Processes for the reduction of transition metal oxides

Abstract

The present disclosure relates generally to a process for reducing a transition metal using an alkali metal to produce a reduced transition metal.

Description

[Technical Field]

[0001] The present disclosure relates generally to processes for the reduction of transition metal oxides using alkali metals to produce reduced transition metals. Specifically, the disclosed process is for the reduction of iron oxide using sodium to produce iron. [Background technology]

[0002] The production of metals (such as zinc, iron, nickel, lead, chromium, palladium, copper, and silver) is typically carried out on a large scale electrochemically and / or by carbothermal reduction. As a result, it usually uses highly polluting and non-reusable catalysts and reagents. Furthermore, it is often expensive and energy-consuming due to the many difficulties associated with pyrometallurgical and electrochemical reduction processes. Traditional metal production plants are large and require significant capital investments to build and operate. Commonly used smelting and other metal extraction processes, often carried out in several steps, are highly energy-intensive, and generate large amounts of carbon dioxide (CO2) and other pollutants.

[0003] A number of alternatives have been proposed for the production of (for example) high quality iron, with a substantially lower environmental footprint and lower energy demands. The most sought-after research concepts are electrochemical refiners and electrowinning-based technologies.

[0004] U.S. Patent Application Publication No. 2020 / 0263313 discloses a system and method for molten oxide electrolysis. A metallurgical assembly and system according to U.S. Patent Application Publication No. 2020 / 0263313 may include a refractory tank including a side and a base. The base may define a plurality of centrally located openings within the base. The side and base may at least partially define an interior volume of the refractory tank. The assembly may include a lid configured to removably couple to the refractory tank and form a seal therewith. The lid may define a plurality of openings therethrough. The assembly may also include a current collector proximate the base of the refractory tank. The current collector may include a conductive extension positioned within a plurality of centrally located openings within the base.

[0005] WO 2011 / 092516 discloses a method for preparing iron or iron alloys from iron ore, the method comprising electrolyzing molten iron ore in an electrolytic bath containing at least one molten salt and optionally molten metal, and separating the resulting iron metal or steel. The at least one molten salt is selected from salts of alkali metals, alkaline earth metals, and transition metals. The method of WO 2011 / 092516 comprises either an electrowinning process or a liquid / liquid metal extraction process.

[0006] No. 8,764,962, a method for extracting a target element from an oxide source of the target element, the method including: providing a liquid oxide electrolyte comprising at least 75% by weight of one or more oxide compounds, wherein the oxide source is dissolved to form ionic oxygen species and ionic target element species; providing an anode comprising a metal anode substrate, wherein one element constitutes at least 50% by weight of the metal anode substrate, the one element being more reactive to oxygen than the target element, the metal anode substrate having a solid oxide layer comprising one or more oxides selected from the group consisting of the target element, the metal anode substrate, and the electrolyte, the anode being in contact with the electrolyte; providing a cathode in contact with the electrolyte; driving electrons from the ionic oxygen species in the electrolyte into the metal substrate across the solid oxide layer thereon to form gaseous oxygen; and reducing the ionic target element species in the electrolyte to form a target element liquid at the cathode, wherein the target element has a melting temperature greater than 1200°C.

[0007] International Application PCT / IL2022 / 050754 discloses a process for the reduction of transition metal oxides, which process comprises: (a) reacting a metal oxide of formula M T n O m wherein each one of n and m is 1, 2, 3, 4, 5, 6, or 7; and M T is a first row transition metal selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn), (b) converting a transition metal oxide into an alkali metal (M A ), and the temperature in the reactor is adjusted to a temperature T, to carry out the reaction scheme I and II:I:M T n O m +2m×M A → m×M A 2O+n×M T , II:M A 2O → 2×M A+0.5O2, resulting in a net reaction of III:III:M T n O m → n×M T +0.5m×O2 does not consume the alkali metal and the resulting reaction mixture contains reduced transition metal, M T or an alloy thereof, an alkali metal, and optionally oxygen, A is Na or K, the temperature T is above the melting point of the alkali metal, and M A (c) isolating the reduced transition metal or alloy thereof from the reaction mixture.

[0008] Many medium-scale electrolysis-based plants / reactors have been built. However, none have demonstrated added value over conventional smelters, owing to issues with construction materials, electrodes, and the electronic conductivity of the melt. Specifically, molten oxide and molten salt electrolysis-based reduction has so far been unsuccessful for transition metals, and cannot meet the EU's requirement to decarbonize steel production by 2030.

[0009] Similarly, hydrogen-based reduction processes for steel and other related metals and alloys still need to overcome major technological barriers to meet such decarbonization demands.

[0010] There is a long-standing need for an environmentally friendly process for metal production that avoids electrolysis and hydrogen reduction, is energy-efficient, cost-effective, and scalable. Summary of the Invention

[0011] The following embodiments and aspects thereof are described and illustrated in conjunction with compositions and methods that are intended to be exemplary and illustrative, not limiting in scope. In various embodiments, one or more of the problems noted above are reduced or eliminated, while other embodiments aim to provide other advantages or improvements.

[0012] The present invention provides a process for producing transition metals and their alloys from the corresponding transition metal oxides, which is simpler, more cost-effective, and typically results in higher purity metals than comparable processes for preparing transition metals (e.g., electrolysis).

[0013] It should be understood that throughout this disclosure, the term "metal" refers to the zero oxidation state of the metallic element unless specified as a metal oxide or a constituent in a metal oxide (i.e., a metal cation).

[0014] The present invention employs two reaction sequences of individual reactions that, according to some embodiments, have been surprisingly found to be compatible in reaction sequences (e.g., within a shared reaction or reaction system), creating a synergistic effect that results in a simple process and high yield and purity. The first reaction (Reaction I) is the reduction of iron metal oxide using sodium metal, and optionally the reaction is neat (i.e., the reaction mixture consists essentially of the transition metal oxide and sodium metal used). Specifically, alkali metals such as sodium are known to have lower (more negative) redox potentials than transition metals such as iron, which facilitates the redox reaction of Scheme I. I:Fe n O m +2m×Na → m×Na2O+n×Fe In the formula, n and m are integers (for example, 1 to 7).

[0015] Thus, according to some embodiments, the first reaction yields the desired products iron and sodium oxide. Advantageously, the reaction is carried out at a temperature T in the range of 100° C. to 5000° C. Also, advantageously, the melting point of sodium is relatively low (97.8° C.), and the redox reaction of Scheme I is exothermic, which facilitates the reaction sequence with minimal external energy input.

[0016] Finally, although sodium does not occur in nature, its preparation by electrolysis is convenient as it does not suffer from the obstacles of direct electrolytic reduction of transition metal oxides, which are typically provided as ores and are difficult to electrolyze in solution. Furthermore, sodium can be produced electrochemically from its salt, NaCl, which is abundant in nature.

[0017] The second reaction (Reaction II) is the thermal decomposition of sodium oxide formed in the previous reaction above. Specifically, this is represented in Scheme II: II: Na2O → 2 × Na + 0.5O2

[0018] Yet another advantage of the process of the present invention arises from the net reaction resulting from the combination of the two reaction sequences. Specifically, the net reaction scheme of Reaction I and Reaction II is shown below as Reaction Scheme III (when the equation is balanced by multiplying Scheme II by m): III:Fe n O m → n×Fe+0.5m×O2

[0019] As will be readily understood by those skilled in the art, the net reaction scheme III does not involve the alkali metal as a substantially consumed reactant; rather, it is used in a regenerative / cyclical manner. This is highly advantageous. First, recycling of materials in chemical and commercial large-scale synthesis is of great importance today, as it is recognized that avoiding material consumption contributes to environmental conservation. Second, because the alkali metal does not react net, the only by-product of the reaction is oxygen, which is a harmless gas and is easy to separate from the transition metal produced. As will be seen throughout the process of the present invention, the intermediate step of separating the products of the reduction reaction, i.e., NaO and Fe, greatly improves the ability to dissociate sodium oxide and complete the regenerative cycle.

[0020] Thus, according to some embodiments, there is provided a process for the reduction of iron metal oxides, the process comprising: (1) Formula Fe n Om wherein each one of n and m is 1, 2, 3, 4, 5, 6, or 7; (2) contacting iron oxide with sodium metal in a reactor and adjusting the temperature in the reactor to a first temperature in the range of 100°C to 500°C, to produce a product according to Scheme I: I:Fe n O m + 2m × Na → m × Na2O + n × Fe, and (3) separating NaO and Fe; (4) increasing the temperature of the separated NaO to a second temperature at least 50° C. higher than the first temperature to form Scheme II: II: NaO → 2 × Na + 0.5O, As a result, the net reaction resulting from the reactions of Schemes I and II is III: III:Fe n O m → n×Fe+0.5m×O2 does not consume sodium metal.

[0021] According to some embodiments, the process includes providing an ore comprising hematite, magnetite, goethite, nacrilite, wustite, or a combination thereof. According to some embodiments, the ore further comprises at least one non-ferrous mineral. According to some embodiments, the non-ferrous mineral comprises gibbsite, calcite, silicon dioxide, or a combination thereof. Each possibility represents a separate embodiment of the present invention. According to some embodiments, the ore further comprises silicon dioxide. According to some embodiments, the iron oxide is selected from the group consisting of Fe2O3, Fe3O4, FeOOH, and combinations thereof. According to some embodiments, the iron oxide comprises Fe2O3.

[0022] According to some embodiments, the reactor includes a crucible, and step (2) includes contacting iron oxide with sodium metal in the crucible. According to some embodiments, the crucible includes stainless steel, silicon carbide, copper, aluminum nitride, aluminum oxide, Inconel, ZrO2, or a combination thereof. According to some embodiments, the crucible includes aluminum nitride, aluminum oxide, copper, Inconel, or a combination thereof.

[0023] According to some embodiments, adjusting the temperature in the reactor in step (2) comprises gradually increasing the temperature in the reactor to the first temperature at a rate of 1°C / min to 100°C / min. According to some embodiments, adjusting the temperature in the reactor in step (2) comprises gradually increasing the temperature in the reactor to the first temperature at a rate of 5°C / min to 20°C / min.

[0024] According to some embodiments, increasing the temperature to the second temperature in step (4) comprises gradually increasing the temperature in the reactor to the second temperature at a rate of 1°C / min to 100°C / min. According to some embodiments, increasing the temperature to the second temperature in step (4) comprises gradually increasing the temperature in the reactor to the second temperature at a rate of 5°C / min to 20°C / min.

[0025] According to some embodiments, the process further comprises step (5) isolating sodium metal from the mixture of step (4). According to some embodiments, the isolation of step (5) involves evaporating the sodium metal from the reactor.

[0026] According to some embodiments, the process further comprises the steps of (6) condensing the evaporated sodium metal and (7) transferring the condensed sodium metal to the reactor, thereby recycling the sodium metal.

[0027] According to some embodiments, the process comprises: (1) providing iron oxide; (2) combining iron oxide with sodium metal in a reactor and adjusting the temperature in the reactor to a first temperature; (3) separating NaO and Fe; (4) increasing the temperature of the separated NaO to a second temperature to induce a reaction according to Scheme III; (5) evaporating the sodium metal formed in step (4); and (6) condensing the evaporated sodium metal; and (7) transferring the condensed sodium metal to a reactor; The process further includes repeating steps (1)-(3) for at least one additional sequence.

[0028] According to some embodiments, evaporating sodium metal is carried out at a temperature in the range of 400° C. to 800° C. and a pressure in the range of 0.001 bar to 0.5 bar.

[0029] According to some embodiments, Fe n O m is Fe2O3, FeO, FeOOH, Fe3O4, or a combination thereof, and Reaction Schemes I and III are I:Fe2O3+6×Na → 3×Na2O+2×Fe, III: Fe2O3 → 2×Fe + 1.5×O2, or I: FeO + 2 × Na → Na2O + Fe, III: FeO → Fe + 0.5 × O2, or I:Fe3O4+8×Na → 4×Na2O+3×Fe, III: Fe3O4 → 3×Fe + 2×O2.

[0030] According to some embodiments, step (3) comprises mechanically separating Na2O and Fe to produce isolated iron metal at a purity of at least 90% w / w.

[0031] According to some embodiments, step (3) comprises magnetically separating Na2O and Fe.

[0032] According to some embodiments, step (4) is carried out at a temperature ranging from 400°C to 800°C.

[0033] According to some embodiments, step (4) is carried out at a pressure ranging from 0.001 bar to 0.5 bar.

[0034] According to some embodiments, the reaction mixture of step (2) is substantially free of additional solvent and carrier and consists essentially of iron metal oxide, sodium metal, and the product reduced iron metal and sodium oxide.

[0035] According to some embodiments, step (2) is carried out in an air and water protected environment.

[0036] According to some embodiments, step (2) comprises contacting iron oxide with sodium metal in a weight ratio ranging from 1:20 to 20:1.

[0037] According to some embodiments, the reaction mixture of step (4) is substantially free of additional solvents and carriers.

[0038] According to some embodiments, step (4) is carried out in an air and water protected environment.

[0039] According to some embodiments, a process for the reduction of a transition metal oxide is provided, the process comprising: (1) Formula M T n O m wherein each one of n and m is 1, 2, 3, 4, 5, 6, or 7; and M T is a first row transition metal selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn; (2) contacting at least one transition metal with an alkali metal in a reactor and adjusting the temperature in the reactor to a first temperature in the range of 100°C to 500°C above the melting point of the alkali metal, to produce a product of Scheme I: I:M T n O m +2m×M A → m×M A 2O+n×M T and inducing a reaction according to the formula: A is Na or K), (3) M A 2O and M T and (4) Separated M A 20 to a second temperature at least 50° C. higher than the reduction temperature to form Scheme II: 1.II:M A 2O → 2×M A and inducing a reaction according to +0.5O2, As a result, the net reaction resulting from the reactions of Schemes I and II is III: III:M T n O m → n×M T +0.5m×O2 does not consume alkali metals.

[0040] According to some embodiments, step (1) includes providing an ore comprising hematite, magnetite, goethite, nacrilite, wustite, or a combination thereof. According to some embodiments, the ore further includes at least one non-ferrous mineral. According to some embodiments, the non-ferrous mineral includes gibbsite, calcite, silicon dioxide, or a combination thereof. According to some embodiments, step (2) includes contacting a transition metal oxide with an alkali metal in a crucible. According to some embodiments, adjusting the temperature in the reactor in step (2) includes gradually increasing the temperature in the reactor to a first temperature at a rate of 1°C / min to 100°C / min. According to some embodiments, increasing the temperature to a second temperature in step (4) includes gradually increasing the temperature in the reactor to the second temperature at a rate of 1°C / min to 100°C / min. According to some embodiments, the process further includes step (5) isolating the alkali metal from the mixture of step (4). According to some embodiments, the isolation in step (5) involves evaporating the alkali metal from the reactor. According to some embodiments, the process further comprises the steps of (6) condensing the vaporized alkali metal and (7) transferring the condensed alkali metal to the reactor, thereby recycling the alkali metal.

[0041] According to some embodiments, the process comprises: (1) providing a transition metal oxide; (2) combining a transition metal oxide with an alkali metal in a reactor and adjusting the temperature in the reactor to a first temperature; (3) M A 2O and M T and (4) Separated M A raising the temperature of the 20 to a second temperature to induce a reaction according to Scheme III; (5) evaporating the alkali metal formed in step (4); and (6) condensing the evaporated alkali metal; and (7) transferring the condensed alkali metal to a reactor; The process further includes repeating steps (1)-(3) for at least one additional sequence.

[0042] According to some embodiments, evaporating the alkali metal is carried out at a temperature in the range of 400° C. to 800° C. and a pressure in the range of 0.001 bar to 0.5 bar.

[0043] According to some embodiments, M T is a first row transition metal selected from the group consisting of Fe, Ni, Cr, Cu, Zn, and Mn.

[0044] According to some embodiments, M T is Fe and M T n O m is Fe2O3, FeO, FeOOH, Fe3O4, or a combination thereof, and Reaction Scheme I is I:Fe2O3+6×M A → 3×M A 2O + 2 × Fe, or I:FeO+2×M A → M A 2O+Fe, or I:Fe3O4+8×M A → 4×M A 2O+3×Fe.

[0045] According to some embodiments, M T is Ni and M T n O m is NiO, and Reaction Scheme I is I:NiO+2×M A → M A 2O+Ni.

[0046] According to some embodiments, M T is Cr and M T n O mis Cr2O3, CrO, CrO3, or a combination thereof, and Reaction Scheme I is I:Cr2O3+6×M A → 3×M A 2O+2×Cr, or I:CrO+2×M A → M A 2O+Cr, or I:CrO3+6×M A → 3×M A 2O+Cr.

[0047] According to some embodiments, M T is Cu and M T n O m is CuO, CuO, CuO, or a combination thereof, and Reaction Scheme I is I: Cu2O+2×M A → M A 2O+2Cu, or I:CuO+2×M A → M A 2O+Cu, or I: CuO2 + 4 × M A → 2M A 2O+Cu.

[0048] According to some embodiments, M T is Zn and M T n O m ZnO, and reaction scheme I is I:ZnO+2×M A → M A 2O+Zn.

[0049] According to some embodiments, M T is Mn and M T n O m is MnO, Mn3O4, Mn2O3, MnO2, Mn2O7, or a combination thereof, and Reaction Scheme I is I:MnO+2×MA → M A 2O+Mn, or I:Mn3O4+8×M A → 4×M A 2O+3×Mn, or I:Mn2O3+6×M A → 3×M A 2O + 2 × Mn, or I:MnO2 + 4 × M A → 2M A 2O+Mn, or I:Mn2O7+14×M A → 7×M A 2O + 2 × Mn.

[0050] According to some embodiments, the process is for the preparation of a metal alloy, Step (1) is a step of reacting a compound of formula M Ta n O m , and M Tb i O j wherein each one of i and j is 1, 2, 3, 4, 5, 6, or 7; and M Ta , M Tb each one of which is a transition metal selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn; Step (2) involves combining a transition metal oxide with an alkali metal, Reaction Scheme I shows: Ia:M Ta n O m +2m×M A → m×M A 2O+n×M Ta , Ib:M Tb i O j +2j×M A → j×M A 2O+i×M Tb and Step (2) is reaction IV to form an alloy: IV:M Ta +M Tb → M Ta M Tb was further induced.

[0051] According to some embodiments, the alkali metal is sodium and Scheme II represents: II: Na2O → 2Na + 0.5O2.

[0052] According to some embodiments, step (3) comprises: A 2O and M T and isolated M with a purity of at least 90% w / w by mechanical separation. T According to some embodiments, step (3) comprises producing M A 2O and M T and magnetically separating the

[0053] According to some embodiments, step (4) is carried out at a temperature ranging from 400° C. to 800° C. According to some embodiments, step (4) is carried out at a pressure ranging from 0.001 bar to 0.5 bar. According to some embodiments, the reaction mixture of step (2) is substantially free of additional solvent and support and consists essentially of transition metal oxide, alkali metal, and product reduced transition metal and alkali metal oxide.

[0054] According to some embodiments, step (2) comprises contacting the transition oxide with an alkali metal in a weight ratio ranging from 1:20 to 20:1.

[0055] According to some embodiments, the reaction mixture of step (4) is substantially free of additional solvents and carriers.

[0056] According to some embodiments, a method for the reduction of a transition metal oxide is provided, the method comprising: contacting a transition metal oxide with an alkali metal to form a mixture; heating the mixture to produce transition metal and alkali metal oxides; isolating the transition metal from the heated mixture; and thermally decomposing the alkali metal oxide to regenerate the alkali metal.

[0057] According to some embodiments, the method includes isolating the alkali metal and recycling the alkali metal in another cycle of transition metal oxide reduction.

[0058] According to some embodiments, the isolated transition metal has a purity of at least 90% w / w.

[0059] According to some embodiments, the alkali metal is sodium. According to some embodiments, the alkali metal is potassium.

[0060] According to some embodiments, the transition metal oxide has the formula M T n O m wherein each of n and m is independently 1, 2, 3, 4, 5, 6, or 7; M T is selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn.

[0061] According to some embodiments, the transition metal is Fe. According to some embodiments, the transition metal is Ni. According to some embodiments, the transition metal is Cr. According to some embodiments, the transition metal is Cu. According to some embodiments, the transition metal is Zn. According to some embodiments, the transition metal is Mn.

[0062] According to some embodiments, the isolated transition metal is Fe, Co, Ni, or Cu and has a purity of at least 99% w / w.

[0063] According to some embodiments, the alkali metal is sodium or potassium and the transition metal is selected from Fe, Ni, Cr, Cu, Zn, and Mn.

[0064] According to some embodiments, the transition metal oxide comprises iron oxide and the alkali metal is sodium. According to some embodiments, the transition metal oxide is Fe2O3, FeO, Fe3O4, or a combination thereof.

[0065] According to some embodiments, the transition metal oxide comprises copper oxide and the alkali metal is sodium. According to some embodiments, the transition metal oxide is Cu2O, CuO, CuO2, or a combination thereof.

[0066] According to some embodiments, the transition metal oxide comprises nickel oxide and the alkali metal is sodium.

[0067] According to some embodiments, the transition metal oxide comprises chromium oxide and the alkali metal is sodium. According to some embodiments, the transition metal oxide is Cr2O3, CrO, CrO3, or a combination thereof.

[0068] According to some embodiments, the mixture comprises a molar equivalent or excess of alkali metal relative to the transition metal oxide.

[0069] According to some embodiments, the mixture is neat. According to some embodiments, heating the mixture comprises heating at a temperature of at least 300°C. According to some embodiments, heating the mixture comprises heating at a temperature in the range of 300°C to 3000°C. According to some embodiments, heating the mixture comprises heating at a temperature of at least 350°C. According to some embodiments, heating the mixture comprises heating at a temperature of at least 400°C. According to some embodiments, heating the mixture comprises heating at a temperature of at least 450°C. According to some embodiments, heating the mixture comprises heating at a temperature of at least 500°C.

[0070] According to some embodiments, pyrolyzing the alkali metal oxide comprises heating at a temperature at or above the decomposition temperature of the alkali metal oxide under reduced pressure. [Brief explanation of the drawings]

[0071] The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention. [Figure 1] FIG. 1 is a block diagram illustrating a process for reducing at least one iron oxide to the corresponding iron metal, according to some embodiments. [Figure 2] FIG. 1 is a block diagram illustrating a process for reducing at least one iron oxide to the corresponding iron metal, according to some embodiments. [Figure 3] FIG. 1 is a block diagram illustrating a process for reducing at least one transition metal oxide to the corresponding transition metal or alloy thereof, according to some embodiments. [Figure 4] FIG. 1 is a block diagram illustrating a process for reducing FeO to iron metal, according to some embodiments. [Figure 5] FIG. 1 is a block diagram illustrating a process for reducing FeO to iron metal, according to some embodiments. [Figure 6] FIG. 1 is a block diagram illustrating a process for reducing Fe3O4 to chromium metal, according to some embodiments. [Figure 7] FIG. 1 is a block diagram illustrating a process for reducing at least one iron oxide to the corresponding iron metal, according to some embodiments. [Figure 8] FIG. 1 is a block diagram illustrating a process for reducing at least one iron oxide to the corresponding iron metal, according to some embodiments. [Figure 9] FIG. 1 is a block diagram illustrating a process for reducing at least one transition metal oxide to the corresponding transition metal or alloy thereof, according to some embodiments. [Figure 10] FIG. 1 is a block diagram illustrating a process for reducing FeO to iron metal, according to some embodiments. [Figure 11] FIG. 1 is a block diagram illustrating a process for reducing FeO to iron metal, according to some embodiments. [Figure 12] FIG. 1 is a block diagram illustrating a process for reducing Fe3O4 to chromium metal, according to some embodiments. [Figure 13] 1 is a graph showing the measured temperature (° C.) versus time (min) in the reactor during four reactions between metallic sodium and iron ore, ORE1 (dotted line), ORE2 (long-dashed line), ORE3 (solid line), and ORE4 (dotted and dashed lines). [Figure 14] 1 is an XRD pattern of iron produced from the reaction between iron ORE1 and metallic sodium. [Figure 15] 1 is an XRD pattern of iron produced from the reaction between iron ORE2 and metallic sodium. [Figure 16] 1 is an XRD pattern of iron produced from the reaction between iron ORE3 and metallic sodium. [Figure 17] 1 is an XRD pattern of iron produced from the reaction between iron ORE4 and metallic sodium. [Figure 18]1 is a graph showing the measured temperature (° C.) versus time (min) in a reactor during a reaction between FeO and Na to form iron metal conducted using crucibles made of stainless steel (SS) 304 (blue) and silicon carbide (dashed line) (solid line), according to some embodiments of the present process. [Figure 19] 10 is an XRD pattern of iron produced from the reaction between Fe2O3 and Na conducted using a SS 304 crucible, according to some embodiments of the present process. [Figure 20] 1 is an XRD pattern of iron produced from the reaction between Fe2O3 and Na conducted using a silicon carbide crucible, according to some embodiments of the present process. [Figure 21A] 1 is a graph showing the measured temperature (° C.) versus time (min) in the reactor during the reaction between iron ore and Na to form iron metal, according to some embodiments of the present process. [Figure 21B] 1 is an X-ray diffraction (XRD) pattern of iron produced from the reaction of iron ore with Na, according to some embodiments of the present process. [Figure 22] 1 is an X-ray diffraction (XRD) pattern of iron produced from the reaction of iron ore with Na, according to some embodiments of the present process. [Figure 23] 1 is an X-ray diffraction (XRD) pattern of iron produced from the reaction of iron ore with Na, according to some embodiments of the present process. [Figure 24] 1 is an X-ray diffraction (XRD) pattern of iron produced from the reaction of iron ore with Na, according to some embodiments of the present process. [Figure 25] 1 is an X-ray diffraction (XRD) pattern of iron produced from the reaction of iron ore with Na, according to some embodiments of the present process. [Figure 26] 1 is an X-ray diffraction (XRD) pattern of the reaction product of sodium oxide dissociation without prior separation of the sodium oxide from the iron, according to some embodiments of the present process. [Figure 27]1 is an X-ray diffraction (XRD) pattern of iron produced from the reaction of iron ore with Na, according to some embodiments of the present process. [Figure 28] 1 is an X-ray diffraction (XRD) pattern of sodium oxide magnetically separated from an iron-sodium oxide mixture, according to some embodiments of the present process. [Figure 29] 1 shows a schematic diagram of a system for carrying out the process of the present invention. [Figure 30A] Photograph of condensed sodium formed upon dissociation of sodium oxide. [Figure 30B] Photograph of condensed sodium formed upon dissociation of sodium oxide. DETAILED DESCRIPTION OF THE INVENTION

[0072] In the following description, various aspects of the present disclosure are described. For purposes of explanation, specific configurations and details are set forth in order to provide a thorough understanding of different aspects of the present disclosure. However, it will be apparent to those skilled in the art that the present disclosure may be practiced without the specific details presented herein. Furthermore, well-known features may be omitted or simplified in order not to obscure the present disclosure.

[0073] Before describing the present disclosure in more detail, it is to be understood that this disclosure is not limited to particular embodiments described, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present disclosure will be limited only by the appended claims.

[0074] According to some embodiments, a process is provided for reducing one or more transition metal oxides to the corresponding transition metal or alloy containing same, the process comprising: I:Fe n O m +2m×Na → m×Na2O+n×Fe, II: Na2O → 2 × Na + 0.5O2 where n and m are as defined herein, which leads to the net reaction scheme III: III:Fe n O m → Result is n×Fe+0.5m×O2.

[0075] Several advantages of this process over the art are detailed herein. (i) According to some embodiments, the reaction can be carried out neat (i.e., without solvent), which is environmentally beneficial. (ii) According to some embodiments, conducting Reaction I at a first temperature in the range of 100° C. to 500° C. obtains a reaction mixture in which sodium metal is in a reactive liquid state. (iii) According to some embodiments, using sodium is advantageous because of its relatively low melting point, resulting in only a moderate or no net energy input being required. (iv) According to some embodiments, the redox reaction I is exothermic, which facilitates the 2 reaction sequence with minimal external energy input, another economic and environmental advantage. (v) According to some embodiments, electrosynthesis of sodium that is recycled during the complete reaction cycle is advantageous. (vi) According to some embodiments, the decomposition temperature of sodium oxide is not too high, which further facilitates the two-reaction procedure with minimal external energy input, yet another economic and environmental advantage. (vii) The net reaction III, which represents the combination of reactions I and II, does not consume sodium, i.e., it is completely recycled. Therefore, only a small amount of sodium is required to produce a large amount of iron through the full cycle process of the present invention, which is also both an economic and an environmental advantage. (vii) According to some embodiments, the only by-product of the reaction sequence of the present invention is oxygen, which is a harmless gas and is easy to separate from the transition metal produced.

[0076] According to some embodiments, there is further provided a process for reducing one or more transition metal oxides to the corresponding transition metal or alloy containing same, which process can be carried out according to Scheme I: I:M T n O m +2m×M A → m×M A 2O+n×M T The reaction sequence of T , M A , n, and m are as described herein; and further isolation of the product reduced transition metal or its alloy from the reaction mixture. According to some embodiments, the isolating comprises evaporating the alkali metal oxide, and optionally oxygen and / or alkali metal, from the reactor. According to some embodiments, the evaporation comprises applying a vacuum to the reaction mixture, applying a stream of inert gas to the reaction mixture, or both. Each possibility represents a separate embodiment of the present invention.

[0077] This allows for easy and side reaction free access to carry out the reaction of Scheme II, according to some embodiments. II:M A 2O → 2×M A +0.5O2 This corresponds to the net reaction scheme III: III:M T n O m → n×M T +0.5m×O2, and complete recycling of the alkali metal.

[0078] As will be appreciated by those skilled in the art, several advantages of this process are detailed above. Additionally, the separation of the alkali metal oxide from the reaction mixture (in Scheme I) allows for a facile and clean conversion in Reaction II.

[0079] As can be further appreciated by one skilled in the art, the following embodiments may be applied to any of the processes disclosed herein.

[0080] According to some embodiments, a process for the reduction of transition metal oxides is provided, the process comprising carrying out steps (1)-(4), and optionally additional steps, as detailed herein.

[0081] Reference is now made specifically to step (1) of the present process, which, according to some embodiments, involves providing at least one transition metal oxide.

[0082] According to some embodiments, step (1) comprises reacting a compound of formula M T n O m According to some embodiments, step (1) comprises providing at least one transition metal oxide having the formula M T n O m According to some embodiments, step (1) comprises providing a transition metal oxide having the formula M T n O m According to some embodiments, step (1) comprises providing a single transition metal oxide having the formula Fe n O m According to some embodiments, step (1) comprises providing an iron oxide having the formula Fe n O m According to some embodiments, step (1) comprises providing a single iron oxide having the formula Fe n O m wherein each one of n and m is 1, 2, 3, 4, 5, 6, or 7.

[0083] Specifically, as can be appreciated by those skilled in the art, according to some embodiments, the compound of formula M in step (1) T n O m Alternatively, according to some embodiments, providing two or more transition metal oxides of formula M in step (1) can result in the formation of a transition metal alloy upon completion of the process, as detailed herein. T n O m The provision of one transition metal oxide of step (4) can result in the formation of a reduced transition metal upon completion of the process. Specifically, according to some embodiments, if the reaction mixture of step (4) does not contain a metal or metal oxide that is alloyable with the transition metal provided in step (1), the result of the two reaction sequences of step (4) is a transition metal. However, if another metal that is alloyable with the transition metal provided in step (1), or an oxide of such an alloyable metal, is present in the reaction mixture of step (4), an alloy may be formed from the two metals.

[0084] According to some embodiments, n is 1, 2, 3, 4, 5, 6, or 7. Each possibility represents a separate embodiment of the present invention. According to some embodiments, n is 1, 2, or 3. According to some embodiments, m is 1, 2, 3, 4, 5, 6, or 7. Each possibility represents a separate embodiment of the present invention. According to some embodiments, m is 1, 2, 3, or 4.

[0085] According to some embodiments, M T is a metal. According to some embodiments, M T is a transition metal. According to some embodiments, M T is a first row transition metal.

[0086] Generally, the term "first row transition metal element" refers to any one of elements 21 to 29, namely, scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu).

[0087] According to some embodiments, M T is selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn. Each possibility represents a separate embodiment of the present invention. According to some embodiments, M T is a first row transition metal selected from the group consisting of Fe, Ni, Cr, Cu, Zn, and Mn. According to some embodiments, the transition metal is Sc. According to some embodiments, the transition metal is Ti. According to some embodiments, the transition metal is V. According to some embodiments, the transition metal is Cr. According to some embodiments, the transition metal is Mn. According to some embodiments, the transition metal is Fe. According to some embodiments, the transition metal is Co. According to some embodiments, the transition metal is Ni. According to some embodiments, the transition metal is Cu. According to some embodiments, the transition metal is Zn.

[0088] According to some embodiments, the transition metal oxide is provided in step (1) as a solid.

[0089] As detailed herein, according to some embodiments, during steps (2) and (4), the transition metal oxide is consumed to provide the transition metal and oxygen, while the alkali metal is conserved and recycled, allowing for the continuous supply of additional transition metal oxide to the reaction mixture and the continuous production of additional transition metal.

[0090] According to some embodiments, during step (2), the alkali metal in the reactor is in molar equivalent or excess relative to the transition metal oxide therein.

[0091] As used herein, it should be understood that "X% molar excess" and "molar equivalent" take into account the molar ratio required for complete reaction according to the schemes presented herein. For example, if the transition metal oxide is FeO, the reaction equation of Scheme I is FeO + 6 × Na → 3 × NaO + 2 × Fe, which requires 6 sodium equivalents per FeO. In such a case, 6 moles of Na per mole of FeO would be considered a molar equivalent, and more than 6 moles of Na per mole of FeO would be considered a molar excess of sodium; for example, 12 moles of Na per mole of FeO would be considered a 100% molar excess.

[0092] According to some embodiments, during step (2), the alkali metal in the reactor is in molar excess relative to the transition metal oxide therein. According to some embodiments, the molar excess is at least 10% mol / mol. According to some embodiments, the molar excess is at least 20% mol / mol. According to some embodiments, the molar excess is at least 30% mol / mol. According to some embodiments, the molar excess is at least 40% mol / mol. According to some embodiments, the molar excess is at least 50% mol / mol. According to some embodiments, the molar excess is at least 75% mol / mol. According to some embodiments, the molar excess is at least 100% mol / mol. According to some embodiments, the molar excess is at least 150% mol / mol.

[0093] According to some embodiments, the at least one transition metal oxide is selected from the group consisting of Sc2O3, TiO2, Ti2O3, VO, VO2, VO5, Cr2O3, CrO, CrO3, MnO, Mn3O4, Mn2O3, MnO2, Mn2O7, Fe2O3, FeO, Fe3O4, CoO, Co2O3, Co3O4, NiO, Cu2O, CuO, CuO2, ZnO, and any combination thereof, with each possibility representing a separate embodiment of the present invention.

[0094] According to some embodiments, M T n O m contains Sc2O3.

[0095] According to some embodiments, M T n O m comprises TiO2, Ti2O3, or a combination thereof. According to some embodiments, M T n O m According to some embodiments, M T n O m According to some embodiments, M T n O m contains a mixture of titanium oxides.

[0096] According to some embodiments, M T n O m comprises VO, V2O3, VO2, V2O5, or a combination thereof. According to some embodiments, M T n O m According to some embodiments, M T n O m According to some embodiments, M T n O m According to some embodiments, M T n Om According to some embodiments, M T n O m contains a mixture of vanadium oxides.

[0097] According to some embodiments, M T n O m comprises Cr2O3, CrO, CrO3, or a combination thereof. According to some embodiments, M T n O m According to some embodiments, M T n O m According to some embodiments, M T n O m According to some embodiments, M T n O m contains a mixture of chromium oxides.

[0098] According to some embodiments, M T n O m comprises MnO, Mn3O4, Mn2O3, MnO2, Mn2O7, or a combination thereof. According to some embodiments, M T n O m According to some embodiments, M T n O m According to some embodiments, M T n O m According to some embodiments, M T n O m According to some embodiments, M T n O m According to some embodiments, M T n Om contains a mixture of manganese oxides.

[0099] According to some embodiments, M T n O m comprises Fe2O3, FeOOH, FeO, Fe3O4, or a combination thereof. According to some embodiments, M T n O m According to some embodiments, M T n O m According to some embodiments, M T n O m According to some embodiments, M T n O m According to some embodiments, M T n O m contains a mixture of iron oxides.

[0100] According to some embodiments, the iron oxide comprises Fe2O3, FeOOH, FeO, Fe3O4, or a combination thereof. According to some embodiments, the iron oxide comprises Fe2O3. According to some embodiments, the iron oxide comprises FeO. According to some embodiments, the iron oxide comprises Fe3O4. According to some embodiments, the iron oxide comprises FeOOH. According to some embodiments, the iron oxide comprises a mixture of iron oxides.

[0101] According to some embodiments, the iron oxide is selected from the group consisting of Fe2O3, FeOOH, FeO, Fe3O4, and combinations thereof. According to some embodiments, the iron oxide is Fe2O3. According to some embodiments, the iron oxide is FeO. According to some embodiments, the iron oxide is Fe3O4. According to some embodiments, the iron oxide is FeOOH. According to some embodiments, the iron oxide is a mixture of iron oxides.

[0102] According to some embodiments, the iron oxide comprises hematite, magnetite, goethite, nacrite, wustite, or a combination thereof. According to some embodiments, the iron oxide comprises hematite. According to some embodiments, the iron oxide comprises magnetite. According to some embodiments, the iron oxide comprises goethite. According to some embodiments, the iron oxide comprises wustite. According to some embodiments, the iron oxide comprises at least two of hematite, magnetite, wustite, and goethite.

[0103] According to some embodiments, step (1) comprises providing an ore comprising a transition metal oxide. According to some embodiments, step (1) comprises providing an ore comprising iron oxide.

[0104] According to some embodiments, the ore comprises Fe2O3, FeOOH, FeO, Fe3O4, or a combination thereof. According to some embodiments, the ore comprises Fe2O3. According to some embodiments, the ore comprises FeO. According to some embodiments, the ore comprises Fe3O4. According to some embodiments, the ore comprises FeOOH. According to some embodiments, the ore comprises a mixture of ores.

[0105] According to some embodiments, the ore comprises hematite, magnetite, goethite, nacrites, wustite, or a combination thereof. According to some embodiments, the ore comprises hematite. According to some embodiments, the ore comprises magnetite. According to some embodiments, the ore comprises goethite. According to some embodiments, the ore comprises wustite. According to some embodiments, the ore comprises at least two of hematite, wustite, magnetite, and goethite.

[0106] According to some embodiments, the ore further comprises at least one of silicon oxide, nacrite, magnesium silicon hydroxide, aluminum hydroxide, and combinations thereof. According to some embodiments, the ore further comprises at least two of silicon oxide, nacrite, magnesium silicon hydroxide, aluminum hydroxide, and combinations thereof. According to some embodiments, the ore further comprises silicon oxide. According to some embodiments, the ore further comprises nacrite. According to some embodiments, the ore further comprises magnesium silicon hydroxide. According to some embodiments, the ore further comprises aluminum hydroxide.

[0107] According to some embodiments, the ore comprises at least 30% w / w hematite. According to some embodiments, the ore comprises at least 35% w / w hematite. According to some embodiments, the ore comprises at least 40% w / w hematite. According to some embodiments, the ore comprises at least 45% w / w hematite. According to some embodiments, the ore comprises at least 50% w / w hematite. According to some embodiments, the ore comprises at least 55% w / w hematite. According to some embodiments, the ore comprises at least 60% w / w hematite. According to some embodiments, the ore comprises at least 65% w / w hematite. According to some embodiments, the ore comprises no more than 95% w / w hematite. According to some embodiments, the ore comprises no more than 90% w / w hematite. According to some embodiments, the ore comprises no more than 85% w / w hematite. According to some embodiments, the ore comprises 40% to 90% w / w hematite.

[0108] According to some embodiments, the ore contains at least 1% w / w magnetite. According to some embodiments, the ore contains at least 2% w / w magnetite. According to some embodiments, the ore contains at least 3% w / w magnetite. According to some embodiments, the ore contains at least 5% w / w magnetite. According to some embodiments, the ore contains at least 10% w / w magnetite. According to some embodiments, the ore contains at least 12% w / w magnetite. According to some embodiments, the ore contains no more than 50% w / w magnetite. According to some embodiments, the ore contains no more than 25% w / w magnetite. According to some embodiments, the ore contains no more than 20% w / w magnetite. According to some embodiments, the ore contains between 1% and 20% w / w magnetite.

[0109] According to some embodiments, the ore comprises at least 0.3% w / w goethite. According to some embodiments, the ore comprises at least 2% w / w goethite. According to some embodiments, the ore comprises at least 5% w / w goethite. According to some embodiments, the ore comprises at least 10% w / w goethite. According to some embodiments, the ore comprises at least 25% w / w goethite. According to some embodiments, the ore comprises at least 40% w / w goethite. According to some embodiments, the ore comprises no more than 75% w / w goethite. According to some embodiments, the ore comprises no more than 50% w / w goethite. According to some embodiments, the ore comprises between 0.3% and 45% w / w goethite.

[0110] According to some embodiments, the ore contains at least 0.5% w / w naclite. According to some embodiments, the ore contains at least 1% w / w naclite. According to some embodiments, the ore contains at least 5% w / w naclite. According to some embodiments, the ore contains at least 2% w / w naclite. According to some embodiments, the ore contains 20% w / w or less naclite. According to some embodiments, the ore contains 15% w / w or less naclite. According to some embodiments, the ore contains 1% to 10% w / w naclite.

[0111] According to some embodiments, the ore contains at least 0.5% w / w nakhlite. According to some embodiments, the ore contains at least 1% w / w wustite. According to some embodiments, the ore contains at least 5% w / w wustite. According to some embodiments, the ore contains at least 2% w / w wustite. According to some embodiments, the ore contains 20% w / w or less wustite. According to some embodiments, the ore contains 15% w / w or less wustite. According to some embodiments, the ore contains 1% to 10% w / w wustite.

[0112] According to some embodiments, the ore further comprises at least one non-ferrous mineral. According to some embodiments, the non-ferrous mineral comprises gibbsite, calcite, silicon dioxide, or a combination thereof.

[0113] According to some embodiments, the ore comprises at least 1% w / w silicon dioxide. According to some embodiments, the ore comprises at least 1.5% w / w silicon dioxide. According to some embodiments, the ore comprises at least 2.5% w / w silicon dioxide. According to some embodiments, the ore comprises at least 5% w / w silicon dioxide. According to some embodiments, the ore comprises no more than 20% w / w silicon dioxide. According to some embodiments, the ore comprises no more than 15% w / w silicon dioxide. According to some embodiments, the ore comprises between 1% and 15% w / w silicon dioxide.

[0114] According to some embodiments, the ore comprises at least 1% w / w gibbsite. According to some embodiments, the ore comprises at least 1.5% w / w gibbsite. According to some embodiments, the ore comprises at least 2.5% w / w gibbsite. According to some embodiments, the ore comprises at least 5% w / w gibbsite. According to some embodiments, the ore comprises no more than 20% w / w gibbsite. According to some embodiments, the ore comprises no more than 15% w / w gibbsite. According to some embodiments, the ore comprises between 1% and 15% w / w gibbsite.

[0115] According to some embodiments, the ore comprises at least 1% w / w calcite. According to some embodiments, the ore comprises at least 1.5% w / w calcite. According to some embodiments, the ore comprises at least 2.5% w / w calcite. According to some embodiments, the ore comprises at least 5% w / w calcite. According to some embodiments, the ore comprises no more than 20% w / w calcite. According to some embodiments, the ore comprises no more than 15% w / w calcite. According to some embodiments, the ore comprises between 1% and 15% w / w calcite.

[0116] According to some embodiments, M T n O mcomprises Co2O3, CoO, Co3O4, or a combination thereof. According to some embodiments, M T n O m According to some embodiments, M T n O m According to some embodiments, M T n O m According to some embodiments, M T n O m comprises a mixture of cobalt oxides. T n O m According to some embodiments, M T n O m comprises Cu2O, CuO, CuO2, or a combination thereof. According to some embodiments, M T n O m According to some embodiments, M T n O m According to some embodiments, M T n O m According to some embodiments, M T n O m According to some embodiments, M comprises a mixture of copper oxides. T n O m contains ZnO.

[0117] Reference is now made specifically to step (2) of the process, which comprises contacting at least one transition metal with an alkali metal in a reactor. According to some embodiments, step (2) comprises contacting iron oxide with sodium metal in a reactor.

[0118] According to some embodiments, step (2) further comprises adjusting the temperature in the reactor to a first temperature. According to some embodiments, the first temperature is in the range of 100 to 500°C. According to some embodiments, step (2) involves inducing a reaction between iron oxide and sodium. According to some embodiments, the reaction is represented by Scheme I: I:Fe n O m +2m×Na → m×Na2O+n×Fe.

[0119] According to some embodiments, step (2) involves inducing a reaction between a transition metal oxide and an alkali metal. According to some embodiments, the reaction is represented by Scheme I: I:M T n O m +2m×M A → m×M A 2O+n×M T is in accordance with.

[0120] According to some embodiments, M A is Na or K.

[0121] According to some embodiments, step (2) comprises annealing a transition metal oxide with an alkali metal (M A ) with an alkali metal. According to some embodiments, the act of combining the transition metal oxide with the alkali metal is carried out at a first temperature. Specifically, according to some embodiments, if the reaction has not yet begun, external heating is required to reach the first temperature. Alternatively, according to some embodiments, after the reaction has begun, its exothermic nature can at least partially maintain or increase the internal temperature, such that less external heating is required, or even external heating can be at least temporarily stopped.

[0122] According to some embodiments, adjusting the temperature in the reactor to a first temperature comprises increasing the temperature in the reactor to the first temperature. According to some embodiments, step (2) comprises adjusting the temperature by induction.

[0123] The term "induction heating" refers to the process of heating electrically conductive materials, i.e., metals or semiconductors, by electromagnetic induction through an induction coil that creates an oscillating electromagnetic field within the coil to heat and sometimes melt steel, copper, brass, graphite, gold, silver, aluminum, or carbides. An induction heater includes an electromagnet and an electronic oscillator, i.e., an antenna, that passes an alternating current (AC) through the electromagnet. The rapidly alternating magnetic field penetrates the object and generates electrical currents within the conductor, called eddy currents. The eddy currents flow through the resistance of the material and heat it by Joule heating.

[0124] According to some embodiments, the value of the first temperature is selected to carry out the reaction of Scheme I. In other words, the first temperature provides sufficient energy to the reaction system to overcome the activation energy of Reaction I and provide suitable reaction conditions.

[0125] For the reaction of Scheme I, according to some embodiments, an important parameter is the physical state of the reactants. Specifically, according to some embodiments, it is advantageous for the reaction of the present method to be carried out neat (i.e., without a solvent). Also, at room temperature, both the alkali metal and transition metal oxide reactants are in the solid state, which tends to slow down or prevent the chemical reaction.

[0126] According to some embodiments, the first temperature is at least 100°C. According to some embodiments, the first temperature is at least 125°C. According to some embodiments, the first temperature is at least 150°C. According to some embodiments, the first temperature is at least 175°C. According to some embodiments, the first temperature is at least 200°C. According to some embodiments, the first temperature is at least 225°C. According to some embodiments, the first temperature is at least 250°C. According to some embodiments, the first temperature is at least 300°C. According to some embodiments, the first temperature is at least 350°C. According to some embodiments, the first temperature is at least 400°C. According to some embodiments, the first temperature is at least 450°C. According to some embodiments, the first temperature is at least 500°C. According to some embodiments, the first temperature is at least 510°C. According to some embodiments, the first temperature is at least 520°C. According to some embodiments, the first temperature is at least 530°C. According to some embodiments, the first temperature is at least 540°C. According to some embodiments, the first temperature is at least 550°C. According to some embodiments, the first temperature is at least 600°C. Each possibility represents a separate embodiment of the present invention. According to some embodiments, the first temperature is in the range of 200-300°C. This includes each value and subrange within the specified range.

[0127] According to some embodiments, the first temperature is 600°C or less. According to some embodiments, the first temperature is 575°C or less. According to some embodiments, the first temperature is 550°C or less. According to some embodiments, the first temperature is 500°C or less. According to some embodiments, the first temperature is 475°C or less. According to some embodiments, the first temperature is 450°C or less. According to some embodiments, the first temperature is 425°C or less. According to some embodiments, the first temperature is 400°C or less.

[0128] According to some embodiments, the reaction of Scheme II is carried out where the sodium oxide is in the solid phase.

[0129] As used herein, the term "alkali metal" includes any compound containing an alkali metal in its 0 (zero) oxidation state. Thus, the term includes sodium metal, Na(0), and potassium metal, K(0), and alloys thereof, in which at least one alkali metal is in its zero oxidation state, e.g., NaK.

[0130] According to some embodiments, alkali metals (M A ) is Na or K. According to some embodiments, the alkali metal is Na. According to some embodiments, the alkali metal is K. According to some embodiments, the alkali metal is NaK.

[0131] Sodium-potassium alloy, colloquially referred to as NaK, is an alloy of the alkali metals sodium potassium, which is normally liquid at room temperature.

[0132] According to some embodiments, the reaction of Scheme I is carried out neat. According to some embodiments, the reaction of Scheme II is carried out neat. According to some embodiments, the two-reaction sequence of step (2) is carried out neat.

[0133] According to some embodiments, the reaction mixture of step (2) is substantially free of additional solvent. According to some embodiments, the reaction mixture of step (2) is substantially free of additional solvent and carrier.

[0134] The term "solvent" refers to a non-reactive component of a composition that reduces the viscosity of the composition. Typically, a solvent has such volatility that it is removed under workup conditions (e.g., elevated temperature and / or reduced pressure) after completion of a chemical reaction. The terms "substantially devoid solvents" or "solvent-free" refer to a composition that does not contain or is substantially free of solvents, as defined above. According to some embodiments, a substantially solvent-free composition may contain trace amounts of solvent, such as 5% w / w or less, 3% w / w or less, 2% w / w or less, 1% or less, or 0.5% w / w or less.

[0135] According to some embodiments, the reaction mixture of step (2) consists essentially of a transition metal oxide, an alkali metal, and the product reduced transition metal or its alloy and alkali metal oxide. According to some embodiments, the condensed phase in the reactor during step (2) consists essentially of a transition metal oxide, an alkali metal, and the product reduced transition metal or its alloy and alkali metal oxide.

[0136] The term "consisting essentially of" means that the reaction mixture of step (2) contains primarily the transition metal oxide, the alkali metal, and the product reduced transition metal or its alloy. Specifically, according to some embodiments, it does not contain substantial amounts of solvent or carrier, or any components not involved in Reaction Schemes I and II. According to some embodiments, the reaction mixture of step (2) contains no more than 5% w / w, no more than 3% w / w, no more than 2% w / w, or no more than 1% w / w of other compounds. Each possibility represents a separate embodiment of the present invention. The other compounds may include impurities from the production or mining of the transition metal oxide.

[0137] According to some embodiments, the resulting reaction mixture formed upon contacting the transition metal oxide and the alkali metal in step (2) is in a solid state. According to some embodiments, the resulting reaction mixture formed upon contacting the transition metal oxide and the alkali metal in step (2) is a heterogeneous mixture.

[0138] According to some embodiments, the reaction mixture of step (2) does not contain any metals or metal oxides that are alloyable with the transition metal provided in step (1).

[0139] According to some embodiments, the reaction mixture of step (2) contains an alloyable metal or metal oxide that is alloyable with the transition metal provided in step (1), as described in more detail below with respect to optional alloy formation.

[0140] According to some embodiments, the alkali metal in the reactor is in a molar equivalent or excess relative to the transition metal oxide therein during step (2). According to some embodiments, the alkali metal in the reactor is in molar excess relative to the transition metal oxide therein during step (2). According to some embodiments, the molar excess is at least 5%, at least 10%, at least 25%, at least 50%, at least 100%, or at least 200%. Each possibility represents a separate embodiment of the present invention.

[0141] According to some embodiments, the reactor in which step (2) is performed comprises a crucible. According to some embodiments, step (2) comprises contacting iron oxide with sodium metal in the crucible. According to some embodiments, step (1) is performed in the crucible. According to some embodiments, step (2) comprises contacting a transition metal oxide with an alkali metal in the crucible.

[0142] The term "crucible" refers to a container in which metals or other substances can be melted or subjected to very high temperatures. Historically, crucibles were usually made from clay, but they can be made from any material that can withstand temperatures high enough to melt or otherwise transform its contents.

[0143] According to some embodiments, the crucible has an open-ended cylindrical or conical shape. According to some embodiments, the crucible is heat resistant. According to some embodiments, the crucible is substantially chemically resistant to reaction with alkali metals. According to some embodiments, the crucible is substantially chemically resistant to reaction with alkali metals at a first temperature.

[0144] According to some embodiments, the crucible comprises stainless steel, silicon carbide, copper, aluminum nitride, alumina, Inconel, ZrO2, or a combination thereof. Each possibility represents a separate embodiment of the present invention. According to some embodiments, the crucible comprises aluminum nitride, aluminum oxide, copper, Inconel, or a combination thereof. According to some embodiments, the crucible comprises silicon carbide.

[0145] According to some embodiments, adjusting the temperature in the reactor in step (2) comprises gradually increasing the temperature in the reactor to a first temperature.

[0146] According to some embodiments, adjusting the temperature in the reactor in step (2) comprises gradually increasing the temperature in the reactor to a first temperature.

[0147] According to some embodiments, adjusting the temperature in the reactor in step (2) comprises gradually increasing the temperature in the reactor to the first temperature at a rate of 1°C / min to 100°C / min. According to some embodiments, adjusting the temperature in the reactor in step (2) comprises gradually increasing the temperature in the reactor to the first temperature at a rate of 5°C / min to 20°C / min. According to some embodiments, adjusting the temperature in the reactor in step (2) comprises gradually increasing the temperature in the reactor to the first temperature at a rate of 5°C / min to 15°C / min.

[0148] According to some embodiments, increasing the temperature to the first temperature is carried out at a rate of at least 1° C. / min. According to some embodiments, increasing the temperature to the first temperature is carried out at a rate of at least 2° C. / min. According to some embodiments, increasing the temperature to the first temperature is carried out at a rate of at least 5° C. / min. According to some embodiments, increasing the temperature to the first temperature is carried out at a rate of at least 7° C. / min. According to some embodiments, increasing the temperature to the first temperature is carried out at a rate of at least 10° C. / min. According to some embodiments, increasing the temperature to the first temperature is carried out at a rate of at least 15° C. / min. According to some embodiments, the rate is no greater than 100° C. / min. According to some embodiments, the rate is no greater than 75° C. / min. According to some embodiments, the rate is no greater than 50° C. / min. According to some embodiments, the rate is no greater than 40° C. / min. According to some embodiments, the rate is no greater than 30° C. / min. According to some embodiments, the rate is no greater than 20° C. / min. According to some embodiments, the rate is 15°C / min or less. According to some embodiments, the rate is in the range of 1°C / min to 100°C / min. According to some embodiments, the rate is in the range of 5°C / min to 20°C / min.

[0149] According to some embodiments, step (2) comprises contacting the transition metal oxide with an alkali metal in a weight ratio ranging from 1:20 to 20:1. According to some embodiments, step (2) comprises contacting the transition metal oxide with an alkali metal in a weight ratio ranging from 1:10 to 10:1. According to some embodiments, step (2) comprises contacting the transition metal oxide with an alkali metal in a weight ratio ranging from 1:5 to 5:1. According to some embodiments, step (2) comprises contacting the transition metal oxide with an alkali metal in a weight ratio ranging from 1:3 to 3:1. According to some embodiments, step (2) comprises contacting the transition metal oxide with an alkali metal in a weight ratio ranging from 1:2 to 2:1.

[0150] According to some embodiments, step (2) comprises contacting the transition metal oxide with the alkali metal in a weight ratio of at least 1:10. According to some embodiments, step (2) comprises contacting the transition metal oxide with the alkali metal in a weight ratio of at least 1:8. According to some embodiments, step (2) comprises contacting the transition metal oxide with the alkali metal in a weight ratio of at least 1:7. According to some embodiments, step (2) comprises contacting the transition metal oxide with the alkali metal in a weight ratio of at least 1:5. According to some embodiments, step (2) comprises contacting the transition metal oxide with the alkali metal in a weight ratio of at least 1:4. According to some embodiments, step (2) comprises contacting the transition metal oxide with the alkali metal in a weight ratio of at least 1:3. According to some embodiments, step (2) comprises contacting the transition metal oxide with the alkali metal in a weight ratio of at least 1:2. According to some embodiments, step (2) comprises contacting the transition metal oxide with the alkali metal in a weight ratio of at least 1:1. According to some embodiments, step (2) comprises contacting the transition metal oxide with an alkali metal in a weight ratio of at least 1.5:1. According to some embodiments, step (2) comprises contacting the transition metal oxide with an alkali metal in a weight ratio of 10:1 or less. According to some embodiments, step (2) comprises contacting the transition metal oxide with an alkali metal in a weight ratio of 7:1 or less. According to some embodiments, step (2) comprises contacting the transition metal oxide with an alkali metal in a weight ratio of 5:1 or less. According to some embodiments, step (2) comprises contacting the transition metal oxide with an alkali metal in a weight ratio of 4:1 or less. According to some embodiments, step (2) comprises contacting the transition metal oxide with an alkali metal in a weight ratio of 3:1 or less. According to some embodiments, step (2) comprises contacting the transition metal oxide with an alkali metal in a weight ratio of 2:1 or less. According to some embodiments, step (2) comprises contacting the transition metal oxide with an alkali metal in a weight ratio of 1:1 or less.According to some embodiments, step (2) comprises contacting the transition metal oxide with an alkali metal in a weight ratio of 1:1.5 or less. In the context of this paragraph, it is understood that "at least" and "less than" refer to the number of molecules. For example, at least 1:10 can include, but is not limited to, 1:10, 3:10, 7:10, 17:10, etc., and 5:1 or less can include, but is not limited to, 5:1, 4:1, 1:1, 0.7:1, etc.

[0151] According to some embodiments, step (2) comprises contacting the iron oxide with sodium metal in a weight ratio of at least 1:10. According to some embodiments, step (2) comprises contacting the iron oxide with sodium metal in a weight ratio of at least 1:8. According to some embodiments, step (2) comprises contacting the iron oxide with sodium metal in a weight ratio of at least 1:7. According to some embodiments, step (2) comprises contacting the iron oxide with sodium metal in a weight ratio of at least 1:5. According to some embodiments, step (2) comprises contacting the iron oxide with sodium metal in a weight ratio of at least 1:4. According to some embodiments, step (2) comprises contacting the iron oxide with sodium metal in a weight ratio of at least 1:3. According to some embodiments, step (2) comprises contacting the iron oxide with sodium metal in a weight ratio of at least 1:2. According to some embodiments, step (2) comprises contacting the iron oxide with sodium metal in a weight ratio of at least 1:1. According to some embodiments, step (2) comprises contacting the iron oxide with sodium metal in a weight ratio of at least 1.5:1. According to some embodiments, step (2) comprises contacting the iron oxide with sodium metal in a weight ratio of 10:1 or less. According to some embodiments, step (2) comprises contacting the iron oxide with sodium metal in a weight ratio of 7:1 or less. According to some embodiments, step (2) comprises contacting the iron oxide with sodium metal in a weight ratio of 5:1 or less. According to some embodiments, step (2) comprises contacting the iron oxide with sodium metal in a weight ratio of 4:1 or less. According to some embodiments, step (2) comprises contacting the iron oxide with sodium metal in a weight ratio of 3:1 or less. According to some embodiments, step (2) comprises contacting the iron oxide with sodium metal in a weight ratio of 2:1 or less. According to some embodiments, step (2) comprises contacting the iron oxide with sodium metal in a weight ratio of 1:1 or less. According to some embodiments, step (2) comprises contacting iron oxide with sodium metal in a weight ratio of 1:1.5 or less.

[0152] In some embodiments, step (2) is carried out in an air-protected environment. In some embodiments, step (2) is carried out in a water-protected environment. In some embodiments, step (2) is carried out in an air- and water-protected environment.

[0153] In particular, it will be appreciated that alkali metals are highly reactive and require specific reaction conditions, such as running under an inert gas.

[0154] According to some embodiments, step 2 further comprises flowing an inert gas through the reactor. According to some embodiments, step 2 is carried out under an inert gas. According to some embodiments, the inert gas is nitrogen or argon. Each possibility represents a separate embodiment of the present invention.

[0155] According to some embodiments, the reactor is closed during step (2). According to some embodiments, the reactor is closed under an inert atmosphere during step (2). According to some embodiments, the reactor is closed under an inert gas atmosphere during step (2). According to some embodiments, the reactor is closed during step (2) and the two reaction sequences are carried out at elevated pressure.

[0156] The term "high pressure" refers to any pressure above atmospheric pressure.

[0157] Advantageously, the reaction time is short, which is economical and energy consuming.

[0158] According to some embodiments, step (2) is carried out for 6 hours or less, 4 hours or less, 3 hours or less, 2 hours or less, 1 hour or less, 45 minutes or less, or 30 minutes or less. Each possibility represents a separate embodiment of the present invention. According to some embodiments, step (2) is carried out for 1 hour or less. According to some embodiments, step (2) is carried out for at least 5 minutes, at least 10 minutes, at least 15 minutes, at least 20 minutes, or at least 25 minutes. Each possibility represents a separate embodiment of the present invention.

[0159] References to the duration of step (2) should be understood to refer to individual runs of step (2). Specifically, as detailed herein, according to some embodiments, the process is carried out cyclically, with the alkali metal being recycled after completion of the reaction and returned for reuse in subsequent runs of step (2). Accordingly, it should be understood that, consistent with the above provisions directed to individual runs of step (2), repetitions of step (2) are permitted to cumulatively exceed the lower threshold established above.

[0160] According to some embodiments, step (2) further comprises providing iron powder and contacting the iron oxide with sodium metal in a reactor in the presence of the iron powder. Specifically, the addition of iron powder has been found to improve the efficiency of Reaction I. According to some embodiments, step (2) further comprises providing a transition metal powder and contacting the transition metal oxide with an alkali metal in the presence of the powder in a reactor.

[0161] where M A 2O and M T Specifically, reference is made to step (3) of the process, which comprises separating NaO and Fe. According to some embodiments, step (3) comprises separating NaO and Fe.

[0162] According to some embodiments, step (3) comprises isolating the reduced transition metal or alloy thereof from the reaction mixture. According to some embodiments, step (3) comprises isolating the reduced transition metal from the reaction mixture. According to some embodiments, step (3) comprises isolating the reduced transition metal alloy from the reaction mixture. According to some embodiments, step (3) comprises isolating the reduced iron from the reaction mixture.

[0163] According to some embodiments, the isolating step (3) further comprises collecting the isolated transition metal or alloy thereof. According to some embodiments, the isolating step (3) further comprises collecting the isolated iron metal or alloy thereof.

[0164] According to some embodiments, the isolated reduced transition metal or alloy thereof is in a condensed phase. According to some embodiments, the isolated reduced transition metal or alloy thereof is isolated as a solid. According to some embodiments, the isolated reduced transition metal or alloy thereof is isolated as a liquid. According to some embodiments, the iron is in a condensed phase. According to some embodiments, the isolated reduced iron is isolated as a solid. According to some embodiments, the isolated iron is isolated as a liquid.

[0165] According to some embodiments, step (3) comprises isolating the alkali metal oxide from the reaction mixture. According to some embodiments, step (3) comprises isolating sodium oxide from the reaction mixture.

[0166] According to some embodiments, the isolating step (3) further comprises collecting the isolated alkali metal oxide. According to some embodiments, the isolating step (3) further comprises collecting the isolated sodium oxide.

[0167] According to some embodiments, step (3) comprises: A 2O and M T and M to produce an isolated transition metal with a purity of at least 90% w / w. According to some embodiments, step (3) comprises separating M A 2O and M T and separating the NaO and Fe to produce isolated transition metal with a purity of at least 95% w / w. According to some embodiments, step (3) comprises separating the NaO and Fe to produce isolated iron metal with a purity of at least 90% w / w. According to some embodiments, step (3) comprises separating the NaO and Fe to produce isolated iron metal with a purity of at least 95% w / w.

[0168] According to some embodiments, step (3) comprises: A 2O and M Tand M to produce an isolated alkali metal with a purity of at least 80% w / w. According to some embodiments, step (3) comprises separating M A 2O and M T and M to produce an isolated alkali metal with a purity of at least 90% w / w. According to some embodiments, step (3) comprises separating M A 2O and M T and separating NaO and Fe to produce isolated alkali metal with a purity of at least 95% w / w. According to some embodiments, step (3) comprises separating NaO and Fe to produce isolated sodium metal with a purity of at least 80% w / w. According to some embodiments, step (3) comprises separating NaO and Fe to produce isolated sodium metal with a purity of at least 90% w / w. According to some embodiments, step (3) comprises separating NaO and Fe to produce isolated sodium metal with a purity of at least 95% w / w.

[0169] According to some embodiments, step (3) comprises: A 2O and M T According to some embodiments, step (3) comprises mechanically separating NaO and Fe.

[0170] According to some embodiments, step (3) comprises: A 2O and M T According to some embodiments, step (3) comprises magnetically separating NaO and Fe.

[0171] Also, in industrial processes, transition metal oxides may be provided from ores that contain contaminants such as silicon oxide (typically silicon dioxide). When such transition metal oxide compositions are provided in step (1) of the present process, they may not react, and the contaminants may be separated using an additional step of melting the transition metal product and filtering / skimming off the contaminants.

[0172] Here, the separated M A

[0023] Reference is made specifically to step (4) of the process, which comprises increasing the temperature of the separated NaO to a second temperature. According to some embodiments, step (4) of the process comprises increasing the temperature of the separated NaO to a second temperature. According to some embodiments, the second temperature is at least 50°C higher than the first temperature.

[0173] According to some embodiments, step (4) is carried out according to Scheme II: 2.II:M A 2O → 2×M A This involves inducing a reaction according to +0.5O2.

[0174] According to some embodiments, the net reaction III resulting from the reactions of Schemes I and II: III:M T n O m → n×M T +0.5m×O2 does not consume alkali metals.

[0175] According to some embodiments, step (4) is carried out according to Scheme II: II: It involves inducing the reaction according to Na2O → 2 × Na + 0.5O2.

[0176] According to some embodiments, the net reaction III resulting from the reactions of Schemes I and II: III:Fe n O m → n×Fe+0.5m×O2 does not consume sodium metal.

[0177] According to some embodiments, the combination of Reaction Schemes I and II (multiplied by m) results in the net reaction represented by Reaction Scheme III. I:M T n O m +2m×M A → m×M A 2O+n×M T , II×m:m×M A 2O → 2m×M A +0.5m×O2, III:M T n O m → n×M T +0.5m×O2

[0178] It should be understood that in order to balance and subtract the equations of Schemes I and II, the equation of Scheme II must be multiplied by m (the number of oxygen atoms in the transition metal oxide compound).

[0179] For clarity, the corresponding iron reaction sequence scheme is provided below. I:Fe n O m +2m×Na → m×Na2O+n×Fe, II×m:m×Na2O → 2m×Na + 0.5m×O2, III:Fe n O m → n×Fe+0.5m×O2

[0180] For the reaction of Scheme II, according to some embodiments, a critical parameter is the activation energy required to decompose the alkali metal oxide. Thus, according to some embodiments, the second temperature is determined based on the M under the specific reactor conditions. A According to some embodiments, the second temperature is equal to or greater than the decomposition temperature of M A above the decomposition temperature of 2O.

[0181] According to some embodiments, upon decomposition of sodium oxide, the resulting products, sodium and oxygen, are initially in the gas phase.

[0182] According to some embodiments, the net reaction III resulting from reactions I and II does not consume alkali metal. According to some embodiments, alkali metal is used and recycled in the two reaction sequences of steps (2) and (4). According to some embodiments, alkali metal is recycled in the two reaction sequences of steps (2) and (4).

[0183] It should be understood that while the net reaction III does not consume the alkali metal, some of the alkali metal may be gradually consumed during step (2). Specifically, side reactions that may occur when the transition metal oxide is impure or of lower grade may gradually consume at least some of the alkali metal. Nevertheless, certain net reaction III does not consume the alkali metal. Also, it has been found that separation of step (III) reduces consumption of the alkali metal (e.g., sodium).

[0184] According to some embodiments, the reaction mixture obtained by performing step (4) is in a fluid state. According to some embodiments, the reaction mixture obtained by performing step (4) is in a liquid state.

[0185] According to some embodiments, the reaction mixture formed in performing step (4) contains a reduced transition metal M T or an alloy thereof. According to some embodiments, the reaction mixture formed in performing step (4) further comprises oxygen. According to some embodiments, oxygen gas is separated from the reaction mixture.

[0186] According to some embodiments, step (4) occurs in the same reactor in which step (2) occurs. According to some embodiments, steps (2) and (4) occur in different parts of the same reactor. According to some embodiments, steps (2) and (4) occur in different chambers of the same reactor.

[0187] According to some embodiments, adjusting the temperature in the reactor in step (4) comprises gradually increasing the temperature in the reactor to a second temperature.

[0188] According to some embodiments, adjusting the temperature in the reactor in step (4) comprises gradually increasing the temperature in the reactor to the second temperature at a rate of 1°C / min to 100°C / min. According to some embodiments, adjusting the temperature in the reactor in step (4) comprises gradually increasing the temperature in the reactor to the second temperature at a rate of 5°C / min to 20°C / min.

[0189] According to some embodiments, increasing the temperature to the second temperature is carried out at a rate of at least 1° C. / min. According to some embodiments, increasing the temperature to the second temperature is carried out at a rate of at least 2° C. / min. According to some embodiments, increasing the temperature to the second temperature is carried out at a rate of at least 5° C. / min. According to some embodiments, increasing the temperature to the second temperature is carried out at a rate of at least 7° C. / min. According to some embodiments, increasing the temperature to the second temperature is carried out at a rate of at least 10° C. / min. According to some embodiments, increasing the temperature to the second temperature is carried out at a rate of at least 15° C. / min. According to some embodiments, the rate is no greater than 100° C. / min. According to some embodiments, the rate is no greater than 75° C. / min. According to some embodiments, the rate is no greater than 50° C. / min. According to some embodiments, the rate is no greater than 40° C. / min. According to some embodiments, the rate is no greater than 30° C. / min. According to some embodiments, the rate is no greater than 20° C. / min. According to some embodiments, the rate is 15°C / min or less. According to some embodiments, the rate is in the range of 1°C / min to 100°C / min. Thus,

[0190] In some embodiments, step (4) is performed in an air-protected environment. In some embodiments, step (4) is performed in a water-protected environment. In some embodiments, step (4) is performed in an air- and water-protected environment.

[0191] In particular, it will be appreciated that alkali metals are highly reactive and require specific reaction conditions, such as running under an inert gas.

[0192] According to some embodiments, step (4) further comprises flowing an inert gas through the reactor. According to some embodiments, step (4) is carried out under an inert gas. According to some embodiments, the inert gas is nitrogen or argon. Each possibility represents a separate embodiment of the present invention.

[0193] According to some embodiments, the reactor is closed during step (4). According to some embodiments, the reactor is closed under an inert atmosphere during step (4). According to some embodiments, the reactor is closed under an inert gas atmosphere during step (4). According to some embodiments, the reactor is closed during step (4) and the two reaction sequences are carried out at elevated pressure.

[0194] Advantageously, the reaction time is short, which is economical and energy consuming.

[0195] According to some embodiments, step (4) is carried out for 6 hours or less, 4 hours or less, 3 hours or less, 2 hours or less, 1 hour or less, 45 minutes or less, or 30 minutes or less. Each possibility represents a separate embodiment of the present invention. According to some embodiments, step (4) is carried out for 1 hour or less. According to some embodiments, step (4) is carried out for at least 5 minutes, at least 10 minutes, at least 15 minutes, at least 20 minutes, or at least 25 minutes. Each possibility represents a separate embodiment of the present invention.

[0196] According to some embodiments, Fe n O m is Fe2O3, FeO, FeOOH, Fe3O4, or a combination thereof, and Reaction Schemes I and III are I:Fe2O3+6×Na → 3×Na2O+2×Fe, III: Fe2O3 → 2×Fe + 1.5×O2, or I: FeO + 2 × Na → Na2O + Fe, III: FeO → Fe + 0.5 × O2, or I:Fe3O4+8×Na → 4×Na2O+3×Fe, III: Fe3O4 → 3×Fe + 2×O2.

[0197] According to some embodiments, M T is Fe and M T n O m is Fe2O3, FeO, FeOOH, Fe3O4, or a combination thereof, and Reaction Scheme I is I:Fe2O3+6×M A → 3×M A 2O + 2 × Fe, or I:FeO+2×M A → M A 2O+Fe, or I:Fe3O4+8×M A → 4×M A 2O+3×Fe.

[0198] According to some embodiments, M T is Ni and M T n O m is NiO, and Reaction Scheme I is I:NiO+2×M A → M A 2O+Ni.

[0199] According to some embodiments, M T is Cr and M T n O m is Cr2O3, CrO, CrO3, or a combination thereof, and Reaction Scheme I is I:Cr2O3+6×M A → 3×M A 2O+2×Cr, or I:CrO+2×M A → M A 2O+Cr, or I:CrO3+6×M A → 3×M A 2O+Cr.

[0200] According to some embodiments, M T is Cu and M T n O m is CuO, CuO, CuO, or a combination thereof, and Reaction Scheme I is I: Cu2O+2×M A → M A 2O+2Cu, or I:CuO+2×M A → M A 2O+Cu, or I: CuO2 + 4 × M A → 2M A 2O+Cu.

[0201] According to some embodiments, M T is Zn and M T n O m ZnO, and reaction scheme I is I:ZnO+2×M A → M A 2O+Zn.

[0202] According to some embodiments, M T is Mn and M T n O m is MnO, Mn3O4, Mn2O3, MnO2, Mn2O7, or a combination thereof, and Reaction Scheme I is I:MnO+2×M A → M A 2O+Mn, or I:Mn3O4+8×M A → 4×M A2O+3×Mn, or I:Mn2O3+6×M A → 3×M A 2O + 2 × Mn, or I:MnO2 + 4 × M A → 2M A 2O+Mn, or I:Mn2O7+14×M A → 7×M A 2O + 2 × Mn.

[0203] According to some embodiments, the second temperature is at least 50° C. higher than the first temperature. According to some embodiments, the second temperature is at least 60° C. higher than the first temperature. According to some embodiments, the second temperature is at least 70° C. higher than the first temperature. According to some embodiments, the second temperature is at least 80° C. higher than the first temperature. According to some embodiments, the second temperature is at least 90° C. higher than the first temperature. According to some embodiments, the second temperature is at least 100° C. higher than the first temperature. According to some embodiments, the second temperature is at least 120° C. higher than the first temperature. According to some embodiments, the second temperature is at least 140° C. higher than the first temperature. According to some embodiments, the second temperature is at least 150° C. higher than the first temperature.

[0204] According to some embodiments, the second temperature is between 50 and 150° C. higher than the first temperature, including each value and subrange within the specified range.

[0205] According to some embodiments, step (4) is carried out at a temperature ranging from 400° C. to 800° C. According to some embodiments, step (4) is carried out at a temperature ranging from 700° C. to 800° C. According to some embodiments, the second temperature is in the range of 700 to 800° C.

[0206] According to some embodiments, step (4) is performed at a temperature of at least 300°C. According to some embodiments, step (4) is performed at a temperature of at least 350°C. According to some embodiments, step (4) is performed at a temperature of at least 400°C. According to some embodiments, step (4) is performed at a temperature of at least 450°C. According to some embodiments, step (4) is performed at a temperature of at least 500°C. According to some embodiments, step (4) is performed at a temperature of at least 550°C. According to some embodiments, step (4) is performed at a temperature of at least 600°C. According to some embodiments, step (4) is performed at a temperature of at least 650°C. According to some embodiments, step (4) is performed at a temperature of at least 700°C. According to some embodiments, step (4) is performed at a temperature of at least 750°C. According to some embodiments, step (4) is performed at a temperature of 1000°C or less. According to some embodiments, step (4) is performed at a temperature of 900°C or less. According to some embodiments, step (4) is carried out at a temperature of 800° C. or less. According to some embodiments, step (4) is carried out at a temperature of 700° C. or less. According to some embodiments, step (4) is carried out at a temperature of 600° C. or less.

[0207] According to some embodiments, step (4) is carried out at a pressure ranging from 0.001 bar to 0.5 bar, including each value and subrange within the specified range.

[0208] According to some embodiments, step (4) is carried out at a pressure of 0.5 bar or less. According to some embodiments, step (4) is carried out at a pressure of 0.25 bar or less. According to some embodiments, step (4) is carried out at a pressure of 0.1 bar or less. According to some embodiments, step (4) is carried out at a pressure of 0.05 bar or less. According to some embodiments, step (4) is carried out at a pressure of 0.01 bar or less. According to some embodiments, step (4) is carried out at a pressure of 0.005 bar or less.

[0209] According to some embodiments, the reaction mixture of step (4) is substantially free of additional solvents and carriers. According to some embodiments, step (4) is carried out in an air and water protected environment.

[0210] According to some embodiments, the process further comprises step (5), with particular reference to step (5) of the process, which comprises isolating the alkali metal from the mixture of step (4). According to some embodiments, step (5) comprises isolating sodium metal from the mixture of step (4).

[0211] According to some embodiments, step (5) comprises isolating the alkali metal from the reaction mixture. According to some embodiments, step (5) comprises isolating sodium from the reaction mixture.

[0212] According to some embodiments, the isolating step (5) further comprises collecting the isolated alkali metal. According to some embodiments, the isolating step (5) further comprises collecting the isolated sodium. According to some embodiments, the isolating step (5) further comprises storing the isolated sodium.

[0213] According to some embodiments, the isolating step (5) involves evaporating the alkali metal from the reactor. According to some embodiments, the isolating step (5) involves evaporating the sodium metal from the reactor.

[0214] According to some embodiments, evaporating the alkali metal is carried out at a temperature of at least 200°C. According to some embodiments, evaporating the alkali metal is carried out at a temperature of at least 250°C. According to some embodiments, evaporating the alkali metal is carried out at a temperature of at least 300°C. According to some embodiments, evaporating the alkali metal is carried out at a temperature of at least 350°C. According to some embodiments, evaporating the alkali metal is carried out at a temperature of at least 400°C. According to some embodiments, evaporating the alkali metal is carried out at a temperature of at least 450°C. According to some embodiments, evaporating the alkali metal is carried out at a temperature of at least 500°C. According to some embodiments, evaporating the alkali metal is carried out at a temperature of at least 550°C. According to some embodiments, evaporating the alkali metal is carried out at a temperature of at least 575°C. According to some embodiments, evaporating the alkali metal is carried out at a temperature of at least 600°C. According to some embodiments, evaporating the alkali metal is carried out at a temperature of at least 650°C. According to some embodiments, evaporating the alkali metal is carried out at a temperature of at least 700°C. According to some embodiments, evaporating the alkali metal is performed at a temperature of at least 570°C. According to some embodiments, evaporating the alkali metal is performed at a temperature of 1000°C or less. According to some embodiments, evaporating the alkali metal is performed at a temperature of 900°C or less. According to some embodiments, evaporating the alkali metal is performed at a temperature of 800°C or less. According to some embodiments, evaporating the alkali metal is performed at a temperature of 700°C or less. According to some embodiments, evaporating the alkali metal is performed at a temperature in the range of 200°C to 1000°C, including each value and subrange within the specified range. According to some embodiments, evaporating the alkali metal is performed at a temperature in the range of 300°C to 900°C. According to some embodiments, evaporating the alkali metal is performed at a temperature in the range of 400°C to 800°C.According to some embodiments, evaporating the alkali metal is carried out at a temperature ranging from 500° C. to 700° C. According to some embodiments, evaporating the alkali metal is carried out at a temperature ranging from 550° C. to 650° C.

[0215] According to some embodiments, evaporating sodium metal is carried out at a temperature of at least 200°C. According to some embodiments, evaporating sodium metal is carried out at a temperature of at least 250°C. According to some embodiments, evaporating sodium metal is carried out at a temperature of at least 300°C. According to some embodiments, evaporating sodium metal is carried out at a temperature of at least 350°C. According to some embodiments, evaporating sodium metal is carried out at a temperature of at least 400°C. According to some embodiments, evaporating sodium metal is carried out at a temperature of at least 450°C. According to some embodiments, evaporating sodium metal is carried out at a temperature of at least 500°C. According to some embodiments, evaporating sodium metal is carried out at a temperature of at least 550°C. According to some embodiments, evaporating sodium metal is carried out at a temperature of at least 575°C. According to some embodiments, evaporating sodium metal is carried out at a temperature of at least 600°C. According to some embodiments, evaporating sodium metal is carried out at a temperature of at least 650°C. According to some embodiments, evaporating sodium metal is carried out at a temperature of at least 700°C. According to some embodiments, evaporating sodium metal is carried out at a temperature of at least 570°C. According to some embodiments, evaporating sodium metal is carried out at a temperature of 1000°C or less. According to some embodiments, evaporating sodium metal is carried out at a temperature of 900°C or less. According to some embodiments, evaporating sodium metal is carried out at a temperature of 800°C or less. According to some embodiments, evaporating sodium metal is carried out at a temperature of 700°C or less. According to some embodiments, evaporating sodium metal is carried out at a temperature in the range of 200°C to 1000°C, including each value and subrange within the specified range. According to some embodiments, evaporating sodium metal is carried out at a temperature in the range of 300°C to 900°C.According to some embodiments, evaporating sodium metal is carried out at a temperature ranging from 400° C. to 800° C. According to some embodiments, evaporating sodium metal is carried out at a temperature ranging from 500° C. to 700° C. According to some embodiments, evaporating sodium metal is carried out at a temperature ranging from 550° C. to 650° C.

[0216] According to some embodiments, evaporating the alkali metal is carried out at reduced pressure. According to some embodiments, evaporating the alkali metal is carried out at a pressure ranging from 0.001 bar to 0.2 bar. According to some embodiments, evaporating the alkali metal is carried out at a pressure ranging from 0.001 bar to 0.5 bar, including each value and subrange within the specified range. According to some embodiments, evaporating the sodium metal is carried out at reduced pressure. According to some embodiments, evaporating the sodium metal is carried out at a pressure ranging from 0.001 bar to 0.2 bar. According to some embodiments, evaporating the sodium metal is carried out at a pressure ranging from 0.001 bar to 0.5 bar, including each value and subrange within the specified range.

[0217] According to some embodiments, the evaporating is carried out for at least 10 minutes, at least 20 minutes, at least 30 minutes, at least 45 minutes, at least 60 minutes, or at least 90 minutes. According to some embodiments, the evaporating is carried out for about 2 hours.

[0218] According to some embodiments, the evaporating in step (5) involves applying a reduced pressure to the reaction mixture. According to some embodiments, the isolating in step (5) involves evaporating the sodium metal produced in Reaction Scheme II and transferring the sodium metal from the reactor. According to some embodiments, the evaporation involves heating the sodium metal. According to some embodiments, the evaporation involves reducing the pressure in the reactor. According to some embodiments, the isolating in step (5) involves evaporating the sodium metal from the reactor. According to some embodiments, the isolating in step (5) involves boiling the sodium metal from the reactor.

[0219] According to some embodiments, the evaporating of step (5) comprises flowing an inert gas through the reaction mixture.

[0220] Now, with specific reference to step (6) of the process.

[0221] According to some embodiments, the process further comprises a step (6) of condensing the vaporized alkali metal. According to some embodiments, the process further comprises a step (6) of condensing the vaporized sodium metal.

[0222] According to some embodiments, the vaporized alkali metal is condensed in a dedicated container in step (6). According to some embodiments, the vaporized sodium metal is condensed in a dedicated container in step (6). According to some embodiments, the container is maintained under air and / or water protective conditions. According to some embodiments, the container is a sealable container.

[0223] Generally, alkali metals are solid materials at room temperature and atmospheric pressure. According to some embodiments, in step (5), the alkali metal is heated and optionally placed under reduced pressure, so that it converts to a vapor. According to some embodiments, step (6) is relevant when the isolation in step (5) includes such evaporation, which includes condensation of the alkali metal vapor in a separate container. While the term "condensing" typically refers to the conversion from a gas to a liquid, it should be understood that the condensed alkali metal may convert to a solid gradually or instantaneously, depending, for example, on the temperature in the alkali metal container. Thus, the term "condensing" in the context of step (6) also includes deposition of a gas onto a solid.

[0224] According to some embodiments, the condensing in step (6) is carried out at a temperature lower than the second temperature. According to some embodiments, the condensing in step (6) is carried out at a temperature at least 100°C lower than the second temperature. According to some embodiments, the condensing in step (6) is carried out at a temperature at least 200°C lower than the second temperature. According to some embodiments, the condensing in step (6) is carried out at a temperature at least 250°C lower than the second temperature. According to some embodiments, the condensing in step (6) is carried out at a temperature at least 300°C lower than the second temperature. According to some embodiments, the condensing in step (6) is carried out at a temperature at least 350°C lower than the second temperature. According to some embodiments, the condensing in step (6) is carried out at a temperature at least 400°C lower than the second temperature.

[0225] According to some embodiments, the pressure in the condensation vessel is substantially equal to the pressure in the reactor during the evaporation and / or condensation steps. In this context, "substantially equal pressure" refers to a range of ±25%, ±20%, ±15%, ±10%, ±5%, ±0.1 bar, ±0.05 bar, ±0.01 bar, or ±0.001 bar. Each possibility represents a separate embodiment of the present invention.

[0226] Now, with specific reference to step (7) of the process.

[0227] According to some embodiments, the process further comprises step (7) of transferring the condensed alkali metal to the reactor, thereby recycling the alkali metal. According to some embodiments, the process further comprises step (7) of transferring the condensed sodium metal to the reactor, thereby recycling the sodium metal.

[0228] According to some embodiments, the alkali metal is transferred to the reactor in step (7) as a condensed material. According to some embodiments, the alkali metal is transferred to the reactor in step (7) as a liquid. According to some embodiments, the alkali metal is transferred to the reactor in step (7) as a solid.

[0229] It should be understood that performing step (7) completes one cycle of the process. According to some embodiments, the process may proceed for additional cycles upon reconstituting the alkali metal and providing further transition metal oxide.

[0230] According to some embodiments, the process further comprises repeating steps (1)-(3) for at least one additional sequence after step (7). According to some embodiments, the process further comprises repeating steps (1)-(4) for at least one additional sequence after step (7). According to some embodiments, the process further comprises repeating steps (1)-(3) for at least one additional sequence.

[0231] According to some embodiments, the process includes performing steps (1)-(4) for at least one cycle, and performing steps (1)-(4). According to some embodiments, the process includes performing steps (1)-(4) for multiple cycles. According to some embodiments, the process includes performing steps (1)-(5) for multiple cycles. According to some embodiments, the process includes performing steps (1)-(6) for multiple cycles. According to some embodiments, the process includes performing steps (1)-(7) for multiple cycles.

[0232] The term "plurality" refers to any integer greater than one.

[0233] According to some embodiments, the process comprises: (1) providing a transition metal oxide; (2) combining a transition metal oxide with an alkali metal in a reactor and adjusting the temperature in the reactor to a first temperature; (3) M A 2O and M T and (4) Separated M A raising the temperature of the 20 to a second temperature to induce a reaction according to Scheme III; (5) evaporating the alkali metal formed in step (4); and (6) condensing the evaporated alkali metal; and (7) transferring the condensed alkali metal to a reactor; The process further includes repeating steps (1)-(3) for at least one additional sequence.

[0234] According to some embodiments, the process comprises: (1) providing iron oxide; (2) combining iron oxide with sodium metal in a reactor and adjusting the temperature in the reactor to a first temperature; (3) separating NaO and Fe; (4) increasing the temperature of the separated NaO to a second temperature to induce a reaction according to Scheme III; (5) evaporating the sodium metal formed in step (4); and (6) condensing the evaporated sodium metal; and (7) transferring the condensed sodium metal to a reactor; The process further includes repeating steps (1)-(3) for at least one additional sequence.

[0235] Reference is now made to Figures 1-2, which are block diagrams illustrating a process for reducing at least one transition metal oxide to the corresponding transition metal or alloy thereof.

[0236] 17 is a block diagram illustrating a process for reducing at least one iron oxide to the corresponding iron, according to some embodiments, including steps (1), (2), (3), and (4) detailed herein. Step (1) is represented by block 2000, step (2) is represented by block 2010, step (3) is represented by block 2020, and step (4) is represented by block 2021.

[0237] 8 is a block diagram representing a process for reducing at least one iron oxide to the corresponding iron, according to some embodiments, including steps (1), (2), (3), (4), (5), (6), and (7) detailed herein. Step (1) is represented by block 2000, step (2) is represented by block 2010, step (3) is represented by blocks 2020 and 2030, step (4) is represented by block 2021, step (5) is represented by block 2035, step (6) is represented by block 2040, and step (7) is represented by block 2050.

[0238] 3 is a block diagram representing a process for reducing at least one transition metal oxide to the corresponding transition metal, according to some embodiments, including steps (1), (2), (3), (4), (5), (6), and (7) detailed herein. Step (1) is represented by block 2000, step (2) is represented by block 2010, step (3) is represented by blocks 2020 and 2030, step (4) is represented by block 2021, step (5) is represented by block 2035, step (6) is represented by block 2040, and step (7) is represented by block 2050.

[0239] Below are provided non-limiting, specific embodiments of specific reaction sequences that may be performed by the process of the present invention. Reference is further made to Figures 4-6, which are block diagrams each representing a selected process (i.e., two specific reaction sequences) for reducing at least one transition metal oxide to the corresponding transition metal or its alloy. Each one of Figures 4-6 represents a process according to some embodiments, including steps (1), (2), (3), and (4) detailed herein, where step (1) is represented by block 2000, step (2) is represented by block 2010, step (3) is represented by block 2020, and step (4) is represented by block 2021.

[0240] According to some embodiments, the alkali metal is Na and Scheme II is II: Na2O → 2Na + 0.5O2.

[0241] 4 to 6 and 10 to 12 show reaction sequences using sodium as the alkali metal.

[0242] According to some embodiments, the alkali metal is K and Scheme II is: II:K2O → 2K+0.5O2.

[0243] According to some embodiments, M Tis Fe and M T n O m is Fe2O3 (iron oxide is Fe2O3), and M A is Na, and reaction schemes I and III are I:Fe2O3+6×Na → 3×Na2O+2×Fe, III: Fe2O3 → 2×Fe + 1.5×O2.

[0244] This transformation is illustrated in FIGS.

[0245] Also, M A Reaction Scheme II for =Na is provided above and can be understood by one skilled in the art in each of the following reaction sequences.

[0246] According to some embodiments, M T is Fe and M T n O m is Fe2O3 (iron oxide is Fe2O3), and M A is K, and reaction schemes I and III are I:Fe2O3+6×K → 3×K2O+2×Fe, III: Fe2O3 → 2×Fe + 1.5×O2.

[0247] Also, M A Reaction Scheme II for =K is provided above and can be understood by one skilled in the art in each of the following reaction sequences.

[0248] According to some embodiments, M T is Fe and M T n O m is FeO (iron oxide is FeO), and M A is Na, and reaction schemes I and III are I: FeO + 2 × Na → Na2O + Fe, III: FeO → Fe + 0.5 × O2.

[0249] This transformation is illustrated in FIGS.

[0250] According to some embodiments, M T is Fe and M T n O m is FeO (iron oxide is FeO), and M A is K, and reaction schemes I and III are I: FeO + 2 × K → K2O + Fe, III: FeO → Fe + 0.5 × O2.

[0251] According to some embodiments, M T is Fe and M T n O m is Fe3O4 (iron oxide is Fe3O4), M A is Na, and reaction schemes I and III are I:Fe3O4+8×Na → 4×Na2O+3×Fe, III: Fe3O4 → 3×Fe + 2×O2.

[0252] This transformation is illustrated in FIGS.

[0253] According to some embodiments, M T is Fe and M T n O m is Fe3O4, and M A is K, and reaction schemes I and III are I:Fe3O4+8×K → 4×K2O+3×Fe, III: Fe3O4 → 3×Fe + 2×O2.

[0254] According to some embodiments, M T is Ni and M T n O m is NiO, and M A is Na, and reaction schemes I and III are I: NiO + 2 × Na → Na2O + Ni, III: NiO → Ni + 0.5 × O2.

[0255] According to some embodiments, M T is Ni and M T n O m is NiO, and M A is K, and reaction schemes I and III are I: NiO + 2 × K → K2O + Ni, III: NiO → Ni + 0.5 × O2.

[0256] According to some embodiments, M T is Cr and M T n O m is Cr2O3, and M A is Na, and reaction schemes I and III are I:Cr2O3+6×Na → 3×Na2O+2×Cr, III: Cr2O3 → 2×Cr + 1.5×O2.

[0257] According to some embodiments, M T is Cr and M T n O m is Cr2O3, and M A is K, and reaction schemes I and III are I:Cr2O3+6×K → 3×K2O+2×Cr, III: Cr2O3 → 2×Cr + 1.5×O2.

[0258] According to some embodiments, M T is Cr and M T n O m is CrO and M A is Na, and reaction schemes I and III are I: CrO + 2 × Na → Na2O + Cr, III: CrO → Cr + 0.5 × O2.

[0259] According to some embodiments, M T is Cr and M T n O m is CrO and M A is K, and reaction schemes I and III are I: CrO + 2 × K → K2O + Cr, III: CrO → Cr + 0.5 × O2.

[0260] According to some embodiments, M T is Cr and M T n O m is CrO3 and M A is Na, and reaction schemes I and III are I:CrO3+6×Na → 3×Na2O+Cr, III: CrO3 → Cr + 1.5 × O2.

[0261] According to some embodiments, M T is Cr and M T n O m is CrO3 and M A is K, and reaction schemes I and III are I: CrO3 + 6 × K → 3 × K2O + Cr, III: CrO3 → Cr + 1.5 × O2.

[0262] According to some embodiments, M T is Cr and M T n O m is CuO, and M A is Na, and reaction schemes I and III are I: Cu2O + 2 × Na → Na2O + 2Cu, III: Cu2O → 2 × Cu + 0.5 × O2.

[0263] According to some embodiments, M Tis Cr and M T n O m is CuO, and M A is K, and reaction schemes I and III are I: Cu2O + 2 × K → K2O + 2Cu, III: Cu2O → 2 × Cu + 0.5 × O2.

[0264] According to some embodiments, M T is Cu and M T n O m is CuO, and M A is Na, and reaction schemes I and III are I: CuO + 2 × Na → Na2O + Cu, III: CuO → Cu + 0.5 × O2.

[0265] According to some embodiments, M T is Cu and M T n O m is CuO, and M A is K, and reaction schemes I and III are I: CuO + 2 × K → K2O + Cu, III: CuO → Cu + 0.5 × O2.

[0266] According to some embodiments, M T is Cu and M T n O m is CuO2 and M A is Na, and reaction schemes I and III are I: CuO2 + 4 × Na → 2Na2O + Cu, III: CuO2 → Cu+O2.

[0267] According to some embodiments, M T is Cu and M T n O m is CuO2 and M Ais K, and reaction schemes I and III are I: CuO2 + 4 × K → 2K2O + Cu, III: CuO2 → Cu+O2.

[0268] According to some embodiments, M T is Zn and M T n O m is ZnO, and M A is Na, and reaction schemes I and III are I: ZnO + 2 × Na → Na2O + Zn, III: ZnO → Zn + 0.5 × O2.

[0269] According to some embodiments, M T is Zn and M T n O m is ZnO, and M A is K, and reaction schemes I and III are I:ZnO+2×K → KO+Zn, III: ZnO → Zn + 0.5 × O2.

[0270] According to some embodiments, M T is Mn and M T n O m is MnO, and M A is Na, and reaction schemes I and III are I: MnO + 2 × Na → Na2O + Mn, III: MnO → Mn + 0.5 × O2.

[0271] According to some embodiments, M T is Mn and M T n O m is MnO, and M A is K, and reaction schemes I and III are I: MnO + 2 × K → KO + Mn, III: MnO → Mn + 0.5 × O2.

[0272] According to some embodiments, M T is Mn and M T n O m is Mn3O4, and M A is Na, and reaction schemes I and III are I:Mn3O4+8×Na → 4×Na2O+3×Mn, III: Mn3O4 → 3 × Mn + 2 × O2.

[0273] According to some embodiments, M T is Mn and M T n O m is Mn3O4, and M A is K, and reaction schemes I and III are I:Mn3O4+8×K → 4×K2O+3×Mn, III: Mn3O4 → 3 × Mn + 2 × O2.

[0274] According to some embodiments, M T is Mn and M T n O m is Mn2O3, and M A is Na, and reaction schemes I and III are I:Mn2O3+6×Na → 3×Na2O+2×Mn, III: Mn2O3 → 2 × Mn + 1.5 × O2.

[0275] According to some embodiments, M T is Mn and M T n O m is Mn2O3, and M A is K, and reaction schemes I and III are I:Mn2O3+6×K → 3×K2O+2×Mn, III: Mn2O3 → 2 × Mn + 1.5 × O2.

[0276] According to some embodiments, M T is Mn and M T n O m is MnO2, and M A is Na, and reaction schemes I and III are I: MnO2 + 4 × Na → 2Na2O + Mn, III: MnO2 → Mn + O2.

[0277] According to some embodiments, M T is Mn and M T n O m is MnO2, and M A is K, and reaction schemes I and III are I: MnO2 + 4 × K → 2K2O + Mn, III: MnO2 → Mn + O2.

[0278] According to some embodiments, M T is Mn and M T n O m is Mn2O7, and M A is Na, and reaction schemes I and III are I:Mn2O7+14×Na → 7×Na2O+2×Mn, III: Mn2O7 → 2 × Mn + 3.5 × O2.

[0279] According to some embodiments, M T is Mn and M T n O m is Mn2O7, and M A is K, and reaction schemes I and III are I:Mn2O7+14×K → 7×K2O+2×Mn, III: Mn2O7 → 2 × Mn + 3.5 × O2.

[0280] According to some embodiments, M T is Sc and MT n O m is Sc2O3, and M A is Na, and reaction schemes I and III are I:Sc2O3+6×Na → 3×Na2O+2×Sc, III: Sc2O3 → 2×Sc + 1.5×O2.

[0281] According to some embodiments, M T is Sc and M T n O m is Sc2O3, and M A is K, and reaction schemes I and III are I:Sc2O3+6×K → 3×K2O+2×Sc, III: Sc2O3 → 2×Sc + 1.5×O2.

[0282] According to some embodiments, M T is Ti and M T n O m is TiO2 and M A is Na, and reaction schemes I and III are I: TiO2 + 4 × Na → 2Na2O + Ti, III: TiO2 → Ti + O2.

[0283] According to some embodiments, M T is Ti and M T n O m is TiO2 and M A is K, and reaction schemes I and III are I: TiO2 + 4 × K → 2K2O + Ti, III: TiO2 → Ti + O2.

[0284] According to some embodiments, M T is Ti and M T n O m is Ti2O3, and M Ais Na, and reaction schemes I and III are I:Ti2O3+6×Na → 3×Na2O+2×Ti, III: Ti2O3 → 2×Ti + 1.5×O2.

[0285] According to some embodiments, M T is Ti and M T n O m is Ti2O3, and M A is K, and reaction schemes I and III are I:Ti2O3+6×K → 3×K2O+2×Ti, III: Ti2O3 → 2×Ti + 1.5×O2.

[0286] According to some embodiments, M T is V and M T n O m is VO and M A is Na, and reaction schemes I and III are I:VO + 2 × Na → Na2O + V, III:VO → V+0.5×O2.

[0287] According to some embodiments, M T is V and M T n O m is VO and M A is K, and reaction schemes I and III are I:VO+2×K → KO+V, III:VO → V+0.5×O2.

[0288] According to some embodiments, M T is V and M T n O m is V2O3 and M A is Na, and reaction schemes I and III are I:V2O3+6×Na → 3×Na2O+2×V, III:V2O3 → 2×V + 1.5×O2.

[0289] According to some embodiments, M T is V and M T n O m is V2O3 and M A is K, and reaction schemes I and III are I:V2O3+6×K → 3×K2O+2×V, III:V2O3 → 2×V + 1.5×O2.

[0290] According to some embodiments, M T is V and M T n O m is VO2 and M A is Na, and reaction schemes I and III are I:VO2 + 4 × Na → 2Na2O + V, III:VO2 → V+O2.

[0291] According to some embodiments, M T is V and M T n O m is VO2 and M A is K, and reaction schemes I and III are I:VO2+4×K → 2K2O+V, III:VO2 → V+O2.

[0292] According to some embodiments, M T is V and M T n O m is V2O5 and M A is Na, and reaction schemes I and III are I:V2O5+10×Na → 5×Na2O+2×V, III:V2O5 → 2×V + 2.5×O2.

[0293] According to some embodiments, MT is V and M T n O m is V2O5 and M A is K, and reaction schemes I and III are I:V2O5+10×K → 5×K2O+2×V, III:V2O5 → 2×V + 2.5×O2.

[0294] According to some embodiments, M T is Co and M T n O m is Co2O3 and M A is Na, and reaction schemes I and III are I:Co2O3+6×Na → 3×Na2O+2×Co, III: Co2O3 → 2 × Co + 1.5 × O2.

[0295] According to some embodiments, M T is Co and M T n O m is Co2O3 and M A is K, and reaction schemes I and III are I:Co2O3+6×K → 3×K2O+2×Co, III: Co2O3 → 2 × Co + 1.5 × O2.

[0296] According to some embodiments, M T is Co and M T n O m is CoO and M A is Na, and reaction schemes I and III are I: CoO + 2 × Na → Na2O + Co, III: CoO → Co + 0.5 × O2.

[0297] According to some embodiments, M T is Co and M T n Om is CoO and M A is K, and reaction schemes I and III are I: CoO + 2 × K → KO + Co, III: CoO → Co + 0.5 × O2.

[0298] According to some embodiments, M T is Co and M T n O m is Co3O4 and M A is Na, and reaction schemes I and III are I:Co3O4+8×Na → 4×Na2O+3×Co, III: Co3O4 → 3 × Co + 2 × O2.

[0299] According to some embodiments, M T is Co and M T n O m is Co3O4 and M A is K, and reaction schemes I and III are I:Co3O4+8×K → 4×K2O+3×Co, III: Co3O4 → 3 × Co + 2 × O2.

[0300] According to some embodiments, a process for the reduction of iron metal oxides is provided, the process comprising: (a) Formula Fe n O m wherein each one of n and m is 1, 2, 3, 4, 5, 6, or 7; (b) contacting iron oxide with sodium metal in a reactor and adjusting the temperature in the reactor to a first temperature in the range of 250°C to 650°C to produce a product of Scheme I: I:Fe n O m + 2m × Na → m × Na2O + n × Fe The temperature is increased to a second temperature at least 50° C. above the reduction temperature to form Scheme II: II: Inducing the reaction according to Na2O → 2 × Na + 0.5O2, As a result, the net reaction resulting from the reactions of Schemes I and II is III: III:Fe n O m → n×Fe+0.5m×O2 does not consume sodium metal, derivatizing the resulting reaction mixture, which comprises reduced iron metal, sodium, and optionally oxygen and / or sodium oxide, NaO; (c) isolating the iron from the reaction mixture.

[0301] Reference is now made specifically to step (a) of the process, which, according to some embodiments, involves providing at least one transition metal oxide.

[0302] According to some embodiments, step (a) comprises reacting a compound of formula M T n O m According to some embodiments, step (a) comprises providing at least one transition metal oxide having the formula M T n O m According to some embodiments, step (a) comprises providing a transition metal oxide having the formula M T n O m According to some embodiments, step (a) comprises providing a single transition metal oxide having the formula Fe n O m According to some embodiments, step (a) comprises providing an iron oxide having the formula Fe n O m The method includes providing a single iron oxide having the formula:

[0303] Specifically, as can be appreciated by one of ordinary skill in the art, according to some embodiments, the compound of formula M T n O mThe provision of two or more transition metal oxides of formula M in step (a) can result in the formation of a transition metal alloy upon completion of the process, as detailed herein. T n O m The provision of one transition metal oxide of step (b) can result in the formation of a reduced transition metal upon completion of the process. Specifically, according to some embodiments, if the reaction mixture of step (b) does not contain a metal or metal oxide that is alloyable with the transition metal provided in step (a), the result of the two reaction sequences of step (b) is a transition metal. However, if another metal that is alloyable with the transition metal provided in step (a), or an oxide of such an alloyable metal, is present in the reaction mixture of step (b), an alloy can be formed from the two metals.

[0304] According to some embodiments, n is 1, 2, 3, 4, 5, 6, or 7. Each possibility represents a separate embodiment of the present invention. According to some embodiments, n is 1, 2, or 3. According to some embodiments, m is 1, 2, 3, 4, 5, 6, or 7. Each possibility represents a separate embodiment of the present invention. According to some embodiments, m is 1, 2, 3, or 4.

[0305] According to some embodiments, M T is selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn. Each possibility represents a separate embodiment of the present invention. According to some embodiments, the transition metal is Sc. According to some embodiments, the transition metal is Ti. According to some embodiments, the transition metal is V. According to some embodiments, the transition metal is Cr. According to some embodiments, the transition metal is Mn. According to some embodiments, the transition metal is Fe. According to some embodiments, the transition metal is Co. According to some embodiments, the transition metal is Ni. According to some embodiments, the transition metal is Cu. According to some embodiments, the transition metal is Zn.

[0306] According to some embodiments, the transition metal oxide is provided in step (a) as a solid.

[0307] As detailed herein, according to some embodiments, during step (b), the transition metal oxide is consumed to provide the transition metal and oxygen, while the alkali metal is conserved and recycled, allowing for the continuous supply of additional transition metal oxide to the reaction mixture and the continuous production of additional transition metal.

[0308] According to some embodiments, step (a) comprises continuously feeding at least one transition metal oxide to a reactor, such that the total transition metal oxides fed in step (a) are in molar excess relative to the alkali metal in step (b). According to some embodiments, step (a) comprises gradually feeding at least one transition metal oxide to a reactor. According to some embodiments, at any point during step (b), the alkali metal may be in molar excess relative to the transition metal oxide therein in the reactor, although it should be understood that according to this embodiment, the transition metal oxide is continuously added and consumed such that the total transition metal oxide provided over time is in molar excess relative to the alkali metal catalyst.

[0309] For purposes of this specification, the term "continuously" means that the transition metal oxide is added to the reactor over time. This term is not limited to uninterrupted or interrupted (e.g., batch) addition of the transition metal oxide.

[0310] According to some embodiments, the molar excess is at least 50% mol / mol, at least 100% mol / mol, at least 200% mol / mol, at least 300% mol / mol, at least 400% mol / mol, at least 500% mol / mol, at least 750% mol / mol, at least 1,000% mol / mol, at least 2,000% mol / mol, at least 5,000% mol / mol, or at least 10,000% mol / mol. Each possibility represents a separate embodiment of the present invention. According to some embodiments, the molar excess ranges from 100% to 1,000,000% mol / mol, 500% to 1,000,000% mol / mol, 1,000% to 1,000,000% mol / mol, or 10,000% to 1,000,000% mol / mol. Each possibility represents a separate embodiment of the present invention, and includes each value and subrange within the specified range.

[0311] When used in the context of steps (a) and (b), a molar excess of X% is understood to mean that the total molar amount of transition metal oxides finally added in step (a) exceeds the molar amount of alkali metal used by X%.

[0312] According to some embodiments, the at least one transition metal oxide is as detailed above with respect to step (1).

[0313] According to some embodiments, step (a) comprises providing an ore comprising transition metal oxides. According to some embodiments, step (a) comprises providing an ore comprising iron oxides. According to some embodiments, the ore is as described in step (1).

[0314] According to some embodiments, M T n O m is as described in step (1).

[0315] Here, in the reactor, the transition metal oxide is mixed with an alkali metal (M A), and adjusting the temperature in the reactor to the first temperature.

[0316] According to some embodiments, step (b) comprises contacting iron oxide with sodium metal in a reactor and adjusting the temperature in the reactor to a first temperature in the range of 100° C. to 500° C. to form a sintered product according to Scheme I: I:Fe n O m + 2m × Na → m × Na2O + n × Fe The temperature is increased to a second temperature at least 50° C. above the reduction temperature to form Scheme II: II: NaO → 2 × Na + 0.5O, As a result, the net reaction resulting from the reactions of Schemes I and II is III: III:Fe n O m → n×Fe+0.5m×O2 does not consume sodium metal, The resulting reaction mixture contains reduced iron metal, sodium, and optionally oxygen and / or sodium oxide Na2O.

[0317] According to some embodiments, step (2) comprises contacting at least one transition metal with an alkali metal in a reactor and adjusting the temperature in the reactor to a first temperature above the melting point of the alkali metal in the range of 100° C. to 500° C. to form a catalyst according to Scheme I: I:M T n O m +2m×M A → m×M A 2O+n×M T and inducing a response according to As a result, the reduced transition metal M T or its alloy, alkali metal oxide M A 2O, and optionally oxygen and / or alkali metal M A resulting in a reaction mixture comprising M A is Na or K, or an alloy thereof.

[0318] According to some embodiments, step (b) comprises reacting a transition metal oxide with an alkali metal (M A ) with an alkali metal. According to some embodiments, the act of combining the transition metal oxide with the alkali metal is carried out at a first temperature. Specifically, according to some embodiments, if the reaction has not yet begun, external heating is required to reach the first temperature. Alternatively, according to some embodiments, after the reaction has begun, its exothermic nature can at least partially maintain or increase the internal temperature, such that less external heating is required, or even external heating can be at least temporarily stopped.

[0319] According to some embodiments, adjusting the temperature in the reactor to a first temperature comprises increasing the temperature in the reactor to the first temperature. According to some embodiments, step (b) comprises adjusting the temperature by induction.

[0320] It should be understood that where the process includes separation of sodium oxide and further dissociation into its elemental components (in step (e)), embodiments herein that refer to the reaction of Scheme II can refer to this reaction in either step (b) or step (e).

[0321] According to some embodiments, the value of the first temperature is selected to effect the reactions of Scheme I. In other words, the first temperature provides sufficient energy to the reaction system to overcome the activation energies of both reactions and provide suitable reaction conditions.

[0322] For the reaction of Scheme I, according to some embodiments, an important parameter is the physical state of the reactants. Specifically, according to some embodiments, it is advantageous for the reaction of the present method to be carried out neat (i.e., without a solvent). Also, at room temperature, both the alkali metal and transition metal oxide reactants are in the solid state, which tends to slow down or prevent the chemical reaction.

[0323] For the reaction of Scheme II, according to some embodiments, a critical parameter is the activation energy required to decompose the alkali metal oxide. Thus, according to some embodiments, the second temperature is determined based on the M under the specific reactor conditions. A According to some embodiments, the second temperature is equal to or greater than the decomposition temperature of M A above the decomposition temperature of 2O.

[0324] The term "alkali metal" is as described above with respect to step (2). According to some embodiments, the alkali metal (M A ) is as described above for step (2).

[0325] According to some embodiments, the first temperature is as described with respect to step (2).

[0326] According to some embodiments, the reaction of Scheme II is carried out where the sodium oxide is in the solid phase.

[0327] According to some embodiments, the reaction of Scheme II is carried out, wherein sodium oxide is in the vapor phase, and step (b) further involves at least partially evaporating the sodium oxide. According to some embodiments, upon decomposition of sodium oxide, the resulting products, sodium and oxygen, are initially in the vapor phase.

[0328] According to some embodiments, the reaction of Scheme I is carried out neat. According to some embodiments, the reaction of Scheme II is carried out neat. According to some embodiments, the two reaction sequences of step (b) are carried out neat. According to some embodiments, the reaction mixture of step (b) is substantially free of additional solvent. According to some embodiments, the reaction mixture of step (b) is substantially free of additional solvent and carrier.

[0329] According to some embodiments, the reaction mixture of step (b) consists essentially of the transition metal oxide, the alkali metal, and the product reduced transition metal or alloy thereof. According to some embodiments, the condensed phase in the reactor during step (b) consists essentially of the transition metal oxide, the alkali metal, and the product reduced transition metal or alloy thereof.

[0330] According to some embodiments, the reaction mixture of step (b) consists essentially of iron oxide, sodium, and optionally product iron oxide and / or sodium oxide.

[0331] According to some embodiments, the net reaction resulting from the two-reaction sequence, III, does not consume alkali metal. According to some embodiments, the alkali metal is used and recycled in the two-reaction sequence of step (b). According to some embodiments, the alkali metal is recycled in the two-reaction sequence of step (b).

[0332] According to some embodiments, the resulting reaction mixture formed upon contacting the transition metal oxide and the alkali metal in step (b) is in a fluid state. According to some embodiments, the resulting reaction mixture formed upon contacting the transition metal oxide and the alkali metal in step (b) is in a liquid state. According to some embodiments, the resulting reaction mixture formed upon contacting the transition metal oxide and the alkali metal in step (b) is a heterogeneous mixture. According to some embodiments, the resulting reaction mixture formed upon contacting the transition metal oxide and the alkali metal in step (b) is a liquid-solid, liquid-liquid, gas-solid, or gas-liquid heterogeneous mixture. Each possibility represents a separate embodiment of the present invention.

[0333] According to some embodiments, the reaction mixture formed in carrying out the two-reaction sequence of step (b) contains a reduced transition metal M Tor an alloy thereof. According to some embodiments, the reaction mixture formed during the two-reaction sequence of step (b) further comprises oxygen. According to some embodiments, oxygen gas is separated from the reaction mixture.

[0334] According to some embodiments, the reaction mixture of step (b) does not contain any metals or metal oxides that are alloyable with the transition metal provided in step (a).

[0335] According to some embodiments, the reaction mixture of step (b) contains an alloyable metal or metal oxide that is alloyable with the transition metal provided in step (a), as described in more detail below with respect to optional alloy formation.

[0336] As detailed herein, step (a) can include continuous addition of a transition metal oxide to the reaction mixture of step (b) such that the transition metal oxide is provided in molar excess relative to the alkali metal added throughout the course of step (b). Specifically, according to some embodiments, the transition metal oxide added to the reactor over the course of step (b) is in molar excess of the alkali metal added thereto. Specific excess amounts are specified above.

[0337] However, while the transition metal oxide added to the reactor is consumed throughout the reaction of Scheme I, the alkali metal is recycled throughout the reaction of Scheme I. Thus, according to some embodiments, at any particular time during step (b), the alkali metal in the reactor is in molar excess relative to the transition metal oxide. According to some embodiments, the transition metal oxide is continuously provided to the reactor at an addition rate that ensures that the alkali metal in the reactor is in molar excess relative to the transition metal oxide at any particular time during step (b). According to some embodiments, the molar excess is at least 5%, at least 10%, at least 25%, at least 50%, at least 100%, or at least 200%. Each possibility represents a separate embodiment of the present invention.

[0338] According to some embodiments, the reactor in which step (b) is performed comprises a crucible. According to some embodiments, step (b) comprises contacting iron oxide with sodium metal in the crucible. According to some embodiments, step (a) is performed in the crucible. According to some embodiments, step (b) comprises contacting a transition metal oxide with an alkali metal in the crucible. According to some embodiments, the crucible is as described in step (2).

[0339] According to some embodiments, adjusting the temperature in the reactor in step (b) comprises gradually increasing the temperature in the reactor to a first temperature. According to some embodiments, increasing the temperature to the first temperature is carried out at a rate defined in step (2).

[0340] According to some embodiments, increasing the temperature in the reactor to the second temperature in step (b) comprises gradually increasing the temperature in the reactor to the second temperature. According to some embodiments, increasing the temperature to the second temperature is carried out at a rate defined in step (4).

[0341] According to some embodiments, step (b) comprises contacting a transition metal oxide with an alkali metal in the weight ratio defined in step (2).

[0342] According to some embodiments, the two-reaction sequence of step (b) is carried out in an air-protected environment. According to some embodiments, the two-reaction sequence of step (b) is carried out in a water-protected environment. According to some embodiments, the two-reaction sequence of step (b) is carried out in an air- and water-protected environment.

[0343] In particular, it will be appreciated that alkali metals are highly reactive and require specific reaction conditions, such as running under an inert gas.

[0344] According to some embodiments, step (b) further comprises flowing an inert gas through the reactor. According to some embodiments, the two reaction sequences of step (b) are carried out under an inert gas. According to some embodiments, the inert gas is nitrogen or argon.

[0345] According to some embodiments, during step (b), the reactor is closed. According to some embodiments, during step (b), the reactor is closed under an inert atmosphere. According to some embodiments, during step (b), the reactor is closed under an inert gas atmosphere. According to some embodiments, during step (b), the reactor is closed and the two reaction sequences are carried out at elevated pressure.

[0346] Advantageously, the reaction time is short, which is economical and energy consuming.

[0347] According to some embodiments, step (b) is carried out for 6 hours or less, 4 hours or less, 3 hours or less, 2 hours or less, 1 hour or less, 45 minutes or less, or 30 minutes or less. Each possibility represents a separate embodiment of the present invention. According to some embodiments, step (b) is carried out for 1 hour or less. According to some embodiments, step (b) is carried out for at least 5 minutes, at least 10 minutes, at least 15 minutes, at least 20 minutes, or at least 25 minutes. Each possibility represents a separate embodiment of the present invention.

[0348] It should be understood that references to the duration of step (b) refer to individual runs of step (b). Specifically, as detailed herein, according to some embodiments, the process is carried out cyclically, with the alkali metal being recycled after completion of the reaction and returned for reuse in subsequent runs of step (b). Thus, it should be understood that, consistent with the above clauses directed to individual runs of step (b), repetitions of step (b) are permitted to cumulatively exceed the lower threshold set forth above.

[0349] c Reference is now made specifically to step (c) of the process, which, according to some embodiments, involves isolating the reduced transition metal or alloy thereof.

[0350] According to some embodiments, step (c) comprises isolating the reduced transition metal or alloy thereof from the reaction mixture. According to some embodiments, step (c) comprises isolating the reduced transition metal from the reaction mixture. According to some embodiments, step (c) comprises isolating the reduced transition metal alloy from the reaction mixture. According to some embodiments, step (c) comprises isolating the reduced iron from the reaction mixture.

[0351] According to some embodiments, isolating comprises evaporating the alkali metal oxide, and optionally oxygen and / or alkali metal, from the reactor. According to some embodiments, isolating comprises evaporating the alkali metal oxide from the reactor. According to some embodiments, isolating comprises evaporating the alkali metal oxide and oxygen from the reactor. According to some embodiments, isolating comprises evaporating the alkali metal oxide and alkali metal from the reactor. According to some embodiments, isolating comprises evaporating the alkali metal oxide, oxygen, and alkali metal from the reactor. According to some embodiments, the isolating in step (c) involves evaporating sodium metal from the reactor, and the process further comprises step (d) of collecting the isolated iron metal or alloy thereof.

[0352] According to some embodiments, step (c) comprises evaporating the sodium metal, oxygen, and optionally sodium oxide from the reactor to produce isolated iron metal.

[0353] According to some embodiments, step (c) comprises first evaporating oxygen and then evaporating alkali metal. According to some embodiments, step (c) comprises first evaporating oxygen and then evaporating sodium metal.

[0354] According to some embodiments, evaporating the alkali metal is carried out at a temperature detailed in step (5) herein.

[0355] According to some embodiments, evaporating the alkali metal is carried out at reduced pressure as specified in step (5) herein.

[0356] According to some embodiments, the evaporating is carried out for a duration specified for step (5) herein.

[0357] According to some embodiments, the isolated reduced transition metal or alloy thereof is in the physical form described in step (3) herein.

[0358] According to some embodiments, the isolating step (c) involves vaporizing the alkali metal produced in Reaction Scheme II and removing the alkali metal from the reactor, thereby leaving the reactor with the reduced transition metal or alloy thereof. According to some embodiments, the vaporizing involves heating the alkali metal. According to some embodiments, the vaporizing involves reducing the pressure within the reactor. According to some embodiments, the isolating step (c) involves vaporizing the alkali metal from the reactor. According to some embodiments, the isolating step (c) involves boiling the alkali metal from the reactor.

[0359] According to some embodiments, the isolating step (c) involves vaporizing the sodium metal produced in Reaction Scheme II and removing the sodium metal from the reactor, thereby leaving the reactor with the reduced transition metal or alloy thereof. According to some embodiments, the vaporizing involves heating the sodium metal. According to some embodiments, the vaporizing involves reducing the pressure within the reactor. According to some embodiments, the isolating step (c) involves vaporizing the sodium metal from the reactor. According to some embodiments, the isolating step (c) involves boiling the sodium metal from the reactor.

[0360] According to some embodiments, transferring sodium metal as a gas from the reactor produces isolated transition metals or alloys thereof.

[0361] Also, in industrial processes, transition metal oxides may be provided from ores that contain contaminants such as silicon oxide (typically silicon dioxide). When providing such transition metal oxide compositions in step (a) of the present process, they may not react, and the contaminants may be separated using an additional step of melting the transition metal product and filtering / skimming off the contaminants.

[0362] According to some embodiments, step (c) comprises isolating the reduced transition metal or alloy thereof from the reaction mixture, wherein isolating comprises evaporating the alkali metal oxide, and optionally oxygen and / or alkali metal, from the reactor, wherein evaporating comprises applying a reduced pressure to the reaction mixture, applying a stream of inert gas to the reaction mixture, or both.

[0363] According to some embodiments, the evaporating of step (c) comprises applying a vacuum to the reaction mixture.

[0364] According to some embodiments, the vaporizing is performed at a pressure ranging from 0.001 bar to 0.5 bar, including each value and subrange within the specified range.

[0365] According to some embodiments, the evaporating of step (c) comprises flowing an inert gas through the reaction mixture.

[0366] Specifically, application of an inert gas stream has been found to promote the evaporation of sodium oxide below its boiling or decomposition point, and at this low temperature, sodium oxide has been found to be unreactive with iron species, thereby avoiding the formation of sodium-iron oxides, according to some embodiments.

[0367] According to some embodiments, the evaporation of step (c) is carried out concurrently with the reaction of step (b). According to some embodiments, the evaporation of step (c) is carried out at least partially concurrently with the reaction of step (b). The phrase "evaporating of step (c) is carried out at least partially concurrently with the reaction of step (b)" means that at least a portion of the duration of step (b) and at least a portion of the duration of step (c) are simultaneous.

[0368] Specifically, according to some embodiments, it is beneficial to rapidly remove alkali metal oxides and oxygen from the reaction mixture to increase the reaction rate.

[0369] According to some embodiments, the evaporating of step (c) is carried out after the reacting of step (b).

[0370] According to some embodiments, the evaporating of step (c) is performed in parallel with the reaction of Scheme I. According to some embodiments, the evaporating of step (c) is performed at least partially in parallel with the reaction of Scheme I. According to some embodiments, the evaporating of step (c) is performed after the reaction of Scheme I.

[0371] According to some embodiments, evaporating the alkali metal oxide from the reactor in step (c) is carried out at about the first temperature. According to some embodiments, evaporating the alkali metal oxide from the reactor in step (c) is carried out at a temperature in the range of ±100°C of the first temperature. According to some embodiments, evaporating the alkali metal oxide from the reactor in step (c) is carried out at a temperature in the range of ±50°C of the first temperature. According to some embodiments, evaporating the alkali metal oxide from the reactor in step (c) is carried out at a temperature in the range of ±25°C of the first temperature. According to some embodiments, evaporating the alkali metal oxide from the reactor in step (c) is carried out at a temperature in the range of ±15°C of the first temperature. According to some embodiments, evaporating the alkali metal oxide from the reactor in step (c) is carried out at a temperature in the range of ±10°C of the first temperature. According to some embodiments, evaporating the alkali metal oxide from the reactor in step (c) is carried out at a temperature in the range of ±5°C of the first temperature.

[0372] d) Now, specific reference is made to step (d) of the process. As detailed above, steps (a)-(c) include several variations. The first main variation involves carrying out the reactions of Schemes I and II (and III), whereby the product iron is isolated in step (c) from a reaction mixture containing iron, sodium, and optionally oxygen. The second main variation involves carrying out the reaction of Scheme I, whereby the product iron is isolated in step (c) from a reaction mixture containing iron, sodium oxide, and optionally sodium. The operation of the steps depends on the route taken.

[0373] Therefore, reference is now made to step (d) of the first main variant.

[0374] Specifically, step (d) is optional and includes condensing alkali metal vaporized during step (c). According to some embodiments, step (d) includes condensing sodium vaporized during step (c).

[0375] According to some embodiments, the method further comprises a step (d) of condensing the evaporated alkali metal. According to some embodiments, the evaporated alkali metal is condensed in a dedicated container. According to some embodiments, the container is maintained under air and / or water protective conditions. According to some embodiments, the container is a sealable container.

[0376] According to some embodiments, the method further comprises a step (d) of condensing the evaporated sodium metal. According to some embodiments, the evaporated sodium metal condenses in a dedicated container. According to some embodiments, the container is maintained under air and / or water protective conditions. According to some embodiments, the container is a sealable container. The sodium metal container is discussed below with respect to the system.

[0377] Generally, alkali metals are solid materials at room temperature and atmospheric pressure. According to some embodiments, in step (c), the alkali metals are heated and optionally placed under reduced pressure, so that they convert to vapor. According to some embodiments, step (d) is relevant when the isolation in step (c) involves such evaporation, which involves condensation of the alkali metal vapor in a separate container. While the term "condensing" typically refers to the conversion from gas to liquid, it should be understood that the condensed alkali metal may convert to a solid gradually or instantaneously, depending, for example, on the temperature in the alkali metal container. Thus, the term "condensing" in the context of step (e) also includes deposition of a gas onto a solid.

[0378] Reference is now made to step (d) of the second main variant.

[0379] As detailed herein, step (d) of the second main variant can, according to some embodiments, be divided into two substeps: step (d1), directed to condensing the transition metal oxides evaporated in step (c), and step (d2), directed to dissociating the condensed transition metal oxides into their corresponding elements.

[0380] Here, reference is made to step (d1).

[0381] According to some embodiments, the process further comprises the step (d1) of condensing the vaporized alkali metal oxide in a condensation vessel. According to some embodiments, the process further comprises the step (d1) of condensing the vaporized alkali metal oxide, and optionally the alkali metal of step (c), in a condensation vessel. According to some embodiments, the process further comprises the step (d1) of condensing the vaporized alkali metal oxide and the alkali metal of step (c) in a condensation vessel.

[0382] According to some embodiments, the condensing in step (d1) is carried out at a temperature lower than the first temperature. According to some embodiments, the condensing in step (d1) is carried out at a temperature at least 100°C lower than the first temperature. According to some embodiments, the condensing in step (d1) is carried out at a temperature at least 200°C lower than the first temperature. According to some embodiments, the condensing in step (d1) is carried out at a temperature at least 250°C lower than the first temperature. According to some embodiments, the condensing in step (d1) is carried out at a temperature at least 300°C lower than the first temperature. According to some embodiments, the condensing in step (d1) is carried out at a temperature at least 350°C lower than the first temperature. According to some embodiments, the condensing in step (d1) is carried out at a temperature at least 400°C lower than the first temperature.

[0383] According to some embodiments, the pressure in the condensation vessel is as described in step (6).

[0384] Reference is now made to step (d2), which may follow step (d1) according to some embodiments.

[0385] According to some embodiments, the process comprises heating the condensed alkali metal oxide of step (d1) to a second temperature to form a condensed alkali metal oxide according to Scheme II: II:M A 2O → 2×M AFurther comprising the step (d2) of inducing the reaction according to +0.5O2, As a result, the net reaction resulting from the reactions of Schemes I and II is III: III:M T n O m → n×M T +0.5m×O2 does not consume alkali metals.

[0386] The second temperature and the reactions of Schemes II and III are described in detail when related to step (b) of the first main variant.

[0387] Now, with specific reference to step (e) of the present process, which is optional and includes returning the alkali metal condensed in step (e) to the reactor. Specifically, because at this stage both the first and second major variants of the present process have already carried out both reactions (I and II) to produce alkali metal, regeneration of alkali metal can occur in both variants of step (e).

[0388] According to some embodiments, the process includes step (e) of transferring the alkali metal formed in step (d) to a reactor. It should be understood that the phrase "transferring the alkali metal formed in step (d)" can refer to the alkali metal (e.g., sodium) formed in step (d) according to the first main variant, or the alkali metal formed in step (d2) according to the second main variant, depending on the context and the preceding steps listed.

[0389] According to some embodiments, the process includes step (e) of returning the sodium metal formed in step (d) to the reactor. According to some embodiments, step (e) includes transferring the condensed alkali metal to the reactor, thereby recycling the alkali metal. According to some embodiments, step (e) includes transferring the condensed sodium metal to the reactor, thereby recycling the sodium metal.

[0390] According to some embodiments, the alkali metal is transferred to the reactor in step (e) as a condensed material. According to some embodiments, the alkali metal is transferred to the reactor in step (e) as a liquid. According to some embodiments, the alkali metal is transferred to the reactor in step (e) as a solid.

[0391] It should be understood that performing step (e) completes one cycle of the process, and according to some embodiments, the process may proceed for additional cycles upon reconstituting the alkali metal and providing further transition metal oxide.

[0392] According to some embodiments, the process further comprises repeating steps (a)-(d) for at least one additional sequence after step (f). According to some embodiments, the process further comprises repeating steps (a)-(d1) for at least one additional sequence after step (f). According to some embodiments, the process further comprises repeating steps (a)-(d2) for at least one additional sequence after step (f). According to some embodiments, the process further comprises repeating steps (a)-(c) for at least one additional sequence after step (f). According to some embodiments, the process further comprises repeating steps (a)-(c) for at least one additional sequence. According to some embodiments, the process further comprises repeating steps (a)-(d) for at least one additional sequence. According to some embodiments, the process further comprises repeating steps (a)-(d1) for at least one additional sequence. According to some embodiments, the process further comprises repeating steps (a)-(d2) for at least one additional sequence.

[0393] According to some embodiments, the process comprises performing steps (a)-(f) and performing steps (a)-(c) for at least one cycle. According to some embodiments, the process comprises performing steps (a)-(f) and performing steps (a)-(c) for multiple cycles.

[0394] Reference is now made specifically to step (f) of the process, which involves isolating the transition metal or alloy thereof. In particular, it is understood that step (f) can be carried out in both variations of step (e).

[0395] Specifically, according to some embodiments, the process further comprises collecting the isolated transition metal or alloy thereof produced in step (c). Specifically, according to some embodiments, the process further comprises collecting the isolated iron produced in step (c).

[0396] According to some embodiments, the isolating step (c) involves evaporating the alkali metal from the reactor, and the process further comprises step (f) of collecting the isolated transition metal or alloy thereof. According to some embodiments, the isolating step (c) involves evaporating the sodium metal from the reactor, and the process further comprises step (f) of collecting the isolated iron metal.

[0397] Reference is now made to Figures 7-8, which are block diagrams illustrating a process for reducing at least one transition metal oxide to the corresponding transition metal or alloy thereof.

[0398] 7 is a block diagram illustrating a process for reducing at least one iron oxide to the corresponding iron, according to some embodiments, including steps (a), (b), and (c) detailed herein. Step (a) is represented by block 1000, step (b) is represented by block 1010, and step (c) is represented by block 1020.

[0399] 8 is a block diagram representing a process for reducing at least one iron oxide to the corresponding iron, according to some embodiments, including steps (a), (b), (c), (d), (e), and (f) detailed herein. Step (a) is represented by block 1000, step (b) is represented by block 1010, step (c) is represented by block 1020, step (f) is represented by block 1030, step (d) is represented by block 1040, and step (e) is represented by block 1050.

[0400] 9 is a block diagram illustrating a process for reducing at least one transition metal oxide to the corresponding transition metal, according to some embodiments, including steps (a), (b), (c), (d1), (d2), (e), and (f) detailed herein. Step (a) is represented by block 1000, step (b) is represented by block 1010, step (c) is represented by block 1025, step (f) is represented by block 1030, step (d1) is represented by block 1040, step (d2) is represented by block 1045, and step (e) is represented by block 1050.

[0401] Below, non-limiting specific embodiments of specific reaction sequences that may be performed by the process of the present invention are provided. Reference is further made to Figures 10-12, which are block diagrams each representing a selected process (i.e., two specific reaction sequences) for reducing at least one transition metal oxide to the corresponding transition metal or its alloy. Each one of Figures 4-6 represents a process according to some embodiments, including steps (a), (b), and (c) detailed herein, where step (a) is represented by block 1000, step (b) is represented by block 1010, and step (c) is represented by block 1020. Related specific examples are presented above in the sections relating to Figures 4-6.

[0402] Reference will now be made specifically to embodiments of the present process directed to the formation of transition metal alloys.

[0403] According to some embodiments, the process is for the preparation of a metal alloy, and step (a) or step (b), or step (1) or step (2), comprises adding a second metal, M b to the reactor, wherein the second metal is M T and step (b) or step (2) combines a second metal with an alkali metal and transition metal oxide to induce the reaction detailed herein, as shown in Scheme IV: IV:M T +M b → M T M b This further induces the reaction.

[0404] According to some embodiments, the second metal, M b is not an alkali metal. According to some embodiments, the second metal, M b is a transition metal, M Tb is.

[0405] The term "alloyable" refers to the ability of two metallic elements to form an alloy. Thus, as used herein, the term "alloyable metal" refers to any metal that can form an alloy with the transition metal formed in the process of the present invention. According to some embodiments, the alloyable metal forms an alloy with the transition metal formed under the conditions of the process of the present invention (i.e., the conditions of step (b) or (2)).

[0406] Also, according to some embodiments, the alloyable metal may be provided as a metal oxide and reduced (ie, reduced by an alkali metal) under the process reaction conditions.

[0407] According to some embodiments, the process is for the preparation of a metal alloy, wherein step (a) or (1) comprises the step of forming a metal alloy of formula M b i O jwherein each one of i and j is 1, 2, 3, 4, 5, 6, or 7, and step (b) or (2) comprises combining the two metal oxides with an alkali metal, and Reaction Schemes I and III are: Ia:M T n O m +2m×M A → m×M A 2O+n×M T , Ib:M b i O j +2j×M A → j×M A 2O+i×M b , IIIa:M T n O m → n×M T +0.5m×O2, IIIb:M b i O j → i×M b +0.5j × O2, Step (b) is reaction IV to form an alloy: IV:M T +M b → M T M b Further induce.

[0408] It should be understood that Reaction Scheme I can be divided into Ia and Ib, while Reaction Scheme III can be divided into IIIa and IIIb.

[0409] According to some embodiments, the second metal, M b is a transition metal, M Tb is.

[0410] Thus, according to some embodiments, step (a) or (1) comprises a compound of formula M Ta n O m , and M Tb i O jwherein each one of i and j is 1, 2, 3, 4, 5, 6, or 7; and M Ta , M Tb is a transition metal selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn), step (b) or (2) comprises combining a transition metal oxide with an alkali metal, and Reaction Schemes I and III are Ia:M Ta n O m +2m×M A → m×M A 2O+n×M Ta , Ib:M Tb i O j +2j×M A → j×M A 2O+i×M Tb , IIIa:M Ta n O m → n×M Ta +0.5m×O2, IIIb:M Tb i O j → i×M Tb +0.5j × O2, Step (b) or (2) is carried out by reaction IV to form an alloy: IV:M Ta +M Tb → M Ta M Tb was further induced.

[0411] According to some embodiments, the transition metal alloy formed by any one of the processes of the present invention is selected from the group consisting of brass (CuZn), constantan (CuNi), CuNiFe (CuNiFe or CuNiFeCo), cupronickel (CuNiFe or CuNiMn), manganin (CuMnNi), nickel silver (CuNi or CuNiZn), Elinvar (NiFeCr), Fernico (FeNiCo), ferromanganese (FeMn), ferronickel (FeNi), ferrotitanium (FeTi), ferrovanadium (FeV), invar (FeNi), kovar (FeNiCo), chromel (NiCr), and nitinol (NiTi). [Example]

[0412] General Procedures - System Reaction of several metal oxides with pure sodium at 900°C to reduce the metal oxide to the pure metal. Fe2O3 metal oxide was tested.

[0413] System components: 1. Reactor - SS304 265mL custom-made. 2.304 SS crucible 25mL. 3. The first induction heating system (Chinese 6kw), induction coil (5 turns). 4. Second heating system (Chinese 3kw), induction coil (3 turns). 5. The system was cooled by one water chiller. 6. SS304 tubing 430mL (sodium waste reactor) and flange (NW50). 7. Parker connector for argon insertion. 8. Thermocouples Type K (three - one external 1 / 2 inch connection, one in the reactor, and one in the crucible). 9. Argon flow control device company "AALBORG". 10. Three 1 / 4 inch on / off valves and one vacuum valve. 11. Bellows trap with ss wool to protect the vacuum pump. 12. Vacuum pump. 13. Stand. 14. Insulating wool.

[0414] The reactor was made of SS304 and had a volume of 265 mL. It was connected to a sodium waste reactor, made of SS304 and having a volume of 430 mL, through a 1 / 2-inch SS316 tube. A 304 SS crucible was placed inside the reactor.

[0415] Protective alumina blocks used in critical positions to protect the induction system and O-rings in KF flanges.

[0416] General experimental procedure A crucible containing 3 grams of metal oxide and 3 grams of pure sodium was placed in a reactor for the reaction. One thermocouple was placed inside the reactor to control the first induction system, and a second thermocouple was placed inside the crucible to measure the reaction, both connected to a data logger.

[0417] The first induction system heats the lower part of the reaction vessel where the crucible is placed to 600° C. during the experiment with a heating rate of 15° C. / min and an argon flow rate of 40 mL / min.

[0418] At the start of the reaction, the vacuum valve and the second argon outlet valve were closed, and the argon flow outlet was routed through the first argon outlet valve. When the temperature reached 500 °C, the first argon outlet valve was closed and the second valve was opened. Furthermore, when the first induction system reached 700 °C, the second induction system was turned on and reached 200 °C. 70 minutes after the start of the reaction, a vacuum of 0.1 bar was slowly applied using a pump until it reached 0.1 bar over 2 hours at 600 °C. After 30 minutes, argon was introduced at a flow rate of 40 mL / min. When the pressure in the system reached 14.6 psi, the first argon outlet was opened and the induction system was turned off.

[0419] Example 1: Reaction of iron ore with metallic sodium The reaction of metallic sodium with four iron ores (ORE1, ORE2, ORE3, and ORE4) was carried out according to the general experimental procedure described above. The ores contained various concentrations of different iron oxides, including hematite (FeO), magnetite (FeO), and goethite (FeOOH), as well as other compounds such as nacrite (AlSiO(OH)), silicon dioxide (SiO), magnesium silicon hydroxide (MgSi(OH)), and aluminum hydroxide (Al(OH)) (Table 1).

[0420] The temperature profiles of the four reactions are shown in Figure 13, and it can be seen that the exotherms occurred at approximately the same temperature of 500°C. However, the reduction reactions with ORE1 and ORE3 experienced a higher temperature increase during the exotherm, reaching approximately 850°C and 700°C. The reaction with ORE2 had a more moderate increase to 620°C, while ORE4 did not exhibit a significant temperature increase. The XRD results for the reactions of metallic sodium with ORE1, ORE2, ORE3, and ORE4 sodium are shown in Figures 14, 15, 16, and 17, respectively.

[0421] [Table 1]

[0422] Example 2: Reduction of Fe2O3 in stainless steel (SS type 304) and silicon carbide (SiC) crucibles. The reduction of FeO to iron metal using sodium was carried out as detailed above in the general experimental procedures. Two separate reactions were performed, one in a stainless steel (SS type 304) crucible and the other in a silicon carbide (SiC) crucible. The temperature profiles of the two reactions are shown in Figure 18, and it can be seen that the exotherm occurred at approximately the same temperature, although a higher temperature rise was observed in the SS crucible (approximately 550°C vs. approximately 650°C, respectively).

[0423] The XRD results for the two reactions are shown in Figures 19 and 20. As shown from the diffractograms, the final product from the reaction using the SS crucible contained mainly different types of sodium iron oxides, with a relatively low selectivity to pure iron (11.5 wt%). This suggests that the reactivity between the sodium substrate and the SS crucible is somehow related to the increased formation of these undesired sodium iron oxides.

[0424] In contrast, the reaction using the SiC crucible was more favorable to producing pure iron with almost 5 times more of this product (wt%) compared to the SS crucible. The percentage of metallization of the reaction can be calculated when referencing the percentage of metallic iron compared to general iron in the examples and is determined to be 89%.

[0425] Example 3: Isolation of Fe by evaporation of sodium metal oxide under vacuum and / or argon flow. The general procedure was modified to first evaporate sodium oxide metal from the reactor. A reduction reaction according to the general experimental procedure was carried out using 20 grams of Fe2O3 and 20 grams of sodium metal. The reactor was then heated to 600°C to evaporate the sodium oxide, which was done using two different methods: under vacuum and under argon gas flow. After evaporation, iron metal was collected as the final product.

[0426] Example 4: Recovery of sodium metal from vaporized sodium oxide To further process and dissociate the sodium oxide of Example 3 into its constituent elements sodium and oxygen, the vaporized sodium oxide was removed from the reactor and condensed in a condensing vessel at a temperature of approximately 200°C.

[0427] Example 5: Scale-up reaction of iron ore with metallic sodium A scale-up using 20 grams of sodium metal and 20 grams of iron ore in a 100 gram stainless steel crucible reactor was then carried out following the modified general procedure of Examples 3 and 4. The temperature profile of the reaction is shown in Figure 21A and shows that the exotherm occurred at approximately 260°C, which is about 200°C lower than that observed in the smaller scale reaction of Example 1. The exotherm peak also persisted for a longer period, resulting in a broader peak. The XRD results for this reaction are shown in Figure 21A.

[0428] Example 6: Reaction of low-grade iron ore with metallic sodium A reaction between low-grade iron ore and metallic sodium was conducted according to step (2) of the present process. A crucible, 2.5 grams of iron oxide (a 50:50 weight / weight mix of hematite and silica), and 2.5 grams of pure sodium were placed in a reactor. One thermocouple was placed inside the reactor to control the first induction system, and a second thermocouple was placed inside the crucible to measure the reaction, both connected to a data logger.

[0429] The first induction system heated the lower part of the reaction vessel, where the crucible was located, to 600° C. at a heating rate of 10° C. / min. An argon flow rate of 100 mL / min was maintained through the reactor throughout the experiment.

[0430] At the start of the reaction, the vacuum valve and the second argon outlet valve were closed and the argon outlet was routed through the first argon outlet valve. 90 minutes after the start of the reaction, the system was turned off.

[0431] The product was in powder form, and analysis revealed that sodium oxide had formed and reacted with silica to form sodium silicate. The product consisted of 36% iron (% by weight of the sample tested by XRD) and 64% sodium silicate. Metallization was 100% (weight of iron converted / weight of total initial iron content). The high silica content can react with sodium oxide to produce sodium silicate.

[0432] The XRD results for this reaction are shown in FIG.

[0433] Example 7: Reaction of iron ore with metallic sodium under nitrogen flow The reaction between iron ore and metallic sodium was carried out according to step (2) of the present process. A crucible, 2 grams of an iron oxide mixture (mainly hematite), and 3.8 grams of pure sodium were placed in a reactor. A thermocouple was placed inside the wall of the crucible to control the induction system.

[0434] Before heating the system, nitrogen gas was flowed through the system at a flow rate of 400 mL / min for 1 hour. During the system heating phase, the induction system heated the reactor containing the crucible to 400 °C at a heating rate of 15 °C / min. A nitrogen flow rate of 100 mL / min was maintained throughout the experiment. After heating the system to 400 °C, the system was left at this temperature for 2 hours. The evaporation phase then began, during which the nitrogen outlet was closed and the vacuum pump was turned on for 1 hour. After the evaporation phase, the vacuum pump and heating system were turned off and the system was allowed to cool. When the pressure in the system reached 14.6 psia, the nitrogen outlet was opened.

[0435] The product was in powder form: iron - 39.4% (w% of the sample tested by XRD), metallization - 90% (weight of converted iron / weight of the initial total iron content). The XRD results for this reaction are shown in FIG.

[0436] Example 8: Reaction of iron ore with metallic sodium in the presence of iron powder The reaction between iron ore and metallic sodium was carried out according to step (2) of the present process. A crucible was placed in a reactor with 2 grams of an iron oxide mixture (mainly hematite), 3.8 grams of pure sodium, and 1 gram of iron powder. A thermocouple was placed inside the wall of the crucible to control the induction system.

[0437] Before heating the system, nitrogen gas was flowed through the system for 1 hour at a flow rate of 400 mL / min. During the system heating phase, the induction system heated the reactor containing the crucible to 400 °C at a heating rate of 15 °C / min, and a nitrogen flow rate of 100 mL / min was maintained throughout the experiment. After heating the system to 400 °C, the system was left at this temperature for 2 hours. The evaporation phase then began, during which the nitrogen outlet was closed and the vacuum pump was turned on for 1 hour. After the evaporation phase, the vacuum pump and heating system were turned off, and the system was allowed to cool. When the pressure in the system reached 14.6 psi, the nitrogen outlet was opened.

[0438] The product was in powder form. Iron content 38.4% (w% of sample tested by XRD), metallization - 97%. Without wishing to be bound by any theory of mechanism of action, it was found in this experiment that the iron powder helps to lower the surface energy of the sodium, enhancing wetting and mass transfer.

[0439] The XRD results for this reaction are shown in FIG.

[0440] Example 9: Reaction of iron ore with metallic sodium at different Na:ore ratios. The reaction between iron ore and metallic sodium was carried out according to step (2) of the present process. A crucible was placed in a reactor with 2 grams of an iron oxide mixture (mainly hematite 97% w / w) and 5.7 grams of pure sodium. A thermocouple was placed inside the wall of the crucible to control the induction system (ore to sodium ratio of 1:2.85).

[0441] During the system heating phase, the induction system heated the reactor containing the crucible to 400°C at a heating rate of 10°C / min, and an argon flow rate of 100 mL / min was maintained throughout the experiment. After heating the system to 400°C, the system was left at this temperature for 2 hours. The heating system was then turned off and the system was allowed to cool.

[0442] The product was in powder form. Iron content 38.4% (w% of sample tested by XRD), metallization - 93%. The addition of extra sodium apparently had no positive effect on the overall metallization or purity of the product.

[0443] The XRD results for this reaction are shown in FIG.

[0444] Example 10: Sodium Oxide Dissociation - Comparative Example The process of the present invention was attempted by (I) reducing iron oxide with sodium (step (2)) immediately followed by dissociating sodium oxide (step (4)) (Example 10A), and (II) separating the sodium oxide formed in step (2) from the iron in step (3) followed by dissociating sodium oxide in step (4) (Example 10B).

[0445] Example 10A: Sodium Oxide Dissociation Without Prior Separation The experiment was carried out in a stainless steel crucible. A combination of sodium (3.8 grams) and an oxide mixture (2 grams of ore 1, mostly hematite) was inserted. The crucible was placed in an induction magnetic field inside a stainless steel 304 reactor. The reactor was filled with N2 and the reduction of the oxide was carried out at 400°C for 1 hour. The dissociation of the sodium oxide was then attempted in the same vessel without separation. The temperature was increased to 800°C and the pressure was reduced to 1 Torr in the reactor over 1 hour.

[0446] Figure 26 shows the significant formation of sodium-ferrite instead of dissociating sodium oxide into sodium and oxygen. Conclusion: XRD analysis shows that a significant amount of the available iron was converted to sodium-ferrite.

[0447] Example 10B: Sodium Oxide Dissociation with Prior Separation of Sodium Oxide from Iron Step (2): A reaction between iron ore and metallic sodium was carried out according to step (2) of the present process. Sodium (3.7 grams) and an iron oxide mixture (2 grams, mostly hematite) were mixed in the same reactor used in Example 10A and heated to 400°C for 1 hour. Excess sodium was evaporated at 400°C and 1 Torr for 2 hours. The reactor was cooled to room temperature, and the sodium oxide and iron were separated using a magnet and a sieve. The effluent was separated into sodium oxide and iron.

[0448] The XRD results for this reaction are shown in FIG.

[0449] Step (3): Separation of iron and sodium oxide was carried out according to step (3) of this process. The reaction products (iron and sodium oxide) from step (2) above were placed in a nitrogen-filled box containing 0% H2O and 1000 ppm O2 and magnetically separated.

[0450] Figure 28 is an XRD of only the sodium oxide extracted from the product.

[0451] Step (4): Dissociation of sodium oxide into recycled sodium and oxygen was carried out according to step (4) of the present process. Two grams of sodium oxide were extracted from iron oxide as detailed above and heated to 750°C at 1 Torr for 1 hour. The dissociated sodium evaporated during the reaction due to the high temperature and low pressure and condensed on a perforated ring and an alumina heat deflector (Figures 30A and 30B). The total mass collected was 1.2, achieving a process mass efficiency of 85% (w / w%). Figure 29 is a schematic diagram of the present system.

[0452] This demonstrates the advantage of the separation in step (3).

[0453] While the present invention has been described in connection with specific embodiments thereof, it is evident that many alternatives, modifications, and variations exist which will be apparent to those skilled in the art. It is to be understood that the invention is not necessarily limited in its application to the details of construction and arrangement of components and / or methods set forth herein. Other embodiments may be implemented and the embodiments may be carried out in various ways. Accordingly, the present invention embraces all such alternatives, modifications, and variations which are within the scope of the appended claims.

Claims

1. 1. A process for the reduction of iron metal oxides, said process comprising: (1) Formula Fe ｎ O ｍ wherein each one of n and m is 1, 2, 3, 4, 5, 6, or 7; (2) contacting the iron oxide with sodium metal in a reactor and adjusting the temperature in the reactor to a first temperature in the range of 100°C to 500°C to produce a product of Scheme I: I: Fe ｎ O ｍ +2m×Na → m×Na ２ Inducing a reaction according to O + n × Fe; (3) Na ２ separating O and Fe; (4) The separated Na ２ and increasing the temperature of O to a second temperature at least 50° C. higher than the first temperature to form a reaction mixture according to Scheme II: II: Na ２ O → 2×Na+0.5O ２ and inducing a response according to As a result, the net reaction resulting from the above reactions of Schemes I and II is III: III: Fe ｎ O ｍ → n × Fe + 0.5 m × O ２ but does not consume said sodium metal.

2. 2. The process of claim 1, wherein step (1) comprises providing an ore comprising hematite, magnetite, goethite, nakhlite, wustite, or a combination thereof.

3. 3. The process of claim 2, wherein the ore further comprises silicon dioxide.

4. The iron oxide is Fe ２ O ３ , Fe ３ O ４ 4. The process of any one of claims 1 to 3, wherein the hydroxybenzoate is selected from the group consisting of: , FeOOH, and combinations thereof.

5. The iron oxide is Fe ２ O ３ The process according to any one of claims 1 to 4, comprising:

6. 6. The process of any one of claims 1 to 5, wherein the reactor comprises a crucible, and step (2) comprises contacting the iron oxide with sodium metal in the crucible.

7. The crucible may be made of stainless steel, silicon carbide, copper, aluminum nitride, aluminum oxide, Inconel, ZrO ２ or a combination thereof.

8. 7. The process of claim 6, wherein the crucible comprises aluminum nitride, aluminum oxide, copper, Inconel, or a combination thereof.

9. 9. The process of any one of claims 1 to 8, wherein adjusting the temperature in the reactor in step (2) comprises gradually increasing the temperature in the reactor to the first temperature at a rate of from 1°C / min to 100°C / min.

10. 10. The process of any one of claims 1 to 9, wherein increasing the temperature to the second temperature in step (4) comprises gradually increasing the temperature in the reactor to the second temperature at a rate of from 1°C / min to 100°C / min.

11. 11. The process of any one of claims 1 to 10, further comprising step (5) isolating the sodium metal from the mixture of step (4).

12. 12. The process of claim 11, wherein the isolating of step (5) involves evaporating the sodium metal from the reactor.

13. 22. The process of claim 21, further comprising the steps of (6) condensing the vaporized sodium metal and (7) transferring the condensed sodium metal to the reactor, thereby recycling the sodium metal.

14. (1) providing the iron oxide; (2) combining the iron oxide with sodium metal in a reactor and adjusting the temperature in the reactor to the first temperature; (3) Na ２ separating O and Fe; (4) The separated Na ２ raising the temperature of O to the second temperature to induce reaction according to Scheme III; (5) evaporating the sodium metal formed in step (4); and (6) condensing the evaporated sodium metal; and (7) transferring the condensed sodium metal to the reactor; The process of any one of claims 1 to 13, wherein the process further comprises repeating steps (1) to (3) for at least one additional sequence.

15. 15. The process of any one of claims 12 to 14, wherein evaporating the sodium metal is carried out at a temperature in the range of 400°C to 800°C and a pressure in the range of 0.001 bar to 0.5 bar.

16. Fe ｎ O ｍ But Fe ２ O ３ , FeO, FeOOH, Fe ３ O ４ or a combination thereof, wherein Reaction Schemes I and III are I:Fe ２ O ３ +6×Na → 3×Na ２ O+2×Fe、 --I:Fe ２ O ３ → 2×Fe+1.5×O ２ 、 or I:FeO+2×Na →Na ２ O+Fe、 I::e →a!!!!!!!!!!! ２ 、 or I:Fe ３ O ４ +8×Na → 4×Na ２ O+3×Fe、 III: Fe ３ O ４ → 3 x Fe + 2 x O ２ The process according to any one of claims 1 to 15, wherein

17. Step (3) is ２ 17. A process according to any one of claims 1 to 16, comprising mechanically separating O and the Fe to produce isolated iron metal with a purity of at least 90% w / w.

18. Step (3) is ２ 18. The process of claim 17, comprising magnetically separating O and the Fe.

19. The process of any one of claims 1 to 18, wherein step (4) is carried out at a temperature in the range of 400°C to 800°C.

20. 20. The process of any one of claims 1 to 19, wherein step (4) is carried out at a pressure in the range of from 0.001 bar to 0.5 bar.

21. 21. The process of any one of claims 1 to 20, wherein the reaction mixture of step (2) is substantially free of additional solvent and carrier and consists essentially of the iron metal oxide, the sodium metal, and product reduced iron metal and sodium oxide.

22. The process of any one of claims 1 to 21, wherein step (2) is carried out in an air and water protected environment.

23. 23. The process of any one of claims 1 to 22, wherein step (2) comprises contacting the iron oxide with the sodium metal in a weight ratio ranging from 1:20 to 20:

1.

24. 24. The process of any one of claims 1 to 23, wherein the reaction mixture of step (4) is substantially free of additional solvents and carriers.

25. The process of any one of claims 1 to 24, wherein step (4) is carried out in an air and water protected environment.

26. 1. A process for the reduction of a transition metal oxide, said process comprising: (1) Formula M Ｔ ｎ O ｍ wherein each one of n and m is 1, 2, 3, 4, 5, 6, or 7; and M Ｔ is a first row transition metal selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn), (2) contacting at least one transition metal with an alkali metal in a reactor and adjusting the temperature in the reactor to a first temperature in the range of 100° C. to 500° C. above the melting point of the alkali metal, to produce a product according to Scheme I: I:M Ｔ ｎ O ｍ +2m×M Ａ → m×M Ａ ２ O+n×M Ｔ and inducing a reaction according to the formula: Ａ is Na or K), (3) M Ａ ２ O and M Ｔ and (4) Separated M Ａ ２ 2. The temperature of O is increased to a second temperature at least 50° C. above the reduction temperature to form Scheme II:

27. II:M Ａ ２ O → 2 × M Ａ +0.5O ２ and inducing a response according to

28. As a result, the net reaction resulting from the above reactions of Schemes I and II is III: III:M Ｔ ｎ O ｍ → n × M Ｔ +0.5m x O ２ but does not consume said alkali metal.

29. 27. The process of claim 26, wherein step (1) comprises providing an ore comprising hematite, magnetite, goethite, nakhlite, wustite, or a combination thereof.

30. 28. The process of claim 27, wherein the ore further comprises silicon dioxide.

31. 29. The process of any one of claims 26 to 28, wherein the reactor comprises a crucible, and step (2) comprises contacting the transition metal oxide with an alkali metal in the crucible.

32. The crucible may be made of stainless steel, silicon carbide, copper, aluminum nitride, aluminum oxide, Inconel, ZrO ２ 30. The process of claim 29, comprising:

33. 31. The process of claim 30, wherein the crucible comprises aluminum nitride, aluminum oxide, copper, Inconel, or a combination thereof.

34. 32. The process of any one of claims 26 to 31, wherein adjusting the temperature in the reactor in step (2) comprises gradually increasing the temperature in the reactor to the first temperature at a rate of from 1°C / min to 100°C / min.

35. 33. The process of any one of claims 26 to 32, wherein increasing the temperature to the second temperature in step (4) comprises gradually increasing the temperature in the reactor to the second temperature at a rate of from 1°C / min to 100°C / min.

36. 34. The process of any one of claims 26 to 33, further comprising step (5) isolating the alkali metal from the mixture of step (4).

37. 35. The process of claim 34, wherein the isolating of step (5) involves evaporating the alkali metal from the reactor.

38. 36. The process of claim 35, further comprising the steps of (6) condensing the vaporized alkali metal and (7) transferring the condensed alkali metal to the reactor, thereby recycling the alkali metal.

39. (1) providing the transition metal oxide; (2) combining the transition metal oxide with the alkali metal in a reactor and adjusting the temperature in the reactor to the first temperature; (3) M Ａ ２ O and M Ｔ and (4) The separated M Ａ ２ raising the temperature of O to the second temperature to induce reaction according to Scheme III; (5) evaporating the alkali metal formed in step (4); and (6) condensing the evaporated alkali metal; and (7) transferring the condensed alkali metal to the reactor; 37. The process of any one of claims 26 to 36, wherein the process further comprises repeating steps (1) through (3) for at least one additional sequence.

40. 38. The process of any one of claims 35 to 37, wherein evaporating the alkali metal is carried out at a temperature in the range of 400°C to 800°C and a pressure in the range of 0.001 bar to 0.5 bar.

41. M Ｔ The process of any one of claims 26 to 38, wherein is a first row transition metal selected from the group consisting of Fe, Ni, Cr, Cu, Zn, and Mn.

42. M Ｔ is Fe, M Ｔ ｎ O ｍ But Fe ２ O ３ , FeO, FeOOH, Fe ３ O ４ or a combination thereof, wherein Reaction Scheme I is I:Fe ２ O ３ +6×M Ａ → 3×M Ａ ２ O+2×Fe、 or I:FeO+2×M Ａ → M Ａ ２ O+Fe、 or I: Fe ３ O ４ +8×M Ａ → 4×M Ａ ２ 40. The process of claim 39, wherein O+3×Fe.

43. M Ｔ is Ni, M Ｔ ｎ O ｍ is NiO and Reaction Scheme I is I: NiO + 2 × M Ａ → M Ａ ２ 40. The process of claim 39, wherein O+Ni.

44. M Ｔ is Cr, M Ｔ ｎ O ｍ But, Cr ２ O ３ , CrO, CrO ３ or a combination thereof, wherein Reaction Scheme I is I:Cr ２ O ３ +6×M Ａ → 3×M Ａ ２ O+2×Cr、 or I:CrO+2×M Ａ → M Ａ ２ O+Cr、 or I: CrO ３ +6×M Ａ → 3×M Ａ ２ 40. The process of claim 39, wherein O+Cr.

45. M Ｔ is Cu, M Ｔ ｎ O ｍ But Cu ２ O, CuO, CuO ２ or a combination thereof, wherein Reaction Scheme I is I: Cu ２ O+2×M Ａ → M Ａ ２ O+2Cu, or __________ Ａ → * Ａ ２ ____、 or I: CuO ２ +4×M Ａ → 2M Ａ ２ 40. The process of claim 39, wherein O+Cu.

46. M Ｔ is Zn, M Ｔ ｎ O ｍ ZnO, and Reaction Scheme I is I: ZnO + 2 × M Ａ → M Ａ ２ 40. The process of claim 39, wherein O+Zn.

47. M Ｔ is Mn, M Ｔ ｎ O ｍ However, MnO, Mn ３ O ４ , Mn ２ O ３ , MnO ２ , Mn ２ O ７ or a combination thereof, wherein Reaction Scheme I is I:MnO+2×M Ａ → M Ａ ２ O+Mn、 or I:Mn ３ O ４ +8×M Ａ → 4×M Ａ ２ O+3×Mn、 or I:Mn ２ O ３ +6×M Ａ → 3×M Ａ ２ O+2×Mn、 or I:MnO ２ +4×M Ａ → 2M Ａ ２ O+Mn、 or I: Mn ２ O ７ +14×M Ａ → 7×M Ａ ２ 40. The process of claim 39, wherein the reaction is O + 2 x Mn.

48. A process according to any one of claims 26 to 45 for the preparation of a metal alloy, comprising: Step (1) is a compound of formula M Ｔａ ｎ O ｍ , and M Ｔｂ ｉ O ｊ wherein each one of i and j is 1, 2, 3, 4, 5, 6, or 7; Ｔａ , M Ｔｂ is a transition metal selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn), Step (2) comprises combining the transition metal oxide with an alkali metal, and Reaction Scheme I comprises: Ia: M Ｔａ ｎ O ｍ +2m×M Ａ → m×M Ａ ２ O+n×M Ｔａ 、 Ib:M Ｔｂ ｉ O ｊ +2j × M Ａ → j × M Ａ ２ O + i × M Ｔｂ and Step (2) forms the alloy according to Reaction IV: IV:M Ｔａ +M Ｔｂ → M Ｔａ ・M Ｔｂ The process of any one of claims 26 to 45, further comprising:

49. When the alkali metal is sodium, Scheme II is II: Na ２ O → 2Na+0.5O ２ The process of any one of claims 26 to 46, wherein

50. Step (3) is the M Ａ ２ O and the above M Ｔ and mechanically separate the isolated M with a purity of at least 90% w / w. Ｔ 48. The process of any one of claims 26 to 47, comprising producing

51. Step (3) is the M Ａ ２ O and the above M Ｔ 49. The process of claim 48, comprising magnetically separating

52. The process of any one of claims 26 to 49, wherein step (4) is carried out at a temperature in the range of from 400°C to 800°C.

53. 51. The process of any one of claims 26 to 50, wherein step (4) is carried out at a pressure in the range of from 0.001 bar to 0.5 bar.

54. 52. The process of any one of claims 26 to 51, wherein the reaction mixture of step (2) is substantially free of additional solvent and carrier and consists essentially of the transition metal oxide, the alkali metal, and product reduced transition metal and alkali metal oxides.

55. 53. The process of any one of claims 26 to 52, wherein the reaction sequence of step (2) is carried out in an air and water protected environment.

56. 54. The process of any one of claims 26 to 53, wherein step (2) comprises contacting the transition oxide with an alkali metal in a weight ratio ranging from 1:20 to 20:

1.

57. 55. The process of any one of claims 26 to 54, wherein the reaction mixture of step (4) is substantially free of additional solvents and carriers.

58. 1. A method for the reduction of a transition metal oxide, said method comprising: contacting a transition metal oxide with an alkali metal to form a mixture; heating the mixture to produce transition metal and alkali metal oxides; isolating the transition metal from the heated mixture; and and thermally decomposing said alkali metal oxide to regenerate said alkali metal.

59. 59. The method of claim 58, further comprising isolating the alkali metal and recycling the alkali metal in another cycle of transition metal oxide reduction.

60. 60. The method of claim 59, wherein the isolated transition metal has a purity of at least 90% w / w.

61. 59. The method of claim 58, wherein the alkali metal is sodium.

62. 59. The method of claim 58, wherein the alkali metal is potassium.

63. The transition metal oxide is represented by the formula M Ｔ ｎ O ｍ wherein each of n and m is independently 1, 2, 3, 4, 5, 6, or 7; M Ｔ 59. The method of claim 58, wherein is selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn.

64. 59. The method of claim 58, wherein the transition metal is Fe.

65. 59. The method of claim 58, wherein the transition metal is Ni.

66. 59. The method of claim 58, wherein the transition metal is Cr.

67. 59. The method of claim 58, wherein the transition metal is Cu.

68. 59. The method of claim 58, wherein the transition metal is Zn.

69. 59. The method of claim 58, wherein the transition metal is Mn.

70. 61. The method of claim 60, wherein the isolated transition metal is Fe, Co, Ni, or Cu and has a purity of at least 99% w / w.

71. the alkali metal is sodium or potassium, 59. The method of claim 58, wherein the transition metal is selected from Fe, Ni, Cr, Cu, Zn, and Mn.

72. the transition metal oxide comprises iron oxide; 59. The method of claim 58, wherein the alkali metal is sodium.

73. The transition metal oxide is Fe ２ O ３ , FeO, Fe ３ O ４ or a combination thereof.

74. the transition metal oxide comprises copper oxide; 27. The method of claim 26, wherein the alkali metal is sodium.

75. The transition metal oxide is Cu ２ O, CuO, CuO ２ or a combination thereof.

76. the transition metal oxide comprises nickel oxide; 59. The method of claim 58, wherein the alkali metal is sodium.

77. the transition metal oxide comprises chromium oxide; 59. The method of claim 58, wherein the alkali metal is sodium.

78. The transition metal oxide is Cr ２ O ３ , CrO, CrO ３ or a combination thereof.

79. 59. The method of claim 58, wherein the mixture comprises a molar equivalent or excess of the alkali metal relative to the transition metal oxide.

80. 59. The method of claim 58, wherein the mixture is neat.

81. 59. The method of claim 58, wherein said heating of said mixture comprises heating at a temperature of at least 300°C.

82. 59. The method of claim 58, wherein said heating of said mixture comprises heating at a temperature in the range of 300°C to 3000°C.

83. 59. The method of claim 58, wherein said heating of said mixture comprises heating at a temperature of at least 350°C.

84. 59. The method of claim 58, wherein said heating of said mixture comprises heating at a temperature of at least 400°C.

85. 59. The method of claim 58, wherein said heating of said mixture comprises heating at a temperature of at least 450°C.

86. 59. The method of claim 58, wherein said heating of said mixture comprises heating at a temperature of at least 500°C.

87. 59. The method of claim 58, wherein said thermal decomposition of said alkali metal oxide comprises heating under reduced pressure at a temperature at or above the decomposition temperature of said alkali metal oxide.

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