WO2019161202A2 - Valorisation des minerais et concentrés contenant du fer et un ou plusieurs métaux par réduction carbothermique sélective et procédé de fusion - Google Patents

Valorisation des minerais et concentrés contenant du fer et un ou plusieurs métaux par réduction carbothermique sélective et procédé de fusion Download PDF

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WO2019161202A2
WO2019161202A2 PCT/US2019/018219 US2019018219W WO2019161202A2 WO 2019161202 A2 WO2019161202 A2 WO 2019161202A2 US 2019018219 W US2019018219 W US 2019018219W WO 2019161202 A2 WO2019161202 A2 WO 2019161202A2
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slag
metal
smelting
product
flux
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WO2019161202A3 (fr
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Basak ANAMERIC
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University of Minnesota Twin Cities
University of Minnesota System
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University of Minnesota Twin Cities
University of Minnesota System
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C35/00—Master alloys for iron or steel
    • C22C35/005—Master alloys for iron or steel based on iron, e.g. ferro-alloys
    • 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
    • Y02P10/20—Recycling

Definitions

  • Embodiments described herein relate to the benefaction of metal-oxide raw materials (such as low-grade ores, concentrates, waste-oxides, and byproducts) to concentrate them, and to produce a metallic product and an upgraded concentrate (slag).
  • the metallic product is either metal itself (containing some amounts of metal-carbides), ferroalloy, or an alternative ferroalloy of the metal intended.
  • the metallic product can be used and marketed as alternative metal or ferroalloy units.
  • the upgraded concentrate can be used as raw material for: (i) further upgrading,
  • Mineral processing or upgrading include treating crude ores and mineral products in order to separate commercially valuable minerals from gangue minerals (waste-rock). This is the first process that most ores undergo after mining in order to provide a more concentrated raw material for further pyrometallurgical and hydrometallurgical or electrometallurgical processes.
  • the primary upgrading operations include comminution and concentration.
  • the comminution step includes crushing and grinding of the ores until the liberation size distribution is achieved.
  • the concentration step includes separation of the valuable minerals from the gangue minerals using differences in their physical or physico-chemical properties.
  • the common commercial concentration steps include: gravity separation (heavy media separation, jigging, shaking tables), flotation, magnetic separation (high intensity magnetic separation, low intensity magnetic separation (LIMS)) and electrostatic separation.
  • a method for upgrading metal-oxide raw materials such as low-grade ores, concentrates, waste-oxides, and byproducts which contain iron and one or more metals includes: (i) selective carbothermic reduction and smelting of the targeted metal producing a metallic product, (ii) selective carbothermic partial reduction of the other metals to a desired oxidation level, (iii) identification and subsequent production of a desired slag composition (designed in accordance to the inherent composition of the ores) can be achieved either via flux addition or manipulation of the inherent concentrate composition, which can fuse and separate from the metallic product, (iv) separation of the metallic product from slag (upgraded concentrate), and (v) subsequent or iterative application of the steps (i) (iv) at different temperatures and residence times with various flux and carbonaceous material additives to produce different metallic products and upgraded concentrates.
  • This method can be repeated subsequently to selectively reduce and smelt different metals from the slag and produce (i) metallic products of the intended metals, and (ii) upgraded concentrates of the other metals.
  • Each selective carbothermic reduction and smelting step would encompass specific operational conditions designed in accordance with composition of the raw materials (the metals in consideration and gangue minerals). These operational conditions include type and amount of flux and carbonaceous material addition, and furnace temperature and residence time.
  • the slag product and the metallic product can each be used as a commodity, in embodiments.
  • further processing can be conducted to remove other metals from slag.
  • the further processing can be additional selective carbothermic reduction and smelting, which can be used to upgrade and extract additional metals from the slag.
  • mineral processing methods, pyrometallurgical, hydrometallurgical or electrometallurgical processing can be used to extract metals and produce pure metals or metal oxides from the slag.
  • the metallic product can be either metal itself (or metal and metal- carbides), or an alternative ferroalloy of the metal or ferroalloy (all with desired composition). In embodiments, the metallic product can be used and marketed as an alternative metal unit in standard metal manufacturing processes.
  • the processes described herein can include use of slag produced during a previous selective carbothermic reduction and smelting (SCRS) step as a raw material, addition of a predetermined amount of a flux (as needed), and a predetermined amount of carbonaceous material in order to achieve a desired finished product.
  • SCRS selective carbothermic reduction and smelting
  • the desired finished product can be produced by repeating the steps of adding the flux material and carbonaceous material, selectively carbothermically reducing and smelting the combination, and fusing the slag product. Each time the step of adding the flux material and carbonaceous material is repeated, the composition of the flux material and the rate of addition of the flux material can be modified to arrive at an intermediate (or final) target composition.
  • the temperature and residence time of the selective carbothermic reduction and smelting process is adjusted to promote reduction and smelting reactions for production of desired products.
  • a method for producing alternative ferro-alloys by manipulation of a flux, carbonaceous material addition rate, raw concentrate composition, furnace temperature and residence time includes determining a desired finished product based on a composition of raw materials, selecting a flux material based upon the composition of raw materials to arrive at a target composition suited for smelting, selecting a carbonaceous material addition rate to support at least partial or complete reduction of at least one metal oxide contained in the raw materials, selecting an adequate furnace temperature and residence time to promote reduction and smelting of the at least one metal oxide, combining the flux material and carbonaceous material with the raw materials to produce a raw material mixture, selectively carbothermically reducing and smelting the raw material mixture at a temperature and residence time that at least partially reduces a desired metal to produce the alternative ferro-alloy, and separating the alternative ferro-alloy from a slag.
  • the composition of raw materials can include at least one metal-oxide raw material such as a low-grade ore, a concentrate,
  • the method can further comprise producing a second alternative ferro-alloy using the slag, wherein producing the second alternative ferro-alloy comprises repeating the steps of determining a second desired finished product, selecting a second flux material, selecting a second carbonaceous material addition rate, selecting a second adequate furnace temperature and residence time, combining the second flux material and the carbonaceous material with the slag, selectively carbothermically reducing and smelting the raw material mixture at a temperature and residence time that at least partially reduces a second desired metal to produce the second alternative ferro-alloy, and separating the second alternative ferro-alloy from a slag.
  • FIG. 1 is a flowchart for the selective carbothermic reduction and smelting process, for production of a metallic product and an upgraded concentrate (slag) from low grade ore deposits, concentrates or waste oxides, according to an embodiment.
  • FIG. 2 is a flowchart for the use of selective carbothermic reduction and smelting process, for production of a metallic product and an upgraded concentrate (slag) from slag produced as described with respect to FIG. 1.
  • FIG. 3 is a flowchart for the use of selective carbothermic reduction and smelting process, for production of ferroalloy or alternative ferroalloy and an upgraded concentrate (slag) from slag and metallic product produced as described with respect to FIG. 1.
  • FIGS. 4 A and 4B are flowcharts for the use of selective carbothermic reduction and smelting process, for production of a metallic product and an iron rich upgraded concentrate (slag).
  • FIG. 5A is a flowchart for the use of selective carbothermic reduction and smelting process, for production of ferroalloy or alternative ferroalloy and an upgraded concentrate (slag) from iron rich slag produced in a preceding step.
  • FIG. 5B is a flowchart for the use of selective carbothermic reduction and smelting process, for production of ferroalloy or alternative ferroalloy and an upgraded concentrate (slag) from iron rich slag produced in a proceeding step, according to another embodiment including the addition of a metallic product.
  • FIG. 6 is a flowchart for the treatment of upgraded concentrate (slag) using hydrometallurgical processes, such as leaching, solution concentration and purification, and metal recovery to produce marketable products including pure metal, metal oxides, or metal sulfides.
  • hydrometallurgical processes such as leaching, solution concentration and purification, and metal recovery to produce marketable products including pure metal, metal oxides, or metal sulfides.
  • FIG. 7 is an Ellingham diagram depicting the Gibbs free energy of various upgradable materials as a function of temperature.
  • FIG. 8 is a CaO MnO x Si0 2 phase diagram depicting a target material composition according to one embodiment.
  • FIG. 9 is a Si0 2 CaO Al 2 0 3 MnO phase diagram that can be used to determine affinity to metal oxides that are intended to be retained in the slag after selective carbothermic reduction and smelting, in embodiments.
  • FIGS. 10A and 10B depict raw material mixtures before and after selective carbothermic reduction and smelting, respectively.
  • FIGS. 11 A, 11B and 11C depict briquetted or densified raw material mixtures before selective carbothermic reduction and smelting, immediately after selective carbothermic reduction and smelting, and after selective carbothermic reduction, smelting, and cooling, respectively.
  • Metal-oxide raw materials such as low grade ores, concentrates, waste-oxides, and byproducts which contain iron (M iron ) and one or more metals (M 2 , M 3 ,....M n ) can be upgraded using selective carbothermic reduction and smelting process as a concentration step. This concentration step allows these ores, concentrates or waste-oxides to be considered for use as viable raw materials for further processing.
  • the other metals contained in the ores or concentrates can include chromium (Cr), manganese (Mn), vanadium (V), silicon (Si), titanium (Ti), barium (Ba), aluminum (Al), magnesium (Mg), or calcium (Ca), for example.
  • Selective carbothermic reduction and smelting process can be applied to ores or concentrates which were previously deemed unusable or uneconomical. This can greatly increase the available quantity of many valuable materials. It can also be used for waste-oxides which are currently being land-filled or beneficiated by other means.
  • a metallic product and an upgraded concentrate are produced.
  • the upgraded concentrate can be used as a raw material for: (i) further selective carbothermic reduction and smelting processing or other pyrometallurgical processing steps to produce ferroalloys or metal itself and metal-carbides (ii) further hydrometallurgical processing to produce pure metals, metal oxides (such as Mn0 2 , Ti0 2 ), and metal sulfates (such as BaS0 4 ).
  • the metallic product is either metal itself (containing some amounts of metal-carbides) or an alternative ferroalloy of the desired metal.
  • the metallic product can be used and marketed as alternative metal units.
  • the process includes: (i) selective reduction and smelting of the targeted metal to produce a metallic product, (ii) selective partial reduction of the other metals to a desired oxidation level, (iii) identification and subsequent production of a desired slag composition, designed in accordance to the inherent composition of the ores either via flux addition or manipulation of the inherent concentrate composition.
  • the slag composition materialized can fuse and separate from the metallic product.
  • separation of the metallic product from slag i.e. upgraded concentrate
  • FIG. 1 is a flowchart that depicts a process 100 according to an embodiment.
  • Process 100 has, as inputs, metal-oxide raw materials (such as a low-grade ore, concentrates, waste-oxides, or byproducts) 102.
  • Process 100 also has, as inputs, flux 104 and carbonaceous material 106.
  • These raw materials (102, 104, 106) are ground to size distribution less than 0.074 mm (200 mesh) and blended. The fine size distribution of the raw materials enables large surface area to improve kinetics of the reactions.
  • the blended raw materials are referred as the raw material mixture.
  • This raw material mixture may be used as-is (fine powder mixture of the raw materials), agglomerated or densified hinged on the processing requirements for the selective carbothermic reduction and smelting (SCRS) reactor intended for use.
  • SCRS reactor intended for use may be an induction furnace, submerged arc furnace, electric arc furnace, or other similar reactor, in embodiments.
  • the flowchart depicted in FIG. 1 describes a method for upgrading a raw material input 102 that includes a several metallic products (M 2 , M 3 , M 4 , ... M n ) in addition to iron (Mi ron ).
  • various other metals could be found in raw materials 102, some of which may not include iron, but could be any of the other metals described above, for example.
  • the method described with respect to FIG. 1 is not limited to any particular material, as each material will have different thermal and kinetic properties that result in the ability to selectively reduce those materials sequentially from an initial, low-quality raw material input.
  • Flux 104 is added or concentrate composition is manipulated based on a desired intermediate or final product.
  • the flux addition rate is determined based on targeted slag composition and initial composition of the low-grade ores or concentrates 102.
  • Flux 104 can be added as necessary to produce a fusible slag and to ensure that smelting interaction of the desired metal ions with slag can be achieved.
  • the inherent composition could be suitable to produce slag with desired properties, or different raw material can be blended achieve this composition. For such cases, the flux addition is not necessary.
  • Selective carbothermic reduction and smelting 108 results in a metallic product 110 as well as a slag product 112 (with the targeted slag composition).
  • the targeted slag product 112 is determined based on its formation energy, melting temperature and affinity to the other metal oxides in the system.
  • Limestone, burnt lime, dolomite, olivine, silica sand, and fly ash are examples of flux 104 that can be added to low-grade ore 102 to produce the targeted slag composition.
  • Carbonaceous material 106 is added to metal-oxide raw materials 102 in along with with flux 104
  • the carbonaceous material type and addition rate is determined based on the amount of carbon 106 required for complete reduction and carburization of the metal from metal-oxide raw materials 102 that is desirably removed and a degree of reduction intended for any other metal or metals.
  • Coal, coke breeze, petroleum coke, bio-coals and graphite are examples of carbonaceous material 106 that can be added to low-grade ore 102 in combination with flux 104.
  • selective carbothermic reduction and smelting is performed on the raw material mixture.
  • the raw material mixture is heated.
  • heating following events, take place: (i) thermal decomposition of the carbonaceous material, (ii) reducing gas generation, (iii) complete reduction of metal oxides in consideration for removal, (iv) partial reduction of the other metals, (v) formation of slag, (vi) reaction of the partially reduced other metals with the slag, (vii) melting of slag, (viii) carburization of the metal, (ix) melting of metal, (x) coalescence of the metal intended for removal, (xi) coalescence of the slag, and (xii) separation of the slag from metal.
  • these events may not take place in the sequence listed, and in some embodiments subsets of these events take place simultaneously.
  • Metallic product 110 and slag product 112 are produced as a result of selective carbothermic reduction and smelting.
  • the metallic product 110 is a marketable product, in embodiments.
  • metallic product 110 can be used as an alternative metal unit for further production schemes including production of ferroalloys, and other alloys containing that metal.
  • first selective carbothermic reduction and smelting step would lead to production of iron as a metallic product.
  • This metallic product can be used as an alternative iron unit, a raw material for steel production and ferroalloy production. Depending on the composition of the raw materials used this metallic product may contain elevated amounts of sulfur and phosphorus. In this case, it can be refined to produce a higher quality product.
  • the slag product 112 is an upgraded concentrate of the other metals (M 2 , M 3 ,M 4 caravan...M n ), after a first desired metal (for example, M iron ) has been selectively smelted as metallic product 110.
  • This upgraded concentrate can be marketed as-is depending on its composition and demands of the market.
  • the upgraded concentrate can be further upgraded using another selective carbothermic reduction and smelting step as shown in FIG. 2.
  • the slag would again be ground (112G) to a size distribution less than 0.074 mm (200 mesh) and blended with appropriate amounts of flux 104' (as needed) and carbonaceous materials 106' to produce another raw material mixture.
  • Flux 104' can be the same as flux 104, or alternatively can have a different composition.
  • carbonaceous material 106' can be the same as carbonaceous material 106 or, in embodiments, carbonaceous material 106' can have a different composition, reactivity, packing density, quantity, or other attributes to affect the chemical and thermal properties of the resulting process.
  • Slag 112 is ground (112G) and combined with flux 104' that has been ground 104G' and carbonaceous material 106' that has been ground 106G'.
  • the resulting combination forms raw material 107'.
  • the raw material 107' is blended, mixed and used as-is, and densified, agglomerated or briquetted based upon the processing requirements for the SCRS reactor intended for use, in embodiments. Heating of this raw material mixture 107', under the specified conditions for selective carbothermic reduction and smelting 208 leads to production of another slag product (202) and metallic product (200).
  • This second slag product is an upgraded concentrate of the other metals (M 3 , M 4 , ...
  • the slag product 112 can also be used as a raw material for ferro-alloy production as shown in FIG. 3, FIG. 5A, and FIG. 5B.
  • slag product is ground (112G) to a size distribution less than 0.074 mm (200 mesh) and blended with appropriate amounts of flux 104" that has been ground (l04"G) and carbonaceous materials 106" that has been ground (l06"G) as needed to produce raw material mixture 107".
  • metallic product 110 can also be added to the system to manipulate the concentration ratio of iron or other metals to other metals before selective carbothermic reduction and smelting 308.
  • This slag product (302) is an upgraded concentrate of the other metals (M 3 , M 4 , ... M n ) and ferroalloy (300) produced is an alloy of iron and one or more of the other metals contained in the system.
  • Operational parameters such as flux and carbonaceous material type and addition rate, the furnace temperature, and residence time used for this second selective carbothermic reduction and smelting step may be different from the one used for the first selective carbothermic reduction and smelting step.
  • the composition of the metallic product and slag produced can be manipulated using the operational parameters for selective carbothermic reduction and smelting process. These operational parameters include: (i) flux type and addition rate, (ii) carbonaceous material type and addition rate, (iii) furnace temperature and (iv) residence time.
  • FIGS. 4 A and 4B depict the flowsheet for production of a metallic product 110 and slag 400 using a selective carbothermic reduction and smelting process.
  • This slag 400 can be used as a raw material for production of ferroalloys or alternative ferroalloys using a consecutive selective carbothermic reduction and smelting process, as described in more detail below with respect to FIGS. 5 A and 5B.
  • low-grade ore, concentrate, or waste-oxide 102 is combined with flux 104 and carbonaceous material 106, as described above with respect to FIGS. 1 and 2, to form raw material mixture 407.
  • the raw material mixture is blended and densified 407 and undergoes selective carbothermic reduction and smelting 408 to produce metallic product 110 as well as slag 400, which is a concentrate that contains remaining metals and some amounts of iron ( ⁇ M 3 , M 4 ,.. ,M n ⁇ )
  • the slag product 112 (or other slag products generated during consecutive selective carbothermic reduction and smelting steps) can be used as a raw material for hydrometallurgical processing as shown in FIG. 6.
  • the hydrometallurgical processes can include leaching, solution concentration and purification, and metal recovery.
  • the marketable product produced could be either pure metal (Mn, Ti, V,..), metal oxides (such as Mn0 2 , Ti0 2 ) or metal sulfides (BaS0 4 ).
  • Slag 112 of FIG. 6 includes remaining metals (M2, M3, M4,...,Mn) from an earlier selective carbothermic reduction and smelting process, such as the process shown in FIGS. 1-5.
  • the slag 112 undergoes grinding 602 and then hydrometallurgical and/or electrometallurgical processing 604.
  • Hydrometallurgical and/or electrometallurgical processing 604 can include leaching, solution concentration and purification, and/or metal recovery, in embodiments.
  • Hydrometallurgical and/or electrometallurgical processing 604 results in marketable product 606, which can be pure metal, metal oxides, or metal sulfides, for example.
  • This process 100 can be used to beneficiate metal-oxide raw materials (e.g., ores, concentrates, byproducts, or waste oxides) that are not suitable for upgrading using other, conventional mineral processing steps such as magnetic separation, flotation, and gravity separation.
  • Process 100 facilitates recovery of all of the metals present in many concentrates.
  • waste oxides or other waste materials or byproducts can even be upgraded to raw materials.
  • the materials added as flux can often be waste or byproducts of other processes, which reduces environmental impact of the mining process, is inexpensive to acquire, and increases yields. Once all metals are removed, remaining slag is often usable for cement production, glass production, or other industrial purposes.
  • the acid consumption for hydrometallurgical processing is lowered by removal of unwanted impurities of other metals, and conversion of all of the desired metal -containing components to a single oxidation state. Furthermore, the properties of the products created using process 100 can be adjusted by varying operational conditions such as furnace temperature and residence time.
  • the selective carbothermic reduction and smelting process is based on the consideration of the thermodynamic stability of the metal oxides.
  • the metal oxides with least stability can be selectively reduced to its metallic form easier than the more stable metal oxides.
  • a metal oxide that has been reduced can be removed from the system by forming two liquid phases (metal and slag).
  • the ability to bind with oxygen and stability of this bind can be evaluated using Gibbs free energy change for generation of oxide components at various temperatures. The temperature dependency of Gibbs free energy change for such reactions are depicted in Ellingham graphs such as the one shown in FIG. 7.
  • the separation of the metallic product from the slag is achieved by formation of two immiscible liquid phases.
  • the slag composition required to attain fusing is calculated using relevant phase diagrams to the raw materials in consideration, and affinity of the identified slag phases to the remaining metal oxides in the system.
  • CaO MnO x Si0 2 and Si0 2 CaO Al 2 0 3 MnO phase diagrams used for suitable slag composition calculations of the example systems presented are shown in FIG. 10.
  • Raw material mixtures which contain low grade ore, concentrates or waste-oxides, flux (as needed) and carbonaceous materials before and after selective carbothermic reduction and smelting processes are shown in FIGS 10A, 10B, 11 A, 11B, and 11C.
  • the metallic product and slag produced are shown.
  • the slag value can be larger than the metallic product volume.
  • SCRS Selective Carbothermic Reduction and Smelting
  • the selective carbothermic reduction and smelting process includes heating of raw material mixtures, which contain metal-oxide raw materials (low-grade ores, concentrates, byproducts, or waste-oxides), reducing carburizing agent (carbonaceous materials) and flux (as needed), at required furnace temperatures and residence times, under reducing conditions.
  • metal-oxide raw materials low-grade ores, concentrates, byproducts, or waste-oxides
  • reducing carburizing agent carbonaceous materials
  • flux as needed
  • metallic product and slag are produced by the selective carbothermic reduction and smelting process.
  • the metallic product can be a marketable product.
  • the composition of the metallic product and slag vary depending on the selective carbothermic reduction and smelting processing conditions and inherent composition of the raw materials used.
  • Metallic product can be metal containing some amounts of metal-carbides, ferroalloy or alternative ferroalloy (alloys containing iron and other metals). It can be used as an alternative metal units, ferroalloy or alternative ferroalloy units. It can also be refined and marketed as high quality alternative metal units.
  • the slag is an upgraded concentrate of the other metals remaining in the system. It can be marketed as-is as a raw material, such as for use as source of the remaining metals. It can be further upgraded using conventional mineral processing techniques. It can be further beneficiated using hydrometallurgical and pyrometallurgical techniques or another selective carbothermic reduction and smelting step or steps (as shown in FIG. 2, FIG. 3, FIG. 4A, FIG. 4B, FIG. 5A, FIG. 5B, and FIG. 6). The selective carbothermic reduction and smelting steps can be applied consequently to recover all the metals contained in the system.
  • Selective carbothermic reduction and smelting process can be used to beneficiate ores, concentrates, waste oxides, or byproducts which are not suitable for upgrading using other mineral processing steps such as magnetic separation, flotation and gravity separation. This in turn facilitates recovery of all or many of the metals present in the concentrate.
  • the raw materials used in selective carbothermic reduction and smelting can include a variety of previously unexploited products such as run of mine ores (ores without any dressing), upgraded ores, or waste oxides. Fluxes likewise can include waste or by-product of other processes.
  • the final slag can be used as raw material for either cement production or glass production, for example.
  • the acid consumption for leaching is lowered by removal of unwanted impurities (other metals) and conversion of all that metal containing components to a single oxidation state.
  • the properties of the finished products produced by selective carbothermic reduction and smelting can be adjusted by varying the operational conditions such as flux type and addition rate, carbonaceous material type and addition rate, furnace temperature and residence time.
  • the selective carbothermic reduction and smelting process is developed based on consideration of the thermodynamic stability of the metal oxides that are present or will be produced during the reaction.
  • the metal oxide with least stability can be selectively reduced to its metallic form easier than the more stable metal oxides.
  • the metal oxide which is reduced can be removed from the system by forming two liquid phases (metal and slag).
  • the ability to bind with oxygen can be evaluated using Gibbs free energy change (AG) for generation of oxide components at various temperatures.
  • Gibbs free energy change (AG) is equal to the difference between enthalpy change and entropy change.
  • T is temperature
  • the metal oxides which are more stable are not reduced completely, they react with slagging components and form a fusible slag.
  • the slagging components include (i) all the rest of the components other than the metal intended for removal and (ii) flux (added on as need basis), and (iii) ash from the carbonaceous material.
  • Melting of the metal which was completely reduced, can be achieved by operating at temperatures higher than the melting temperature of this metal.
  • the melting temperature of the iron can be lowered as carburization of the iron takes place.
  • the lowest melting temperature of H35°C can be achieved at a eutectic composition of 4.3%C.
  • operating at this temperature and carbon content is not realistic, due to availability of carbon and melting temperature of slag (often times higher than 1 l35°C).
  • Melting of the slag is achieved by establishing a slag phase (or phases) which is stable, has a low melting temperature and has affinity to more stable metal oxides which were inherent in the raw materials. Flux is added to the system to enable formation of this slag phase or the composition of the metal-oxide raw materials is manipulated to enable formation of this slag phase.
  • the products are metallic product and slag.
  • the slag is an upgraded concentrate of the more stable metal oxides, which were inherent in the raw materials used.
  • these metals may be in the form of oxides, silicates, and/or carbonates depending on the initial composition of the raw materials and flux used.
  • raw material which contains oxides of iron, manganese and titanium the most stable oxide is titanium oxide, and the least stable oxide is the iron oxide.
  • the iron can be selectively smelted (removed) from the concentrate using selective carbothermic reduction and smelting process.
  • the products of the selective carbothermic reduction and smelting would be metallic iron product and slag.
  • the slag here is an upgraded concentrate of manganese and titanium.
  • Manganese and titanium in the slag can be present as oxides, carbonates or silicates depending on the initial composition of the raw materials and flux used.
  • This slag can be further processed using another (second) selective carbothermic reduction and smelting step, where manganese can be removed from the system by production of metallic manganese product and slag.
  • This second slag is even more upgraded concentrate of titanium. Additional rounds of selective carbothermic reduction and smelting can be used to remove additional rounds of materials as desired until all marketable materials or other desired compounds have been removed.
  • the slag from the second selective carbothermic reduction and smelting process can be used as a raw material for a third selective carbothermic reduction and smelting process.
  • titanium can be removed from the system by production of metallic titanium product and a third slag.
  • This third slag can be used as raw material for other industries such as cement of glass.
  • the metallic product can be used as a raw material for ferroalloy production and slag can be used as a raw material for further processing using pyrometallurgical and hydrometallurgical process.
  • Carbonaceous material addition rates dictate the availability of the reducing agents.
  • the carbonaceous material addition need to be sufficient to supply: (i) reducing agents required for the complete reduction of the metal in consideration for removal, (ii) reducing agents required for the partial reduction of the other metals, and (iii) carbon required for sufficient carburization and melting of the metal (at operational temperatures).
  • Heat transfer is controlled by uniform heating of the raw materials.
  • the raw materials is a mixture of ore or concentrate with carbonaceous material and flux. Depending on the reactor used this mixture may need to be agglomerated, briquetted or densified by other means.
  • the porosity, pore size distribution of these agglomerates need to support: (i) efficient heating and heat transfer of the raw materials, (ii) efficient diffusion of the reducing agents and (iii) efficient diffusion of the reduction reaction products.
  • the selective carbothermic reduction and smelting process operational temperatures are generally higher than the melting temperature of the metal being removed, higher than the fusion temperature of the slag being formed, and lower than the thermodynamic reduction temperature conditions defined for the other metals in the raw materials.
  • the appropriate temperature can be determined using the Gibbs free energy change and Ellingham diagram, shown in FIG. 7, and appropriate phase diagrams (used for desired slag composition calculations). The temperature is higher than the melting temperature of the slag that will result in formation of two immiscible phases (metal and slag).
  • the furnace temperatures need to be lower than l425°C, and higher than l200°C, for effective use of selective carbothermic reduction and smelting to remove iron.
  • This operational temperature range is based on the following considerations: - Furnace temperatures in excess of l425°C are needed for complete reduction of manganese oxides to manganese metal (via carbon monoxide). At temperatures lower than l425°C, reduction of manganese-containing mineral phases to manganese oxide will take place. Concurrently, reduction of iron oxide containing minerals, carburization of the iron, coalescence of the iron, and melting of the iron will take place. The manganese oxide produced will react with the slagging components and form a fusible slag.
  • the slagging components will only include Si0 2 , CaO and MnO. Suitable composition of the slag phase for these oxides is identified. Flux is added to the raw material mixture to produce this slag phase. The composition of this slag phase (marked as target H) on the Si0 2 CaO MnO phase diagram is shown in FIG 8. The melting temperature of this slag phase is l200°C. Thus, the operation temperatures need to be higher than l200°C to achieve smelting and removal of iron.
  • Slag is formed by reaction of all the other components in the ore or concentrate (all the components besides the metal being removed) with ash contained in the carbonaceous material used and flux.
  • the composition of the slag will have a low formation energy, low melting temperature, and high affinity to all the other metals contained in the ore or concentrate. This desired slag composition will vary in accordance to the inherent composition of the raw materials.
  • the main components which make the slag were three oxides Si0 2 , CaO, and MnO.
  • the number of major oxides which make up the slag are more than three.
  • the phase diagram shown in FIG. 8 is considered for favorable slag composition calculation.
  • each example takes as input raw materials that include mixtures of metals and possibly other materials, and by using SCRS in one or more“rounds” desirable materials are removed.
  • FIGS. 3, 5 A and 5B provide a schematic flowpath for the examples that follow.
  • slag or upgraded concentrate 400 is an input material to the process.
  • the raw material slag 400 includes one or more metals.
  • the metals include iron (Mi ron ), as well as other metals M 2 , M 3 , M 4 , ... M n.
  • the process shown in FIGS. 5 A and 5B can be repeated so that in the second round of SCRS there will be n-l metals remaining in the slag 400, then in the subsequent round n-2, and so on.
  • the slag 400 is ground, as is an additive flux (104) as needed and carbonaceous material (106). These materials are only ground to the extent that they are mixed together and blended and densified.
  • the combined slag (400), flux (104), and carbonaceous material (106) is heated for the desired temperature and time to carry out SCRS (508).
  • SCRS SCRS
  • a metal or alloy is separated from a slag.
  • the ferroalloy or alternative ferroalloy (500) can be an alloy of M 2 or a metallic product of M 2 (containing carbides) or an alloy of Mi ron , M 2 , M 3 , M 4 , etc. in FIG. 5A, but it should be understood that as additional rounds of SCRS are carried out other metals or alloys can be extracted from the raw material.
  • the slag (502) produced in FIG. 5A is an“upgraded concentrate” in that, with the iron or other metal, metals, or alloy removed, the remaining materials may be more easily beneficiated.
  • metals M 3 and M may be more easily accessible to beneficiation from the slag (502).
  • the process shown in FIG. 5A can be repeated to acquire metal or alloy corresponding to each of the metals in the initial material. In this way, material in deposits that was previously considered commercially inaccessible can be extracted and used.
  • FIG. 5B is an alternative embodiment in which a metallic product 510 is added to the raw material mixture preparation before SCRS.
  • Metallic product 510 can be the same metallic product (110) described previously with respect to FIG. 1, or it can be a different composition in other embodiments.
  • the process kinetics and thermodynamics are largely based upon the expected interactions between metals, metal oxides, and slag, as well as nucleation sites provided by addition of the metallic product, during heating and SCRS.
  • addition of a metal product to the material mixture before SCRS can make beneficiation of additional desired end products feasible or more practicable, such as by reducing process time or input energy requirements.
  • FIG 1. depict a process for upgrading a low-grade iron-manganese concentrate to a metallic product 110 and a slag 112, using selective carbothermic reduction and smelting 108.
  • the processing conditions are identified based on the chemical and mineralogical characteristics of the raw materials.
  • the processing conditions include: carbonaceous material and flux type and addition rates, furnace temperature and residence time.
  • flux addition 104 may not be necessary for selective carbothermic reduction and smelting 108, since the composition of the slag forming components inherent to the raw materials are suitable for fusible slag formation.
  • This evaluation is conducted using the phase diagram shown in FIG 9, or phase diagrams which include the major slagging components. It is preferred that all of the raw materials are ground (102G, 104G, 106G), in order to have a suitable size distribution (often times 74 micron (200 mesh)) to ensure sufficient surface is available for reactions to proceed.
  • Raw materials including low-grade concentrate 102, carbonaceous material 106 and flux 104 (if needed) are blended uniformly to form a mixture 107.
  • raw material mixture 107 may be agglomerated (using either balling or briquetting).
  • the carbonaceous material 106 added to the raw material mixture is based on the amount of carbon needed for reduction and smelting of the metal (Mi) (for this example iron, M iron ) in consideration for removal in the metallic product 110, and partial reduction of other metal or metals (M 2 , . M n ) (for this example manganese) intended to remain in the slag 112.
  • the flux 104 type and addition is based on the requirements for production of a fusible slag 112 that would melt at the processing temperatures with an affinity to the oxides of the metal or metals (M 2 , . M n ) (manganese oxide) intended to remain in the slag.
  • the raw material mixture 107 is heated at an operational temperature identified, under reducing conditions to promote selective carbothermic reduction and smelting 108, for required amount of residence time.
  • the products are metallic product 110 and slag 112.
  • the metallic product, Mi is iron and iron carbides in this example.
  • the slag is an upgraded concentrate of the other metal or metals (M 2 , . M n ), including upgraded manganese concentrate in this example.
  • these metals will be present in the slag as oxides, silicates or carbonates (for this example manganese oxide, manganese silicate or manganese carbonate).
  • oxides, silicates or carbonates for this example manganese oxide, manganese silicate or manganese carbonate.
  • the metallic product 110 for the first selective carbothermic reduction and smelting step is iron.
  • This metallic product can be marketed either as-is, or can be further refined.
  • sulfur, phosphorus and alkalis inherent to the raw materials would yield in the metallic product. If sulfur, phosphorus and alkali content of the metallic product were higher than intended for the specific use, refining, removal of sulfur and phosphorus is required.
  • Upgraded concentrate 112 of the other metal or metals (M 2 , . M n ) (for this example manganese concentrate) are present in the slag, which can be further processed using additional selective carbothermic reduction and smelting steps to separate/remove the remaining metals to metallic product 110 (for this example it would be manganese or manganese carbide) or to produce ferroalloys of the other metals (for this example, ferro-manganese) as shown in FIG 2 and FIG 3 and FIG 5.
  • the additional selective carbothermic reduction and smelting steps could include grinding of the slag and adding flux and carbonaceous material at producing a second raw material mixture.
  • This second raw material mixture is heated to obtain another metallic product and slag via, selective carbothermic reduction and smelting FIG 2.
  • the furnace temperature and residence time required for this second carbothermic reduction and smelting step would be different from ones used for the first selective carbothermic reduction and smelting.
  • a low-grade iron manganese concentrate was upgraded using selective carbothermic reduction and smelting.
  • This low-grade concentrate contained approximately 33% Fe (iron) and 13% Mn (manganese) and 23% Si0 2.
  • the composition of the low-grade concentrate was evaluated using the phase diagram shown in FIG 9. and it was determined that it was suitable for formation of a fusible slag with desired properties.
  • the low-grade concentrate was blended with coal (reducing carburizing agent) and a raw material mixture 1000 was produced as shown in FIG 10A. The coal addition to the raw material mixture is sufficient to reduce all the iron oxides inherent to the concentrate 100 and partially reduce manganese oxide, and carburize the iron to an extent (for this example 3.5 % C of the metal was targeted).
  • the raw material mixture was heated at a furnace temperature of l400°C and a residence time of 20 min under reducing conditions.
  • a metallic product 1004 and slag 1002 shown in FIG 10B were produced.
  • the metallic product produced was iron; it contained approximately 93% Fe, 0.5% Mn, and 3.3% C.
  • the iron yield to the metallic product was 93%.
  • the slag contained approximately 25% Mn, 5% Fe.
  • the manganese yield to the slag was over 98%.
  • This slag is suitable for further treatment using another selective carbothermic reduction and smelting process to produce ferromanganese metallic product and another upgraded concentrate of the remaining metals.
  • the slag would be ground, blended with appropriate amount of flux and coal and heated at furnace temperatures higher than l500°C, the processing scheme would be as shown in FIG 2.
  • the slag is also suitable for further treatment using hydrometallurgical processes as shown in FIG 6.
  • the manganese contained in the slag was in the form of manganese silicate (Mn 2 Si0 4 ) and manganese oxide (MnO).
  • the slag was leached using and acid lixiviant (H 2 S0 4 or HNO3) and filtered, primary liquor which contain either MnS0 4 or Mh(NO,)? was produced. This liquor was processed with ozone precipitation and filtering to produce high quality manganese dioxide (Mn0 2 ) product.
  • Manganese dioxide is an important raw material for the battery industry.
  • the amount of iron retained in the slag may reduce the leaching efficiency for such processing scheme. Thus if the slag is produced as a raw material for hydrometallurgical processing the amount of iron retained in the slag can be lowered by increasing the furnace temperature (up to l500°C) or increasing the furnace residence time.
  • a low-grade iron manganese concentrate was upgraded using selective carbothermic reduction and smelting.
  • This low-grade concentrate contained approximately 39% Fe (iron) and 19% Mn (manganese) and 7% Si0 2.
  • the composition of this low-grade concentrate was evaluated and sufficient flux was added to produce a fusible slag.
  • a blend of low-grade concentrate, flux and coal was prepared. This raw material mixture was heated at a furnace temperature of l400°C and a residence time of 20 min under reducing conditions.
  • a metallic product and slag were produced.
  • the metallic product produced was an alternative ferroalloy containing approximately 80% Fe, 10% Mn, and 5% C.
  • the iron yield to the metallic product was higher than 98%.
  • the slag produced contained 43% Mn and 2% Fe.
  • the manganese yield to the slag was approximately 74%.
  • the metallic product, alternative ferromanganese produced can be used in steelmaking, and alloying operations as alternative iron and manganese units.
  • the slag can be used as a raw material for either pyrometallurgical or hydrometallurgical processes.
  • the manganese yield in the alternative ferromanganese produced in this example can be manipulated with flux type and addition rate, furnace temperature, furnace residence time and carbonaceous material addition rates.
  • a low-grade iron titanium (ilmenite) concentrate was upgraded using selective carbothermic reduction and smelting.
  • This low-grade concentrate contained approximately 50% Fe, 8% Ti0 2 and 8% Al 2 0 3.
  • Concentrate was blended with limestone as flux and coke as reducing-carburizing agent, and raw material mixtures were produced.
  • Raw materials were briquetted 11000 prior to heating as shown in FIG 11 A. These briquettes were heated in a laboratory scale furnace at a furnace temperature of l400°C and residence time of 20 min, using a graphite crucible filled with coke as a bedding material. It should be noted that the laboratory testing conditions mentioned here should not be considered specific to the selective carbothermic reduction and smelting process. These conditions were picked arbitrarily to demonstrate heating at the required furnace temperatures and residence times.
  • the type of bed used can vary. Although shown as a bed of carbon granules in FIGS. 11A-11C, carbon powder, crucibles, coal, peat, or other carbon-containing sources could be used in alternative embodiments.
  • FIG 11B and 11C A picture of the products soon after completion of the heating (slag (1102)) and metallic product (1004)) and after cooling (slag 1106) and metallic product (1108) are shown in FIG 11B and 11C.
  • the metallic product contained higher than 98% Fe and 1.6% C.
  • the titanium content in the metallic product was less than 0.02%.
  • the slag contained higher than 30% Ti02, and 11% Fe. This high iron containing slag can be further treated using another selective carbothermic reduction and smelting step as shown in FIG 5 for production of iron titanium ferroalloy.
  • the iron content of the slag produced in the flow sheet shown in FIG 4 can be manipulated by altering some of the processing conditions. For example for the same concentrate mentioned in this example the flux amount was adjusted and the residence time was increased to produce slag which contain 39% Ti0 2 and 2% Fe.
  • a low-grade ilmenite (iron titanium) concentrate was upgraded using conventional mineral processing methods. During the concentration process, run off mine ore was ground to liberation size, and low intensity magnetic separation was used to separate non-magnetic portion. The non-magnetic portion of the concentrate was an upgraded concentrate of ilmenite. This upgraded concentrate was further treated using hydrometallurgical methods to produce titanium dioxide (Ti0 2 ) . The magnetic portion separated as a waste product, and contained high concentrations of iron. Thus, it was not suitable for further processing using hydrometallurgical methods.
  • This waste product contained 30.4% Fe and 16.5% Ti0 2. It was upgraded using selective carbothermic reduction and smelting. Approximately 95% of the iron contained in the system yielded in the metallic product.
  • the slag produced was an upgraded concentrate of the ilmenite, approximately 97% Ti0 2 yielded in the slag. The slag only contained 1.6% Fe, indicating a high level of recovery in the metallic product. The resulting slag was suitable for hydrometallurgical processing.
  • the use of selective carbothermic reduction and smelting allowed beneficiation of waste- product as a useful source of iron and titanium.
  • the metallic product (alternative iron) produced is a marketable by-product and slag is an upgraded concentrate of titanium produced from waste rock, which would be discarded without the use of selective carbothermic reduction and smelting process.
  • Slag is an upgraded concentrate of the remaining metals that are not recovered in the metallic product.
  • the slag can be used as a raw material for conventional mineral processing operations, pyrometallurgical processes, hydrometallurgical or electrometallurgical processes and consequent selective carbothermic reduction and smelting processes, in embodiments.
  • pyrometallurgical processes hydrometallurgical or electrometallurgical processes
  • consequent carbothermic reduction and smelting processes in embodiments.
  • other valuable metals contained in the slag can be upgraded and smelted.
  • the metallic product is a by-product. It can be metal itself with metal carbide inclusions, ferroalloys or alternative ferroalloys. This metallic product can be marketed as an alternative metal unit.
  • the first selective carbothermic reduction and smelting step include production of iron as a metallic product.
  • This metallic product can be used as an alternative iron unit for steel production (for basic oxygen furnace steelmaking and electric arc furnace steelmaking), and for ferrous foundry operations.
  • basic oxygen steelmaking the iron could be used as an iron unit and coolant
  • electric arc steelmaking the iron could be used as an iron unit
  • foundry operations the iron could be used as an iron unit and coolant
  • blast furnace operations the iron could be used as an iron unit to increase yield.
  • ferroalloys or alternative ferroalloys produced can also be incorporated in the steel industry.
  • manganese ferroalloys are used to influence steel properties to increase hardenability, strength, toughness, and hot workability.
  • the chrome ferroalloys are used to influence steel properties to increase hardenability, strength and corrosion resistivity.
  • the silicon ferroalloys are used to influence steel properties to improve deoxidation and ferrite handling.
  • the chrome, titanium and vanadium ferroalloys are used to increase hardness, strength, and wear resistance.
  • the products metallic product and slag can be used in the industry as follows:
  • iron can be used as an alternative iron unit for steel production or ferrous foundry operations,
  • Slag can be used as a raw material for ferro manganese or ferro silico manganese production using another selective carbothermic reduction and smelting step or other pyrometallurgical processes.
  • Slag can also be used as a raw material for hydrometallurgical processes to produce manganese dioxide for battery industry.
  • Iron-manganese ore is used as an example for the example provided above, but it should be understood that the invention is not limited to iron and manganese but rather to any metal- containing compound in which selective reduction and smelting could be used to extract target materials.
  • selective carbothermic reduction and smelting includes addition of a sufficient amount of carbonaceous material to the raw material mixture to carry out the complete reduction of iron oxides and partial reduction of the manganese oxides.
  • a flux can be added along with carbonaceous material.
  • flux can include limestone, hydrated lime, dolomite, bauxite, or silica sand. Flux is added to the raw material mixture so that a fusible slag which has affinity manganese oxide can be produced, in one embodiment.
  • metallic product and slag are separated from each other.
  • This separation is based on formation of two immiscible liquids (metal and slag), with different densities and wetting tendency.
  • a picture of hot metallic product and slag produced is shown in FIG 10B. It can be seen from this picture that low density molten slag floats on top of the higher density molten metallic product.
  • the slag separated from the system can be used as a raw material for subsequent selective carbothermic reduction and smelting steps.
  • a flux (e.g., flux 104) can be selected based upon phase diagrams that indicate, based upon a ratio of available compounds and temperature, what materials will be produced.
  • the flux type and amount to be added are based on the desired formation of fusible slag, and its affinity to metal oxides that are intended to be retained in the slag after selective carbothermic reduction and smelting.
  • a phase diagram of Si0 2 , CaO, A1 2 0 3 , and MnO is depicted in FIG. 9
  • targets can be identified that will result in fusible slag during heating. Flux can be added so that the ore has the particular ratios of input materials corresponding to that target composition.
  • the flux composition is chosen to reach the target slag composition, and also to selectively remove metals from the original low-grade ore sequentially.
  • an Ellingham diagram and appropriate phase diagrams can be used to determine the order in which the metals are reduced and thermodynamic conditions for the reduction reactions to take place.
  • the temperature dependency of Gibbs free energy change for such reactions is depicted in the Ellingham graph shown in FIG. 7.
  • Selective carbothermic reduction and smelting are conducted based on the thermodynamic stability of the metal oxides (i.e., removing the metals in order from least to most stable).
  • the metal oxide with the least thermodynamic stability can be selectively reduced to its metallic form more easily than the more stable metal oxides.
  • the metal oxide which is reduced first can be removed from the system by forming two liquid phases, metallic product 110 and slag product 112.
  • the remaining metals that are more stable may begin to reduce.
  • reduction is limited by the thermodynamic and kinetic conditions. These conditions include furnace temperature, residence time, heat transfer and diffusion aspects, as well as the availability of reducing agents, as dictated by the quantity of carbonaceous material (carbon) 106 added.
  • Carbonaceous materials added such that carbon required for the complete reduction of metal intended for removal, partial reduction of the other metals as well as carburization of the metal intended for removal and for the melting of that metal can be supplied to the system. Melting of the metal that is completely reduced to the metallic product 110 can be achieved by operating at temperatures higher than the melting temperature of this metal or melting temperature of this metal and its carbides.
  • Both the metallic product 110 and the slag product 112 are melted during selective carbothermic reduction and smelting 108. Melting of the slag product 112 is achieved by adding a proper flux 104 or manipulation of the metal -oxide raw material composition to establish a slag phase (or phases) which is stable, has a low melting temperature, and has affinity to more stable metal oxides which are present in the raw materials 102. Flux 104 is added to the system to enable formation of this slag product 112.
  • the slag product 112 is an upgraded concentrate of the more stable metal oxides from low-grade ore 102 and can be in the form of oxides, silicates, and/or carbonates depending on the initial composition of the low-grade ore 102 and upon the composition of flux 104.
  • Carbonaceous material addition rate was based on intended metal-oxide reduction degree and intended degree of carburization. For example, trials have shown that when raw material mixtures which contain adequate amount of coal/carbon for complete reduction of the metal (Ml) oxides (intended for removal) were heated (at an adequate furnace temperature and residence time) metallic product that mainly contained that metal (Ml) and an upgraded concentrate virtually free of that metal (Ml) was produced. When raw material mixtures that contain adequate amount of coal/carbon for complete reduction of the metal (Ml) oxides and partial reduction of the other metal (M2) oxides were heated (at an adequate furnace temperature and residence time), metallic product which contain the completely reduced metal (Ml) and partially reduced metal (M2), and an upgraded concentrate was produced.
  • the metallic product was then referred as an alternative ferro-alloy (rich in metal Ml).
  • metallic product which contain both metals (Ml and M2) and a concentrate was produced.
  • the metallic product was then referred as an alternative ferro-alloy.
  • the concentrate produced contained minimal amounts of the metals (Ml and M2). It can be further processes using another SCRS step (to recover other metals or as flux) or another pyrometallurgical, hydrometallurgical or electrometallurgical process.
  • the techniques described above can be used more generally to create metallic product and slag components from raw materials which contain iron and one or more metals (M 2 , M 3 , M 4 , ... M n ).
  • the other metals can be chromium (Cr), manganese (Mn), vanadium (V), silicon (Si), titanium (Ti), barium (Ba), aluminum (Al), magnesium (Mg) and calcium (Ca).
  • FIG. 3 shows addition of metallic product 110 that could be used to form recoverable ferroalloys.

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Abstract

Cette invention concerne un procédé de création d'un minerai de faible qualité valorisé comprenant la détermination du produit fini souhaité en fonction de la composition du minerai de qualité inférieure, du concentré ou des oxydes résiduaires. Le mélange de cette source de matières premières de qualité inférieure avec une matière et un flux carbonés (selon les besoins) en tenant compte de la réduction complète et de la carburation du métal à enlever peut être mis en œuvre de façon que le métal à enlever soit séparé d'un laitier fusible ayant de l'affinité pour d'autres métaux dans le minerai de faible qualité. La réduction carbothermique sélective et la fusion du mélange de matières premières génèrent un produit métallique et un laitier, et le laitier peut être porté à fusion pour le séparer du produit métallique. Ces étapes peuvent être répétées pour réduire sélectivement les métaux séquentiellement, et les transformer en produits à usage commercial.
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CN113549768A (zh) * 2021-07-26 2021-10-26 广东飞南资源利用股份有限公司 一种用于处理冶金冷渣的方法、系统及系统的控制方法

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US2653867A (en) * 1951-07-27 1953-09-29 Quebec Metallurg Ind Ltd Reduction of metal oxides
US3910787A (en) * 1971-07-21 1975-10-07 Ethyl Corp Process for inhibiting formation of intermetallic compounds in carbothermically produced metals
US4036636A (en) * 1975-12-22 1977-07-19 Kennecott Copper Corporation Pyrometallurgical process for smelting nickel and nickel-copper concentrates including slag treatment
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