100% fused into metallic nuggets.
  • the analytical results are shown in FIG. 30 .
  • the metallic iron nuggets analyzed 0.030% S and 3.68% C, while the slag analyzed low in iron and 1.39% S.
  • the ratio of sulfur in the slag over sulfur in the metallic nuggets by weight, (S)/[S] was calculated to be 46.
  • Test LHF 27 were mounds of reducible mixtures with different degrees of coarse coke overlayer.
  • two trays of reducible feed mixtures in mounds with 80% stoichiometric coal were prepared, as shown in FIG. 34 .
  • the mounds were divided into three equal rows and the rows were overlayered with coarse coke of between 1/4" (6.35 mm) and 1/2" (12.7 mm) particle size at 1.25, 1.0 and 0.75 lb/ft 2 (6.1, 4.88 and 3.66 kg/m 2 ) in Rows (a), (b), and (c), respectively.
  • a sheet of paper was placed over the feed mixtures before spreading the coarse coke, as shown in FIG. 35 .
  • the tray was sent through the furnace according to the standardized heating schedule of these tests and heated to 2600 °F (1427 °C) for 20 minutes in Zone 3.
  • the products are shown in FIG. 36 .
  • the products could not be seen, but iron nuggets associated with the black-overlayered slag are seen in the outside columns on both sides, overlayered with 0.75 and 1.0 lb/ft 2 (3.66 and 4.88 kg/m 2 ) of coarse coke and in the top row.
  • the products were separated into nuggets, micro-nuggets, +20 mesh mag. and slag fractions and shown in FIG. 37 .
  • the weights and analytical results of the products are shown in FIGS. 29 and 30 , respectively.
  • Sample (b) was the iron nuggets and associated black-colored slag from the outer columns at the periphery where the coarse overlayer slid off. Iron analysis of the slag was notably higher than those from the interior, which were 0.82% Fe and 1.20% FeO. Sulfur analysis of the iron nuggets was 0.076% S with the ratio, (S)/[S], of 10.8. The results show that an exposure of the products to the furnace atmosphere was detrimental to the removal of sulfur from iron oxides into the slag.
  • Test LHF 28 were mounds with different degrees of coarse coke overlayer. Another tray of reducible feed mixtures in mounds with 80% stoichiometric coal, covered with coarse coke of between 1/4" (6.3 mm) and 1/2" (12.7 mm) particle size at 1.25, 1.0 and 0.75 lb/ft 2 (6.1, 4.88 and 3.66 kg/m 2 )in Rows (a), (b), and (c), respectively, was sent through the furnace according to the standardized heating schedule for these tests, but the temperature of Zone 3 was lowered to 2550 °F (1399 °C) and kept at that temperature for 20 minutes.
  • the products are shown in FIG. 38 .
  • the products were hidden from view by the coke overlayer.
  • the products were separated and shown in FIG. 39 . More than one half of the iron products were reduced, but not fused into metallic nuggets, as seen in the mounds to the right of the fused iron nuggets. With a coarse coke overlayer coverage of 0.75 lb/ft 2 , the amount of fully fused iron nuggets approached one half of the product.
  • the weights of the products are shown in parentheses in FIG. 29 .
  • Test LHF 29 was briquettes with different degrees of coarse coke overlayer at a lower temperature.
  • Test LHF 26 the products formed at 1427 °C (2600 °F) were all fused into metallic iron nuggets.
  • an identical tray of dry briquettes overlayered with coarse coke, as shown in FIG. 31 was sent through the furnace according to the standardized heating schedule, but with the temperature of Zone 3 lowered to 1399 °C (2550 °F) and kept at that temperature for 20 minutes.
  • the products are shown in FIG. 40 and the separated products are shown in FIG. 41 .
  • All of the briquettes were fully fused into metallic iron nuggets.
  • the iron nuggets were notably smaller than those from the mounds as the briquettes were only half the size and weight of the mounds.
  • the weights of the metallic nuggets are shown in FIG. 29 .
  • Micro-nuggets at 80% stoichiometric amount of coal were low, 1.0 and 0.5%, for coarse coke overlayers of between 1/4" (6.35 mm) and 1/2" (12.7 mm) particle size at 1.0 and 0.75 lb/ft 2 (4.88 and 3.77 kg/m 2 ) coverage, respectively. Meanwhile, those at 110% stoichiometric amount of coal were notably higher, 5.0 and 3.5%, for coarse coke overlayers of 1.0 and 0.75 lb/ft 2 (4.88 and 3.77 kg/m 2 ) coverage, respectively. Therefore, again, as previously observed, the generation of micro-nuggets was less at 80% stoichiometric amount of coal in the reducible mixture. It is also noted that the lower coverage by coarse coke overlayer generated less micro-nuggets.
  • the analytical results are shown in FIG. 30 .
  • the results showed that the iron nuggets had undergone substantially complete metallization. It was determined that the iron nuggets analyzed were 0.016 to 0.029% S, while the slag analyzed essentially no Fe and 0.23 FeO.
  • the relationship (i.e., the ratio) of sulfur in the slag over sulfur in the metallic nuggets, (S)/[S], is plotted as a function of the percent by weight sulfur in the nuggets for the various tests that have been done.
  • the filled squares ( ⁇ ) are for the LHF tests on reducible feed mixtures using 5.3% SiO 2 taconite concentrate, a Slag Composition L 1.5 FS 2 , and 80% stoichiometric Fording Standard coal.
  • the open squares ( ⁇ ) are for box furnace tests on reducible feed mixture using 3.6% SiO 2 taconite concentrate, a Slag Composition L 1.5 FS 2 , and 80% stoichiometric Jim Walter coal.
  • ratio (S)/[S] below 12 were for tests without the coarse coke overlayer and the others are for tests with the coarse coke overlayer with no deliberately added Mg producing levels between 5% and 13% of MgO in the slag.
  • sulfur is increased in the slag by the use of the coarse carbonaceous overlayer, and that when the ratio (S)/[S] is 30 or more, sulfur content in the metallic iron nuggets that are produced was 0.03% or less.
  • These latter metallic iron nuggets are particularly useful in steelmaking processes such as the electric arc furnace, because the iron nuggets may be substituted for scrap in the charge.
  • the coarse coke overlayer enabled carburizing both from the hearth layer and the coarse coke overlayer.
  • the availability of carbon from the coarse overlayer is advantageous in lowering the overall processing temperature requirements, while creating the necessary reduction conditions to allow effective separation of sulfur into the slag.
  • the use of a reducible feed mixture that includes a reducible mixture, on the hearth layer, that has a predetermined quantity of reducing material between about 70 percent and about 90 percent of the stoichiometric amount of reducing material and with a coarse carbonaceous material over at least a portion of the layer of the reducible mixture results in complete metallization thereof, and also reduce the potential for formation of micro-nuggets.
  • the result was reproduced with the box and tube furnaces.
  • reducing material e.g., coal
  • the overlayer may be used with the overlayer to obtain almost complete metallization and formation of metallic iron nuggets from a predetermined quantity of reducible iron bearing material, the reducing material (e.g., coal) and the iron bearing material providing a reducible feed mixture for processing according to one or more embodiments described herein.

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EP0952230A1 (de) * 1998-03-24 1999-10-27 KABUSHIKI KAISHA KOBE SEIKO SHO also known as Kobe Steel Ltd. Verfahren zur Herstellung von reduzierten Eisenagglomeraten
US6126718A (en) 1999-02-03 2000-10-03 Kawasaki Steel Corporation Method of producing a reduced metal, and traveling hearth furnace for producing same
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EP1167547A1 (de) * 2000-06-28 2002-01-02 Midrex International B.V. Zürich Branch Verfahren zur Erzeugung von stückigen Eisenerz
US20040076539A1 (en) * 2001-05-15 2004-04-22 Shuzo Ito Granular metallic iron
US20050229748A1 (en) 2004-03-31 2005-10-20 Regents Of The University Of Minnesota Linear hearth furnace system and methods regarding same
EP1605067A1 (de) 2003-03-20 2005-12-14 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Herstellungsverfahren für partikelförmiges eisenmetall
WO2006061790A1 (en) * 2004-12-07 2006-06-15 Nu-Iron Technology, Llc Method and system for producing metallic iron nuggets

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DE19543074A1 (de) * 1995-11-13 1997-05-15 Mannesmann Ag Direktreduktionsverfahren und Einrichtung
EP0952230A1 (de) * 1998-03-24 1999-10-27 KABUSHIKI KAISHA KOBE SEIKO SHO also known as Kobe Steel Ltd. Verfahren zur Herstellung von reduzierten Eisenagglomeraten
US6126718A (en) 1999-02-03 2000-10-03 Kawasaki Steel Corporation Method of producing a reduced metal, and traveling hearth furnace for producing same
US20010037703A1 (en) * 2000-04-10 2001-11-08 K. K. Kobe Seiko Sho (Kobe Steel, Ltd.) Method for producing reduced iron
EP1167547A1 (de) * 2000-06-28 2002-01-02 Midrex International B.V. Zürich Branch Verfahren zur Erzeugung von stückigen Eisenerz
US20040076539A1 (en) * 2001-05-15 2004-04-22 Shuzo Ito Granular metallic iron
EP1605067A1 (de) 2003-03-20 2005-12-14 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Herstellungsverfahren für partikelförmiges eisenmetall
US20050229748A1 (en) 2004-03-31 2005-10-20 Regents Of The University Of Minnesota Linear hearth furnace system and methods regarding same
WO2006061790A1 (en) * 2004-12-07 2006-06-15 Nu-Iron Technology, Llc Method and system for producing metallic iron nuggets

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