Processes for the reduction of transition metal oxides

Abstract

The present disclosure relates generally to processes for the reduction of transition metals using alkali metals to produce reduced transition metals.

Description

[Technical field]

[0001] The present disclosure relates generally to processes for the reduction of transition metals using alkali metals to produce reduced transition metals. [Background technology]

[0002] The production of metals (such as zinc, iron, nickel, lead, chromium, palladium, copper and silver) is usually carried out on a large scale electrochemically or / and by carbothermal reduction. As a result, they use catalysts and reagents that are usually highly polluting and non-reusable. Furthermore, electrochemical reduction processes have many difficulties and are therefore often expensive and energy consuming. Conventional metal production plants are large and require huge capital investments for construction and operation. Commonly used smelting and other metal extraction processes, which are often carried out in several steps, are energy intensive and produce carbon dioxide (CO 2 ) and other pollutants.

[0003] A commonly used method of producing nickel involves the reverberatory furnace followed by electrolytic refining.

[0004] Numerous alternatives have been proposed for the production of high-quality iron (for example) with a substantially lower environmental footprint and lower energy demands. The most sought-after and researched concepts are technologies based on electrochemical refining and electrowinning.

[0005] US Patent Publication No. 2020 / 0263313 discloses a system and method for molten oxide electrolysis. Metallurgical assemblies and systems according to US Patent Publication No. 2020 / 0263313 may include a refractory vessel including a side and a base. The base may define a plurality of openings centrally disposed within the base. The side and base may at least partially define an interior volume of the refractory vessel. The assembly may include a lid configured to removably couple with the refractory vessel and form a seal with the refractory vessel. The lid may define a plurality of openings therethrough. The assembly may also include a current collector proximate the base of the refractory vessel. The current collector may include a conductive extension located within the plurality of openings centrally disposed within the base.

[0006] WO 2011 / 092516 discloses a method for the preparation of iron or iron alloys from iron ore, which comprises the steps of electrolyzing molten iron ore in an electrolytic bath containing at least one molten salt and optionally dissolved metal, and separating the resulting ferrous 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.

[0007] US Patent No. 8,764,962 discloses a method for extracting a target element from an oxide feedstock of the target element, the method comprising: providing a liquid oxide electrolyte comprising at least 75% by weight of one or more oxide compounds, in which the oxide feedstock dissolves to form ionic oxygen species and ionic target element species; providing an anode in contact with the electrolyte, the anode comprising a 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 comprising at least 50% by weight of the metal anode substrate, the one element being more reactive to oxygen than the target element; providing a cathode in contact with the electrolyte; transporting electrons from the ionic oxygen species in the electrolyte across the solid oxide layer on the metal substrate to the metal substrate to form gaseous oxygen; and reducing the ionic target element species in the electrolyte to form a liquid of the target element at the cathode, the melting temperature of which exceeds 1200°C.

[0008] A number of medium-scale electrolysis-based plants / reactors have been built, but due to issues with the construction materials, electrodes and electrical conductivity of the melt, none have been shown to hold any additional value over conventional smelters. In particular, electrolysis-based reduction has not been successful so far and cannot meet the EU requirement to decarbonize steel production by 2030.

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

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

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

[0012] The present invention provides a process for the production of transition metals and their alloys from the corresponding transition metal oxides, which is simple and cost-effective compared to corresponding processes for preparing transition metals (e.g. electrolysis) and usually results in high purity metals.

[0013] Throughout this disclosure, the term "metal" should be understood to refer to the zero oxidation state of the metallic element, unless specified as a metal oxide or a component of a metal oxide (i.e., a metal cation).

[0014] The present invention uses two reaction sequences of individual reactions, and has surprisingly found that, according to some embodiments, there is an affinity between the reaction sequences (e.g., within a shared reaction or reaction system) resulting in a synergistic effect that results in a simple process and high yield and purity. The first reaction (reaction I) is the reduction of a transition metal oxide using an alkali metal, and in some cases, the reaction is neat (i.e., the reaction mixture consists essentially of a transition metal oxide and an alkali metal). Specifically, alkali metals are known to have lower (more negative) redox potentials than transition metals, and can be represented as shown in Scheme I:

[0015] [ka]

[0016] (In the formula, M T is a transition metal atom; n and m are integers (e.g., 1 to 7); M A It promotes the oxidation-reduction reaction of ZnO (an alkali metal).

[0017] Thus, the first reaction, according to some embodiments, produces the desired products, transition metal and alkali metal oxide. Advantageously, the reaction is carried out at a temperature T above the melting point of the alkali metal to obtain a reaction mixture in which the alkali metal is in a fluid state and is therefore highly reactive towards the transition metal oxide. Advantageously, the alkali metals also have relatively low melting points (Na at 97.8° C.; K at 63.5° C.), and the redox reaction of Scheme I is exothermic, facilitating the two reaction sequences with minimal input of external energy.

[0018] Finally, although alkali metals such as sodium and potassium do not occur in nature, their preparation through electrolysis is convenient; they are usually provided as ores and do not suffer from the hurdles of direct electrolytic reduction of transition metal oxides, such as the difficulty of electrolysis in solution. Furthermore, sodium and potassium metals are produced electrochemically from their salts, NaCl and KCl, respectively, which are abundant in nature. These metals are usually considered to be industrial by-products of the chlorine gas industry. As such, their use does not consume net energy, but rather avoids disposal efforts and associated environmental damage.

[0019] The second reaction (Reaction II) is the thermal decomposition of the alkali metal oxide formed in the previous reaction described above. Specifically, this is shown in Scheme II:

[0020] [ka]

[0021] It is depicted in.

[0022] Advantageously, the decomposition temperatures of alkali metal oxides are not very high (Na - 540°C; K - 300°C), and in combination with their low melting temperatures, the exothermic nature of Reaction I results in a significant synergistic effect, making the present process greater than known processes for transition metal production.

[0023] Yet another advantage of the present process is the net reaction resulting from the combination of the two reaction sequences. Specifically, the net reaction scheme for reactions I and II is shown in reaction scheme III (multiplying scheme II by m and balancing the equation):

[0024] [ka]

[0025] Shown below as;

[0026] As those skilled in the art can readily appreciate, in the net reaction scheme III, the alkali metal is not included as a reactant to be consumed, but is used as a catalyst. This is very advantageous. First, recycling materials in chemical and commercial large-scale synthesis is very important today, as it is recognized that avoiding consumption of materials leads to environmental conservation. Second, since the alkali metal does not react net, the only by-product of the reaction is oxygen, a harmless gas, which is also easy to separate from the transition metal produced.

[0027] Yet another advantage of the process relates to the relative inertness of alkali metals with respect to transition metals, whereby alkali-transition metal alloys do not form even at high temperatures. The relatively low boiling temperatures of the alkali metals (Na 882.8°C; K 758.8°C, lower under reduced pressure) combined with the high boiling points of the first row transition metals (e.g. Fe 2,862°C; Ni 2,730°C; Cu 2,562°C) allow the product transition metal to be easily isolated via evaporation of oxygen and the alkali metal upon completion of the reaction.

[0028] Finally, the present process has distinct advantages over known transition metal preparations, as it makes the formation of transition metal alloys easily accessible. In particular, there are many highly desirable transition metal-containing alloys (e.g., brass, constantan, nitinol, etc.) that require high temperatures or other extreme conditions for preparation. The present process provides a clear route to their formation. In particular, as detailed above, the reaction of Scheme I is exothermic, and, according to some embodiments, high temperatures are reached with heating of the reaction mixture. Therefore, the process is carried out in the presence of a second metal oxide, as detailed herein, and both metals can be reduced at high temperatures (Scheme I), and, according to some embodiments, can also induce an alloy-forming reaction between the two metals.

[0029] Thus, according to some embodiments, a process for the reduction of a transition metal oxide is provided, the process comprising: (a) Formula M T n O m wherein each one of n and m is 1, 2, 3, 4, 5, 6, or 7; M T is a first row transition metal selected from: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn; (b) In the reactor, a transition metal oxide is mixed with an alkali metal (M A ) and adjusting the temperature in the reactor to a temperature T to react with the reactants according to Reaction Schemes I and II:

[0030] [ka]

[0031] Thus, the net reaction obtained from the two reaction sequences is III

[0032] [ka]

[0033] However, no alkali metal is consumed and the resulting reaction mixture contains reduced transition metal, M T or alloys thereof, alkali metals, and optionally oxygen. (In the formula, M A is Na or K; and the temperature T is higher than the melting point of the alkali metal, M A 2 is equal to or higher than the decomposition temperature of O); and (c) isolating the reduced transition metal or alloy thereof from the reaction mixture. Includes.

[0034] According to some embodiments, a process for the reduction of a transition metal oxide is provided, the process comprising: (a) Formula M T n O m wherein each one of n and m is 1, 2, 3, 4, 5, 6, or 7; M T is a first row transition metal selected from: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn; (b) In the reactor, a transition metal oxide is mixed with an alkali metal (M A ) and adjust the temperature in the reactor to a temperature T to produce a reduced transition metal, M T or an alloy thereof, an alkali metal, and optionally oxygen. (In the formula, M A is Na or K; and the temperature T is higher than the melting point of the alkali metal, M A 2 is equal to or higher than the decomposition temperature of O); and (c) isolating the reduced transition metal or alloy thereof from the reaction mixture. Includes.

[0035] According to some embodiments, a process for the reduction of a transition metal oxide is provided, the process comprising: (a) A transition metal (M T ) oxides and alkali metals (MA ) in contact with each other; (b) Heating the transition metal oxide and alkali metal in a reactor to a temperature (T) to produce a reduced transition metal (M T ) and alkali metals (M A forming a reaction mixture comprising (Wherein, the temperature (T) is the alkali metal (M A ) and the melting point of alkali metal oxides (M A 2 is equal to or higher than the decomposition temperature of (c) Reduced transition metal (M T from the reaction mixture. Includes.

[0036] According to some embodiments, step (a) comprises continuously providing at least one transition metal oxide to a reactor such that the total transition metal oxide provided in step (a) is in molar excess over the alkali metal in step (b), the molar excess being at least 400%.

[0037] According to some embodiments, the temperature T is equal to or greater than the boiling point of the alkali metal.

[0038] According to some embodiments, the isolation of step (c) requires evaporating the alkali metal from the reactor; and the process further comprises a step (d) of recovering the isolated transition metal or alloy thereof.

[0039] According to some embodiments, the temperature T is at or above the boiling point of the alkali metal, and the isolation of step (c) requires evaporating the alkali metal from the reactor; and the process further comprises a step (d) of recovering the isolated transition metal or alloy thereof.

[0040] According to some embodiments, the process further includes the steps of (e) condensing the evaporated alkali metal; and (f) transferring the condensed alkali metal to the reactor, thereby recycling the alkali metal.

[0041] According to some embodiments, the process includes: (a) providing at least one transition metal oxide (b) combining a transition metal oxide with an alkali metal at a temperature T to induce two reaction sequences; (c) evaporating the alkali metal from the reactor to produce an isolated transition metal or alloy thereof; (d) recovering the isolated transition metal or alloy thereof; (e) condensing the evaporated alkali metal; and (f) transferring the condensed transition metal to a reactor. Includes; Step (e) may occur before step (d), and the process further includes repeating steps (a)-(d) for at least one additional sequence.

[0042] 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. Each possibility represents a separate embodiment of the present invention.

[0043] According to some embodiments, M T is Fe; M T n O m is Fe 2 O 3 , FeO, Fe 3 O 4 or a combination thereof; and Reaction Schemes I and III are:

[0044] [ka]

[0045] or

[0046] [ka]

[0047] or

[0048] [ka]

[0049] Each possibility represents a separate embodiment of the present invention.

[0050] According to some embodiments, M T is Ni; M T n O m is NiO; and Reaction Schemes I and III are:

[0051] [ka]

[0052] It is.

[0053] According to some embodiments, M T is Cr; M T n O m Cr 2 O 3 , CrO, CrO 3 or a combination thereof; and Reaction Schemes I and III are:

[0054] [ka]

[0055] or

[0056] [ka]

[0057] or

[0058] [ka]

[0059] Each possibility represents a separate embodiment of the present invention.

[0060] According to some embodiments, M T is Cu; M T n O m Cu 2 O, CuO, CuO 2 or a combination thereof; and Reaction Schemes I and III:

[0061] [ka]

[0062] or

[0063] [ka]

[0064] or

[0065] [ka]

[0066] Each possibility represents a separate embodiment of the present invention.

[0067] According to some embodiments, M T is Zn; M T n O m ZnO; and Reaction Schemes I and III:

[0068] [ka]

[0069] It is.

[0070] According to some embodiments, M T is Mn; M T n O m MnO, Mn 3 O 4 , Mn 2 O 3 , MnO 2 , Mn 2 O 7 or a combination thereof; and Reaction Schemes I and III are:

[0071] [ka]

[0072] or

[0073] [ka]

[0074] or

[0075] [ka]

[0076] or

[0077] [ka]

[0078] or

[0079] [ka]

[0080] Each possibility represents a separate embodiment of the present invention.

[0081] According to some embodiments, the process is for the preparation of a metal alloy, Step (a) is a reaction of formula M Ta n O m , and formula M Tb i O j wherein each one of i and j is 1, 2, 3, 4, 5, 6, or 7; 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; and Step (b) involves combining a transition metal oxide with an alkali metal, Reaction Schemes I and III show:

[0082] [ka]

[0083] and step (b) further comprises reaction IV to form an alloy:

[0084] [ka]

[0085] This induced.

[0086] According to some embodiments, the alkali metal is Na and Scheme II is:

[0087] [ka]

[0088] It is.

[0089] According to some embodiments, T is at least 540°C.

[0090] According to some embodiments, the alkali metal is K and Scheme II is:

[0091] [ka]

[0092] It is.

[0093] According to some embodiments, T is at least 300° C.

[0094] According to some embodiments, step (c) comprises evaporating the alkali metal and oxygen from the reactor to produce an isolated transition metal or alloy thereof with a purity of at least 90% w / w.

[0095] According to some embodiments, the transition metal is Fe, Co, Ni or Cu and has a purity of at least 99% w / w.

[0096] According to some embodiments, the reaction mixture of step (b) is substantially free of additional solvent and carrier, and consists essentially of the transition metal oxide, the alkali metal, and the product reduced transition metal or alloy thereof.

[0097] According to some embodiments, the two reaction sequences of step (b) are carried out in an air- and water-protected environment.

[0098] According to some embodiments, the process further comprises: a housing defining a reaction chamber; and a transition metal oxide inlet, an alkali metal inlet, an alkali metal outlet, and an isolated transition metal or alloy outlet, each of said inlets and outlets being in fluid communication with the reaction chamber; Reactor; an alkali metal container including an alkali metal inlet and an alkali metal outlet; an isolated transition metal or alloy container containing a transition metal inlet; a condenser configured to condense the evaporated alkali metal, the condenser including a proximal end connected to the alkali metal outlet of the reactor and a distal end connected to the alkali metal inlet of the alkali metal container; an alkali metal transfer tube including a proximal end connected to the alkali metal inlet of the reactor and a distal end connected to the alkali metal outlet of the alkali metal container; a transition metal transfer tube including a proximal end connected to the transition metal outlet of the reactor and a distal end connected to the transition metal inlet of the isolated transition metal or alloy container; The method includes providing a system comprising:

[0099] According to some embodiments, the reactor further includes an inert gas inlet and a gas outlet, each in fluid communication with the reaction chamber, the inert gas inlet being in fluid communication with a source of inert gas.

[0100] According to some embodiments, the process includes: (a) providing at least one transition metal oxide to a reaction chamber through a transition metal oxide inlet; (b) combining a transition metal oxide with an alkali metal in a reaction chamber to induce two reaction sequences; (c) vaporizing the alkali metal through an alkali metal outlet of the reactor to produce an isolated transition metal or alloy thereof; (d) transferring the isolated transition metal or alloy thereof through a transition metal transfer tube to a container of isolated transition metal or alloy; (e) condensing the evaporated alkali metal into an alkali metal container using a condenser; and (f) transferring the condensed alkali metal from the alkali metal container to the reactor through an alkali metal transfer tube. Includes; Step (e) may be performed before step (d).

[0101] According to some embodiments, step (b) further comprises inserting an inert gas into the reaction chamber through an inert gas inlet, thereby maintaining a reaction environment protected from air.

[0102] According to certain embodiments, step (b), step (c), or both, further comprises venting the formed oxygen gas through a gas outlet of the reactor.

[0103] According to some embodiments, the condenser further includes a one-way valve disposed between the proximal end and the distal end thereof, the valve configured to regulate the flow of evaporated alkali metal from the rector to the alkali metal container; the alkali metal transfer tube further includes a one-way valve disposed between the proximal end and the distal end thereof, the valve configured to regulate the flow of condensed alkali metal from the alkali metal container to the rector; The transition metal transfer tube further includes a one-way valve disposed between the proximal and distal ends thereof, the valve configured to regulate the flow of the isolated transition metal or metal alloy from the rector to the container of isolated transition metal or alloy.

[0104] Further embodiments and the full scope of the present invention will become apparent from the detailed description given hereinafter. It should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

[0105] In addition to the exemplary aspects and embodiments described above, further aspects and embodiments will become apparent by reference to the drawings and by study of the following detailed descriptions.

[0106] The accompanying drawings are included to provide a further understanding of the invention, 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. [Brief description of the drawings]

[0107] [Figure 1] FIG. 1 is a block diagram illustrating a process for the reduction of at least one transition metal oxide to a corresponding transition metal or an alloy thereof, according to some embodiments. [Diagram 2] FIG. 2 is a block diagram illustrating a process for the reduction of at least one transition metal oxide to a corresponding transition metal or an alloy thereof, according to some embodiments. [Diagram 3] FIG. 3 is a block diagram illustrating a process for the reduction of Fe2O3 to iron metal, according to some embodiments. [Figure 4] FIG. 4 is a block diagram illustrating a process for the reduction of FeO to iron metal, according to some embodiments. [Diagram 5] FIG. 5 is a block diagram illustrating a process for the reduction of NiO to nickel metal, according to some embodiments. [Figure 6] FIG. 6 is a block diagram illustrating a process for the reduction of Cr2O3 to chromium metal, according to some embodiments. [Figure 7] FIG. 7 is a block diagram illustrating a process for the reduction of Cu2O to copper metal, according to some embodiments. [Figure 8] FIG. 8 is a block diagram illustrating a process for the reduction of ZnO to zinc metal, according to some embodiments. [Figure 9] FIG. 9 is a block diagram illustrating a process for the reduction of TiO2 to titanium metal, according to some embodiments. [Figure 10] FIG. 10 is a block diagram illustrating a process for the simultaneous reduction of ZnO to zinc metal and CuO 2 to copper metal and the formation of a Cu·Zn alloy therefrom, according to some embodiments. [Figure 11] FIG. 11 is a block diagram illustrating a process for the simultaneous reduction of NiO to nickel metal and Fe2O3 to iron metal and the formation of an Fe·Ni alloy therefrom, according to some embodiments. [Figure 12] 12A and 12B are X-ray diffraction (XRD) patterns of iron produced from two separate reactions between Fe2O3 and Na according to some embodiments of the present process. [Figure 13A] FIG. 13A is a graph that depicts temperature (° C.) measured in a reactor versus time (min) during the reaction between CuO and Na to form copper metal according to some embodiments of the present process. [Figure 13B] FIG. 13B is an XRD pattern of copper produced in the reaction between Cu2O and Na according to some embodiments of the present process. [Figure 14A] FIG. 14A is a graph depicting temperature (° C.) measured in a reactor versus time (min) during the reaction between NiO and Na to form nickel metal according to some embodiments of the present process. [Figure 14B] FIG. 14B is an XRD pattern of nickel produced in the reaction between NiO and Na according to some embodiments of the present process. [Figure 15A] FIG. 15A is a graph that represents the temperature (° C.) measured in the reactor versus time (min) during the reaction between Cr2O3 and Na to form chromium metal according to some embodiments of the present process. [Figure 15B] FIG. 15B is an XRD pattern of chromium produced in the reaction between Cr2O3 and Na according to some embodiments of the present process. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0108] In the following description, various aspects of the present disclosure will be described. For purposes of explanation, specific configurations and details are shown 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 so as not to obscure the present disclosure.

[0109] Before describing the present disclosure in more detail, it is to be understood that the present disclosure is not limited to particular embodiments described, which 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, as the scope of the present disclosure will be limited only by the appended claims.

[0110] According to some embodiments, a process is provided for the reduction of one or more transition metal oxides to the corresponding transition metal or an alloy containing same. The process comprises:

[0111] [ka]

[0112] (In the formula, M T , M A , n and m are as described herein), which results in a net reaction scheme III:

[0113] [ka]

[0114] Becomes;

[0115] Several advantages of this process over the art are detailed herein. In summary:

[0116] (i) Reactions I and II have been found to be compatible with one another and can therefore be carried out sequentially (e.g., in one reaction system), which according to some embodiments has proven to be a simple procedure.

[0117] (ii) Reactions I and II have been found to have a synergistic effect, according to some embodiments, resulting in high yields.

[0118] (iii) The above synergistic effects further result in high purity metals and alloys according to some embodiments.

[0119] (iv) The reaction can, according to some embodiments, be carried out neat (i.e., without solvent), which is environmentally beneficial.

[0120] (v) Carrying out the reaction at a temperature above the melting point of the alkali metal results in a reaction mixture in which the alkali metal, according to some embodiments, is in a reactive fluid state.

[0121] (iv) The use of alkali metals is advantageous due to their relatively low melting points, which, according to some embodiments, require only moderate or no net energy input. For example, sodium and potassium metals are considered by-products that can be used instead of being wasted, which are economic and environmental advantages.

[0122] (vii) Redox reaction I is exothermic, driving the two reaction sequences with minimal input of external energy - according to some embodiments, this is another economic and environmental advantage.

[0123] (viii) According to some embodiments, electrosynthesis of the alkali metal that catalyzes the reaction is convenient.

[0124] (ix) The decomposition temperatures of alkali metal oxides are not very high, further facilitating the two reaction sequences with minimal input of external energy - according to some embodiments, this is yet another economic and environmental advantage.

[0125] (x) The net reaction III, which depicts the combination of reactions I and II, does not consume alkali metals, i.e., they are used as catalysts. Because they are used as catalysts, they are essentially recycled, and therefore only small amounts of alkali metals are needed to produce large amounts of transition metals or alloys through the process, which is both an economic and environmental advantage.

[0126] (xi) the only by-product of the reaction sequence of the present invention is oxygen, which is a harmless gas and, according to some embodiments, is easily separated from the transition metal produced.

[0127] (xii) The alkali metal does not readily react with the transition metal (i.e., such that alkali metal-transition metal alloys are not formed under the conditions of the present process) and the reaction mixture remains substantially clean from by-product contaminants, according to some embodiments.

[0128] (xiii) While alkali metals have low boiling temperatures, first row transition metals have high boiling points, which, according to some embodiments, allow for easy isolation of the product transition metal or alloy through evaporation of oxygen and the alkali metal after completion of the reaction.

[0129] (xiv) When the process is carried out in the presence of a second metal or metal oxide, according to some embodiments, the exothermicity of Reaction I in combination with heating of the reaction mixture may result in the formation of an alloy from the first metal (i.e., the transition metal initially provided as an oxide) and the second metal.

[0130] According to some embodiments, there is provided a process for the reduction of transition metal oxides, the process comprising carrying out steps (a)-(c) and optionally additional steps, as detailed herein.

[0131] Reference is now made specifically to step (a) of the process, which, according to some embodiments, comprises providing at least one transition metal oxide.

[0132] According to some embodiments, step (a) comprises reacting a compound of formula M T n O m According to some embodiments, step (a) includes providing at least one transition metal oxide having the formula M T n O m According to some embodiments, step (a) includes providing a transition metal oxide having the formula M T n O m The method includes providing a single transition metal oxide having the following formula:

[0133] Specifically, as can be understood by those skilled in the art, in step (a) T n O m According to some embodiments, providing one 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 mThe provision of one of the transition metal oxides can result in the formation of a reduced transition metal upon completion of the process. In particular, if the reaction mixture of step (b) does not contain a metal or metal oxide capable of alloying with the transition metal provided in step (a), the result of the two reaction sequences of step (b) will be a transition metal, according to some embodiments. However, if another metal capable of alloying 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 may be formed from the two metals.

[0134] 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.

[0135] According to some embodiments, m is 1, 2, 3, 4, 5, 6, or 7. Each possibility represents a separate embodiment of the present invention.

[0136] 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.

[0137] In general, the term "first row transition metal element" refers to any one of elements 21-29, namely, scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu).

[0138] According to some embodiments, M Tis 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.

[0139] According to some embodiments, the transition metal oxide is provided in step (a) as a solid.

[0140] As detailed herein, during step (b), the transition metal oxide is consumed to provide the transition metal and oxygen, while according to some embodiments the alkali metal is conserved or recycled, such that additional transition metal oxide can be continuously provided to the reaction mixture and additional transition metal can be continuously obtained.

[0141] According to some embodiments, step (a) comprises continuously providing at least one transition metal oxide to the reactor, such that the total transition metal oxide provided in step (a) is in molar excess over the alkali metal in step (b). According to some embodiments, step (a) comprises gradually providing at least one transition metal oxide to the reactor. According to some embodiments, at any time during step (b), the alkali metal may be in molar excess over the transition metal oxide therein in the reactor, but 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 over the alkali metal catalyst.

[0142] For purposes of this specification, the term "continuously" means that the transition metal oxide is added to the reactor over time. The term is not limited to continuous or interrupted (e.g., batch) addition of the transition metal oxide.

[0143] 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 is in the range of 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, including each value and subrange within the specified range.

[0144] It should be understood that "X% molar excess" as used herein means that the total molar amount of transition metal oxides ultimately added in step (a) exceeds the molar amount of alkali metal used by X%. For example, if the reaction in step (b) starts with 10 moles of sodium metal in the reactor and continues until the reaction stops with 100 moles of Fe 2 O 3 is added to the reactor over a period of 5 hours, the transition metal oxide Fe 2 O 3 was said to be added in 900% molar excess over the alkali metal.

[0145] According to some embodiments, the at least one transition metal is: Sc 2 O 3 , TiO 2 , Ti 2 O 3, V.O., V. 2 O 3 , V.O. 2 , V 2 O 5 , Cr 2 O 3 , CrO, CrO 3 , MnO, Mn 3 O 4 , Mn 2 O 3 , MnO 2 , Mn 2 O 7 , Fe 2 O 3 , FeO, Fe 3 O 4 , CoO, Co 2 O 3 , Co 3 O 4 , NiO, Cu 2 O, CuO, CuO 2 , ZnO, and any combination thereof. Each possibility represents a separate embodiment of the present invention.

[0146] According to some embodiments, M T n O m Sc 2 O 3 Includes.

[0147] According to some embodiments, M T n O m is TiO 2 , Ti 2 O 3 or a combination thereof. T n O m is TiO 2 According to some embodiments, M T n O m is Ti 2 O 3 According to some embodiments, M T n O m contains a mixture of titanium oxides.

[0148] According to some embodiments, M T n O m VO, V 2 O 3 , V.O. 2 , V 2 O 5 or a combination thereof. T n O m According to some embodiments, M T n O m V 2 O 3 According to some embodiments, M T n O m VO 2 According to some embodiments, M T n O m V 2 O 5 According to some embodiments, M T n O m contains a mixture of vanadium oxides.

[0149] According to some embodiments, M T n O m Cr 2 O 3 , CrO, CrO 3 or a combination thereof. T n O m Cr 2 O 3 According to some embodiments, M T n O m According to some embodiments, M comprises CrO. T n O m is CrO 3 According to some embodiments, M T n Om contains a mixture of chromium oxides.

[0150] According to some embodiments, M T n O m MnO, Mn 3 O 4 , Mn 2 O 3 , MnO 2 , Mn 2 O 7 or a combination thereof. T n O m According to some embodiments, M T n O m is Mn 3 O 4 According to some embodiments, M T n O m is Mn 2 O 3 According to some embodiments, M T n O m MnO 2 According to some embodiments, M T n O m is Mn 2 O 7 According to some embodiments, M T n O m contains a mixture of manganese oxides.

[0151] According to some embodiments, M T n O m is Fe 2 O 3 , FeO, Fe 3 O 4 or a combination thereof. T n O m is Fe 2 O 3According to some embodiments, M T n O m According to some embodiments, M T n O m is Fe 3 O 4 According to some embodiments, M T n O m contains a mixture of iron oxides.

[0152] According to some embodiments, M T n O m Co 2 O 3 , CoO, Co 3 O 4 or a combination thereof. T n O m Co 2 O 3 According to some embodiments, M T n O m According to some embodiments, M T n O m Co 3 O 4 According to some embodiments, M T n O m contains a mixture of cobalt oxides.

[0153] According to some embodiments, M T n O m contains NiO.

[0154] According to some embodiments, M T n O m Cu 2 O, CuO, CuO 2 or a combination thereof. Tn O m Cu 2 According to some embodiments, M T n O m According to some embodiments, M comprises CuO. T n O m CuO 2 According to some embodiments, M T n O m contains a mixture of copper oxides.

[0155] According to some embodiments, M T n O m contains ZnO.

[0156] Here, according to some embodiments, a transition metal oxide is mixed with an alkali metal (M A ) and adjusting the temperature in the reactor to a temperature T or higher to induce the two reaction sequences of Schemes I and II.

[0157] According to some embodiments, step (b) comprises reacting the transition metal oxide with an alkali metal at a temperature T. According to some embodiments, step (b) comprises reacting the transition metal oxide with an alkali metal at a temperature T or above.

[0158] According to some embodiments, step (b) comprises reacting the transition metal oxide with an alkali metal (M A) according to some embodiments, the act of combining the transition metal oxide with the alkali metal is carried out at a temperature T. In particular, if the reaction has not yet started, according to some embodiments, it requires external heating to reach the temperature T. Instead, after the reaction has started, its exothermicity can at least partially maintain or increase the internal temperature, so that according to some embodiments, less external heating is required or even the external heating may be at least temporarily stopped.

[0159] According to some embodiments, the combination of a transition metal oxide and an alkali metal in a reactor at a temperature T is carried out according to Reaction Schemes I and II:

[0160] [ka]

[0161] This leads to two reaction sequences:

[0162] According to some embodiments, the combination of a transition metal oxide and an alkali metal in a reactor at temperature T gives rise to two reaction sequences, Schemes I and II.

[0163] 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.

[0164] [ka]

[0165] 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.

[0166] According to some embodiments, the value of temperature T is selected such that the reactions of Schemes I and II are carried out. In other words, the temperature T exceeds the activation energy of both reactions and provides sufficient energy to the reaction system to provide suitable reaction conditions.

[0167] For the reaction of Scheme I, a key parameter, according to some embodiments, 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 any solvent). Also, at room temperature, both the alkali metal and transition metal oxide reactants are in a solid state, which tends to slow or prevent the chemical reaction. Thus, according to some embodiments, the temperature T is higher than the melting point of the alkali metal. According to some embodiments, at temperature T, the alkali metal is in a fluid state. According to some embodiments, at temperature T, the alkali metal is in a liquid state. According to some embodiments, at temperature T, the alkali metal is in a gaseous state.

[0168] For the reaction of Scheme II, the primary parameter, according to some embodiments, is the activation energy required to decompose the alkali metal oxide. Therefore, according to some embodiments, the temperature T is determined by the activation energy required to decompose the alkali metal oxide. A 2 According to some embodiments, the temperature T is equal to or greater than the decomposition temperature of M A 2 higher than the decomposition temperature of O.

[0169] The term "alkali metal" as used herein covers 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), as well as alloys thereof, containing at least one alkali metal in the zero oxidation state, e.g., NaK.

[0170] According to some embodiments, an alkali metal (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.

[0171] Sodium-potassium alloy, colloquially referred to as NaK, is an alloy of the alkali metals sodium and potassium that is normally liquid at room temperature.

[0172] According to some embodiments, the temperature T is at least 300° C., at least 350° C., at least 400° C., at least 450° C., at least 500° C., at least 540° C., at least 600° C., at least 700° C., at least 800° C., or at least 900° C. Each possibility represents a separate embodiment of the present invention. According to some embodiments, the temperature T is in the range of 300° C. to 3,000° C., 540° C. to 3,000° C., or 900° C. to 3,000° C. Each possibility represents a separate embodiment of the present invention, including each value and subrange within the specified range.

[0173] According to some embodiments, the alkali metal is sodium, and the temperature T is higher than the melting point of sodium. According to some embodiments, the alkali metal is sodium, and at the temperature T, sodium is in a fluid state. According to some embodiments, the alkali metal is sodium, and at the temperature T, sodium is in a liquid state. According to some embodiments, the alkali metal is sodium, and at the temperature T, sodium is in a gaseous state. At standard conditions, the boiling point and melting point of sodium are 97.8° C. and 883° C., respectively, and Na 2 The decomposition temperature of O is 540° C. According to some embodiments, the alkali metal is sodium and T is at least 100° C. According to some embodiments, the alkali metal is sodium and T is at least 540° C. According to some embodiments, the alkali metal is sodium and T is at least 883° C.

[0174] According to some embodiments, the alkali metal is potassium and the temperature T is greater than the melting point of potassium. According to some embodiments, the alkali metal is potassium and at the temperature T, potassium is in a fluid state. According to some embodiments, the alkali metal is potassium and at the temperature T, potassium is in a liquid state. According to some embodiments, the alkali metal is potassium and at the temperature T, potassium is in a gaseous state. At standard conditions, the boiling and melting points of potassium are 63.5° C. and 758.8° C., respectively, and K 2 The decomposition temperature of O is 300° C. According to some embodiments, the alkali metal is potassium and T is at least 63° C. According to some embodiments, the alkali metal is potassium and T is at least 758.8° C. According to some embodiments, the alkali metal is potassium and T is at least 300° C.

[0175] 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.

[0176] 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.

[0177] The term "solvent" refers to a non-reactive component of the composition that reduces the viscosity of the composition. Typically, solvents are volatile and therefore are removed under work-up conditions (such as elevated temperature and / or reduced pressure) after the chemical reaction is complete. The term "substantially solvent-free" or "solvent-free" refers to a composition that does not contain a solvent or is substantially free of a solvent as defined above. A substantially solvent-free composition can, according to some embodiments, contain a trace amount of solvent, for example ≦5% w / w, ≦3% w / w, ≦2% w / w, ≦1% or ≦0.5% w / w.

[0178] 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.

[0179] The term "consisting essentially of" means that the reaction mixture of step (b) comprises primarily the transition metal oxide, the alkali metal, and the product reduced transition metal or alloy thereof. Specifically, according to some embodiments, it does not contain a significant amount of solvent or carrier or any component not involved in Reaction Schemes I and II. According to some embodiments, the reaction mixture of step (b) comprises 5% w / w or less, 3% w / w or less, 2% w / w or less, or 1% w / w or less of other compounds. Each possibility represents a separate embodiment of the invention. The other compounds may include impurities resulting from the production or mining of the transition metal oxide.

[0180] According to some embodiments, the net reaction III resulting from the two reaction sequences does not consume alkali metal. According to some embodiments, alkali metal is used as a catalyst in the two reaction sequences of step (b). According to some embodiments, alkali metal is recycled in the two reaction sequences of step (b).

[0181] It should be understood that while the net reaction III does not consume the alkali metal, some alkali metal may be gradually consumed during step (b). In particular, side reactions that may occur when the transition metal oxide is impure or of low quality may gradually consume at least a portion of the alkali metal. However, certain net reactions III do not consume the alkali metal.

[0182] According to some embodiments, the resulting reaction mixture formed by 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 by 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 by 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 by 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.

[0183] According to some embodiments, the reaction mixture formed by carrying out the two reaction sequences of step (b) contains a reduced transition metal, M T or an alloy thereof. According to some embodiments, the reaction mixture formed by carrying out the two reaction sequences of step (b) further comprises oxygen. According to some embodiments, oxygen gas is separated from the reaction mixture.

[0184] 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).

[0185] According to some embodiments, the reaction mixture of step (b) comprises an alloyable metal or metal oxide that is alloyable with the transition metal provided in step (a), as described in more detail below in relation to optional alloy formation.

[0186] As detailed herein, step (a) may include a continuous addition of transition metal oxide to the reaction mixture of step (b), such that throughout step (b), the transition metal oxide is provided in molar excess over the added alkali metal. Specifically, according to some embodiments, throughout step (b), the transition metal oxide added to the reactor is in molar excess over the added alkali metal. Specific excess amounts are specified above.

[0187] However, the transition metal oxide added to the reactor is consumed through the reactions of Scheme I, while the alkali metal is recycled through the reactions of Scheme I. Thus, according to some embodiments, at any given time during step (b), the alkali metal in the reactor is in molar excess over the transition metal oxide. According to some embodiments, the transition metal oxide is continuously provided to the reactor at a constant addition rate, ensuring that the alkali metal in the reactor is in molar excess over the transition metal oxide at any given 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.

[0188] According to some embodiments, the two reaction sequences of step (b) are carried out in an environment protected from air. According to some embodiments, the two reaction sequences of step (b) are carried out in an environment protected from water. According to some embodiments, the two reaction sequences of step (b) are carried out in an environment protected from air and water.

[0189] In particular, it should be appreciated that alkali metals are highly reactive and require specific reaction conditions, such as performance under inert gas.

[0190] According to some embodiments, step (b) further comprises flowing an inert gas into 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.

[0191] 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.

[0192] The term "high pressure" refers to any pressure higher than atmospheric pressure.

[0193] Advantageously, the reaction period is short, economical and energy consuming.

[0194] 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.

[0195] It should be understood that the reference to the duration of step (b) refers to each individual execution of step (b). Specifically, as detailed herein, according to some embodiments, the process is carried out periodically, and the alkali metal recycled after completion of the reaction is returned to be reused in subsequent executions of step (b). It should be understood that the repetition of step (b) thus allows the cumulative exceedance of the lower threshold set above, without contradicting the above provisions directed to each individual execution of step (b).

[0196] Particular reference is now made to step (c) of the process, which, according to some embodiments, comprises isolating the reduced transition metal or alloy thereof.

[0197] 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.

[0198] 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.

[0199] According to some embodiments, the isolating step (c) involves evaporating the alkali metal produced in Reaction Scheme II and removing the alkali metal from the reactor, leaving the reduced transition metal or alloy therein. According to some embodiments, the evaporation involves heating the alkali metal. According to some embodiments, the evaporation involves reducing the pressure in the reactor. According to some embodiments, the isolating step (c) involves evaporating the alkali metal from the reactor. According to some embodiments, the isolating step (c) involves boiling the alkali metal from the reactor.

[0200] According to some embodiments, the step of transferring the alkali metal as a gas from the reactor produces an isolated transition metal or alloy thereof.

[0201] According to some embodiments, step (c) comprises isolating the transition metal or alloy thereof to a purity of at least 70% w / w, at least 80% w / w, at least 90% w / w, at least 95% w / w, or at least 99% w / w. Each possibility represents a separate embodiment of the present invention.

[0202] According to some embodiments, step (c) includes evaporating the alkali metal and oxygen from the reactor to produce an isolated transition metal or alloy thereof with a purity of at least 70% w / w, at least 80% w / w, at least 90% w / w, at least 95% w / w, or at least 99% w / w. Each possibility represents a separate embodiment of the present invention.

[0203] Purity can be conveniently determined by X-ray diffraction (XRD), as exemplified herein.

[0204] Specifically, it has been found that when starting with pure transition metal oxides, the products produced by the process of the present invention are substantially pure, even when isolated crude, however, some transition metals are reactive to air and therefore require protection from air when isolated.

[0205] According to some embodiments, the transition metal is Fe, Co, Ni, or Cu and has a purity of at least 99% w / w. Each possibility represents a separate embodiment of the present invention.

[0206] Also, in industrial processes, transition metal oxides may be provided from ores that contain contaminants such as silicon dioxide. When providing such transition metal oxide compositions in step (a) of the process, they are unable to react and the contaminants may be separated using an additional step of melting the transition metal product and filtering / skimming off the contaminants.

[0207] Particular reference is now made to step (d) of the process, which is optional and includes recovering the isolated transition metal or alloy thereof.

[0208] Specifically, according to some embodiments, the process further comprises recovering the isolated transition metal or alloy thereof produced in step (c).

[0209] According to some embodiments, the isolation of step (c) entails evaporating the alkali metal from the reactor; and the process further comprises a step (d) of recovering the isolated transition metal or alloy thereof.

[0210] According to some embodiments, step (d) further comprises placing the isolated reduced transition metal or alloy thereof in a dedicated container. According to some embodiments, the container is maintained in an air and / or water protected condition. According to some embodiments, the container is a sealable container. The transition metal container is discussed below in connection with the system.

[0211] Particular reference is now made to step (e) of the process, which is optional and comprises the step of condensing the alkali metal evaporated during step (c).

[0212] According to some embodiments, the process further comprises a step (e) 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 in an air and / or water protected condition. According to some embodiments, the container is a sealable container. The alkali metal container is discussed later in connection with the system.

[0213] Generally, alkali metals are solid substances at room temperature and atmospheric pressure. In step (c), the alkali metals are heated and possibly placed under reduced pressure so that, according to some embodiments, they change to vapor. Step (e) is relevant when the isolation of step (c) includes such vaporization, and according to some embodiments, includes condensation of the alkali metal vapor in a separate container. Although the term "condensing" typically refers to a change from gas to liquid, it should be understood that the condensed alkali metal may change to a solid gradually or instantly, depending on, for example, the temperature in the alkali metal container. Thus, the term "condensing" in the context of step (e) further includes deposition of the gas onto a solid.

[0214] Also, because step (d) involves the treatment of a transition metal or alloy and step (e) involves the treatment of an alkali metal, it should be appreciated by one of skill in the art that these steps are separate such that step (d) may occur before step (e), step (e) may occur before step (d), or they may be performed simultaneously.

[0215] According to some embodiments, step (d) occurs before step (e), step (e) occurs before step (d), or steps (d) and (e) are performed simultaneously. According to some embodiments, step (d) occurs before step (e). According to some embodiments, step (e) occurs before step (d).

[0216] Reference is now made specifically to step (f) of the process which, optionally, if step (e) is carried out, comprises returning the alkali metal condensed in step (e) to the reactor.

[0217] Specifically, in step (c), the alkali metal is optionally removed from the reactor, so that, according to some embodiments, the formed transition metal or alloy is isolated and recovered (in optional step (d)). The removed alkali metal may then, according to some embodiments, be returned to the reactor for further reaction according to the reaction sequence, to complete the recycling of the alkali metal. This is carried out in step (f) of returning the alkali metal to the reactor.

[0218] According to some embodiments, the alkali metal is transferred to the reactor in step (f) as a condensed material. According to some embodiments, the alkali metal is transferred to the reactor in step (f) as a liquid. According to some embodiments, the alkali metal is transferred to the reactor in step (f) as a solid.

[0219] Thus, according to some embodiments, the process further includes the step (e) of condensing the evaporated alkali metal in the alkali metal container; and the step (f) of transferring the condensed alkali metal to the reactor, thereby recycling the alkali metal.

[0220] It should be understood that performing step (f) completes one cycle of the process. With reformulation of the alkali metal and additional provision of transition metal, the process may continue for additional cycles according to some embodiments.

[0221] According to some embodiments, the process further includes repeating steps (a)-(d) for at least one additional sequence after step (f). According to some embodiments, the process further includes repeating steps (a)-(c) for at least one additional sequence after step (f). According to some embodiments, the process further includes repeating steps (a)-(d) for at least one additional sequence.

[0222] According to some embodiments, the process includes: performing steps (a)-(f) and performing steps (a)-(c) for at least one cycle. According to some embodiments, the process includes: performing steps (a)-(f) and performing steps (a)-(c) for multiple cycles.

[0223] The term "plurality" refers to any integer greater than one.

[0224] Reference is now made to FIGS. 1-2, which are block diagrams illustrating a process for the reduction of at least one transition metal oxide to a corresponding transition metal or an alloy thereof.

[0225] 1 is a block diagram illustrating a process for the reduction of at least one transition metal oxide to a corresponding transition metal or an alloy thereof, comprising steps (a), (b) and (c), according to some embodiments, as detailed herein. Step (a) is represented by block 1000, step (b) is represented by block 1010, and step (c) is represented by block 1020.

[0226] 2 is a block diagram illustrating a process for the reduction of at least one transition metal oxide to a corresponding transition metal or an alloy thereof, according to some embodiments, as detailed herein, comprising steps (a), (b), (c), (d), (e) and (f), where step (a) is represented by block 1000, step (b) is represented by block 1010, step (c) is represented by block 1020, step (d) is represented by block 1030, step (e) is represented by block 1040, and step (f) is represented by block 1050.

[0227] 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 3-9, which are block diagrams each representing a selected process (i.e., two specific reaction sequences) for the reduction of at least one transition metal oxide to a corresponding transition metal or alloy thereof. Each one of Figures 3-5, according to some embodiments, represents a process including steps (a), (b) and (c) as 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. Each one of Figures 6-9 represents a process including steps (a), (b), (c), (d), (e) and (f) as detailed herein, according to some embodiments, where step (a) is represented by block 1000, step (b) is represented by block 1010, step (c) is represented by block 1020, step (d) is represented by block 1030, step (e) is represented by block 1040, and step (f) is represented by block 1050.

[0228] According to some embodiments, the alkali metal is Na and Scheme II is:

[0229] [ka]

[0230] It is.

[0231] Figures 3, 5, 6 and 7 refer to reaction sequences using sodium as the alkali metal.

[0232] According to some embodiments, the alkali metal is K and Scheme II is:

[0233] [ka]

[0234] It is.

[0235] Figures 4, 8 and 9 refer to reaction sequences using potassium as the alkali metal.

[0236] According to some embodiments, M T is Fe;M T n O m Fe 2 O 3 And M A is Na, and reaction schemes I and III are:

[0237] [ka]

[0238] It is.

[0239] This change is depicted in FIG.

[0240] Also, M A Reaction Scheme II for =Na is given above and can be understood by one of ordinary skill in the art in each of the following reaction sequences.

[0241] According to some embodiments, M T is Fe;M T n O m Fe 2 O 3 And M A is K, and reaction schemes I and III are:

[0242] [ka]

[0243] It is.

[0244] Also, M AReaction Scheme II for =K is given above and can be understood by one of skill in the art in each of the following reaction sequences.

[0245] According to some embodiments, M T is Fe;M T n O m is FeO, and M A is Na, and reaction schemes I and III are:

[0246] [ka]

[0247] It is.

[0248] According to some embodiments, M T is Fe;M T n O m is FeO, and M A is K, and reaction schemes I and III are:

[0249] [ka]

[0250] It is.

[0251] This change is depicted in FIG.

[0252] According to some embodiments, M T is Fe;M T n O m Fe 3 O 4 And M A is Na, and reaction schemes I and III are:

[0253] [ka]

[0254] It is.

[0255] According to some embodiments, M T is Fe;M T n O m Fe 3 O 4 And M A is K, and reaction schemes I and III are:

[0256] [ka]

[0257] It is.

[0258] According to some embodiments, M T is Ni;M T n O m is NiO, M A is Na, and reaction schemes I and III are:

[0259] [ka]

[0260] It is.

[0261] This change is depicted in FIG.

[0262] According to some embodiments, M T is Ni;M T n O m is NiO, M A is K, and reaction schemes I and III are:

[0263] [ka]

[0264] It is.

[0265] According to some embodiments, M T is Cr;M T n O m is Cr 2 O 3 And M A is Na, and reaction schemes I and III are:

[0266] [ka]

[0267] It is.

[0268] This change is illustrated in FIG.

[0269] According to some embodiments, M T is Cr;M T n O m is Cr 2 O 3 And M A is K, and reaction schemes I and III are:

[0270] [ka]

[0271] It is.

[0272] According to some embodiments, M T is Cr;M T n O m is CrO, M A is Na, and reaction schemes I and III are:

[0273] [ka]

[0274] It is.

[0275] According to some embodiments, M T is Cr;M T n O m is CrO, M A is K, and reaction schemes I and III are:

[0276] [ka]

[0277] It is.

[0278] According to some embodiments, M T is Cr;M T n O m is CrO 3 And M A is Na, and reaction schemes I and III are:

[0279] [ka]

[0280] It is.

[0281] According to some embodiments, M T is Cr;M T n O m is CrO 3 And M A is K, and reaction schemes I and III are:

[0282] [ka]

[0283] It is.

[0284] According to some embodiments, M T is Cr;M T n O mCu 2 O and M A is Na, and reaction schemes I and III are:

[0285] [ka]

[0286] is;

[0287] According to some embodiments, M T is Cr;M T n O m Cu 2 O and M A is K, and reaction schemes I and III are:

[0288] [ka]

[0289] is;

[0290] This change is illustrated in FIG.

[0291] According to some embodiments, M T is Cu;M T n O m is CuO, M A is Na, and reaction schemes I and III are:

[0292] [ka]

[0293] It is.

[0294] According to some embodiments, M T is Cu;M T n O m is CuO, M Ais K, and reaction schemes I and III are:

[0295] [ka]

[0296] It is.

[0297] According to some embodiments, M T is Cu;M T n O m CuO 2 And M A is Na, and reaction schemes I and III are:

[0298] [ka]

[0299] It is.

[0300] According to some embodiments, M T is Cu;M T n O m CuO 2 And M A is K, and reaction schemes I and III are:

[0301] [ka]

[0302] It is.

[0303] According to some embodiments, M T is Zn; M T n O m is ZnO, M A is Na, and reaction schemes I and III are:

[0304] [ka]

[0305] It is.

[0306] This change is illustrated in FIG.

[0307] According to some embodiments, M T is Zn; M T n O m is ZnO, M A is K, and reaction schemes I and III are:

[0308] [ka]

[0309] It is.

[0310] According to some embodiments, M T is Mn; M T n O m is MnO, and M A is Na, and reaction schemes I and III are:

[0311] [ka]

[0312] It is.

[0313] According to some embodiments, M T is Mn; M T n O m is MnO, and M A is K, and reaction schemes I and III are:

[0314] [ka]

[0315] It is.

[0316] According to some embodiments, M T is Mn; M T n O m is Mn 3 O 4 And M A is Na, and reaction schemes I and III are:

[0317] [ka]

[0318] It is.

[0319] According to some embodiments, M T is Mn; M T n O m is Mn 3 O 4 And M A is K, and reaction schemes I and III are:

[0320] [ka]

[0321] It is.

[0322] According to some embodiments, M T is Mn; M T n O m is Mn 2 O 3 And M A is Na, and reaction schemes I and III are:

[0323] [ka]

[0324] It is.

[0325] According to some embodiments, M T is Mn; M T n O m is Mn 2 O 3 And M A is K, and reaction schemes I and III are:

[0326] [ka]

[0327] It is.

[0328] According to some embodiments, M T is Mn; M T n O m MnO 2 And M A is Na, and reaction schemes I and III are:

[0329] [ka]

[0330] It is.

[0331] According to some embodiments, M T is Mn; M T n O m MnO 2 And M A is K, and reaction schemes I and III are:

[0332] [ka]

[0333] It is.

[0334] According to some embodiments, M T is Mn; M Tn O m is Mn 2 O 7 And M A is Na, and reaction schemes I and III are:

[0335] [ka]

[0336] It is.

[0337] According to some embodiments, M T is Mn; M T n O m is Mn 2 O 7 And M A is K, and reaction schemes I and III are:

[0338] [ka]

[0339] It is.

[0340] According to some embodiments, M T is Sc;M T n O m Sc 2 O 3 And M A is Na, and reaction schemes I and III are:

[0341] [ka]

[0342] It is.

[0343] According to some embodiments, M T is Sc;M T n O m Sc2 O 3 And M A is K, and reaction schemes I and III are:

[0344] [ka]

[0345] It is.

[0346] According to some embodiments, M T is Ti;M T n O m is TiO 2 And M A is Na, and reaction schemes I and III are:

[0347] [ka]

[0348] It is.

[0349] According to some embodiments, M T is Ti;M T n O m is TiO 2 And M A is K, and reaction schemes I and III are:

[0350] [ka]

[0351] It is.

[0352] This change is illustrated in FIG.

[0353] According to some embodiments, M T is Ti;M T n O m Ti 2O 3 And M A is Na, and reaction schemes I and III are:

[0354] [ka]

[0355] It is.

[0356] According to some embodiments, M T is Ti;M T n O m Ti 2 O 3 And M A is K, and reaction schemes I and III are:

[0357] [ka]

[0358] It is.

[0359] According to some embodiments, M T is V;M T n O m is VO and M A is Na, and reaction schemes I and III are:

[0360] [ka]

[0361] It is.

[0362] According to some embodiments, M T is V;M T n O m is VO and M A is K, and reaction schemes I and III are:

[0363] [ka]

[0364] It is.

[0365] According to some embodiments, M T is V;M T n O m is V 2 O 3 And M A is Na, and reaction schemes I and III are:

[0366] [ka]

[0367] It is.

[0368] According to some embodiments, M T is V;M T n O m is V 2 O 3 And M A is K, and reaction schemes I and III are:

[0369] [ka]

[0370] It is.

[0371] According to some embodiments, M T is V;M T n O m VO 2 And M A is Na, and reaction schemes I and III are:

[0372] [ka]

[0373] It is.

[0374] According to some embodiments, M T is V;M T n O m VO 2 And M A is K, and reaction schemes I and III are:

[0375] [ka]

[0376] It is.

[0377] According to some embodiments, M T is V;M T n O m is V 2 O 5 And M A is Na, and reaction schemes I and III are:

[0378] [ka]

[0379] It is.

[0380] According to some embodiments, M T is V;M T n O m is V 2 O 5 And M A is K, and reaction schemes I and III are:

[0381] [ka]

[0382] It is.

[0383] According to some embodiments, M T is Co;M T n O m Co 2 O 3 And M A is Na, and reaction schemes I and III are:

[0384] [ka]

[0385] It is.

[0386] According to some embodiments, M T is Co;M T n O m Co 2 O 3 And M A is K, and reaction schemes I and III are:

[0387] [ka]

[0388] It is.

[0389] According to some embodiments, M T is Co;M T n O m is the CoO, and M A is Na, and reaction schemes I and III are:

[0390] [ka]

[0391] It is.

[0392] According to some embodiments, M T is Co;MT n O m is the CoO, and M A is K, and reaction schemes I and III are:

[0393] [ka]

[0394] It is.

[0395] According to some embodiments, M T is Co;M T n O m Co 3 O 4 And M A is Na, and reaction schemes I and III are:

[0396] [ka]

[0397] It is.

[0398] According to some embodiments, M T is Co;M T n O m Co 3 O 4 And M A is K, and reaction schemes I and III are:

[0399] [ka]

[0400] It is.

[0401] Reference will now be made specifically to embodiments of the present process directed to the formation of transition metal alloys.

[0402] According to some embodiments, the process is for the preparation of a metal alloy, and step (a) or step (b) further comprises the addition of a second metal, M b to a reactor, the second metal being M T step (b) combines a second metal with an alkali metal and a transition metal oxide to induce the two reaction sequences of reaction schemes I and II, and further to Scheme IV:

[0403] [ka]

[0404] Induces a reaction.

[0405] According to some embodiments, the second metal, M b According to some embodiments, the second metal, M b is a transition metal, M Tb It is.

[0406] The term "alloyable" refers to the ability of two metallic elements to form an alloy. Thus, the term "alloyable metal" as used herein 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 in the conditions of the process of the present invention (i.e., the conditions of step (b)).

[0407] Additionally, the alloyable metal may be provided as a metal oxide, and according to some embodiments, may be reduced (ie, reduced by an alkali metal) under the reaction conditions of the present process.

[0408] According to some embodiments, the process is for the preparation of a metal alloy, and step (a) comprises: b i O jwherein each one of i and j is 1, 2, 3, 4, 5, 6 or 7; and step (b) comprises combining the two metal oxides with an alkali metal, Reaction Schemes I and III provide:

[0409] [ka]

[0410] and step (b) further comprises reaction IV to form an alloy:

[0411] [ka]

[0412] This induced.

[0413] It should be understood that Reaction Scheme I is divided into Ia and Ib, while Reaction Scheme III is divided into IIIa and IIIb.

[0414] According to some embodiments, the second metal, M b is a transition metal, M Tb It is.

[0415] Thus, according to some embodiments, step (a) comprises 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; M Ta , M Tb wherein each one of: is a transition metal selected from the group consisting of: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn; and step (b) comprises combining the transition metal oxide with an alkali metal, Reaction Schemes I and III are:

[0416] [ka]

[0417] and step (b) further comprises reaction IV to form an alloy:

[0418] [ka]

[0419] This induced.

[0420] 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), ferric oxide (FeNiCo), ferromanganese (FeMn), ferronickel (FeNi), ferrotitanium (FeTi), ferrovanadium (FeV), invar (FeNi), kovar (FeNiCo), chromel (NiCr), and nitinol (NiTi).

[0421] 10-11 are block diagrams showing processes for the reduction of two transition metal oxides to their corresponding transition metal alloys (CuZn alloy in FIG. 10 and FeNi alloy in FIG. 11), respectively.

[0422] Reference is now made to a reaction system that, according to some embodiments, is configured to carry out the processes of the present invention.

[0423] According to some embodiments, the process further comprises: a housing defining a reaction chamber; and a transition metal oxide inlet, an alkali metal inlet, an alkali metal outlet, and an isolated transition metal or alloy outlet, each of said inlets and outlets being in fluid communication with the reaction chamber; Reactor; an alkali metal container including an alkali metal inlet and an alkali metal outlet; an isolated transition metal or alloy container containing a transition metal inlet; a condenser configured to condense the evaporated alkali metal, the condenser including a proximal end connected to the alkali metal outlet of the reactor and a distal end connected to the alkali metal inlet of the alkali metal container; an alkali metal transfer tube including a proximal end connected to the alkali metal inlet of the reactor and a distal end connected to the alkali metal outlet of the alkali metal container; a transition metal transfer tube including a proximal end connected to the transition metal outlet of the reactor and a distal end connected to the transition metal inlet of the isolated transition metal or alloy container; providing a transition metal oxide reducing system comprising:

[0424] According to some embodiments, the reactor further includes an inert gas inlet and a gas outlet, each in fluid communication with the reaction chamber, the inert gas inlet being in fluid communication with an inert gas source. According to some embodiments, the inert gas inlet is connected to the inert gas source through a gas tube. According to some embodiments, the gas tube has a valve configured to regulate the flow of inert gas from the inert gas source to the reaction chamber.

[0425] According to some embodiments, the process includes: (a) providing at least one transition metal oxide to a reaction chamber through a transition metal oxide inlet; (b) combining a transition metal oxide with an alkali metal in a reaction chamber to induce two reaction sequences; (c) evaporating the alkali metal through an alkali metal outlet of the reactor to isolate the transition metal or alloy thereof in the reaction chamber; (d) transferring the isolated transition metal or alloy thereof through a transition metal transfer tube to a container of isolated transition metal or alloy; (e) condensing the evaporated alkali metal into an alkali metal container using a condenser; and (f) transferring the condensed alkali metal from the alkali metal container to the reactor through an alkali metal transfer tube. Including, Step (e) may be performed before step (d).

[0426] According to some embodiments, step (b) further comprises inserting an inert gas into the reaction chamber through an inert gas inlet, thereby maintaining a reaction environment protected from air.

[0427] According to certain embodiments, step (b), step (c), or both, further comprises venting the formed oxygen gas through a gas outlet of the reactor.

[0428] According to some embodiments, the condenser further includes a one-way valve disposed between the proximal end and the distal end, the valve configured to regulate the flow of evaporated alkali metal from the rector to the alkali metal container. According to some embodiments, step (f) further includes regulating the flow of condensed alkali metal from the alkali metal container to the rector using the valve.

[0429] According to some embodiments, the transition metal transfer tube further includes a one-way valve disposed between its proximal and distal ends, the valve configured to regulate the flow of the isolated transition metal or metal alloy from the receptor to the container of isolated transition metal or alloy. According to some embodiments, step (c) or step (d) further includes regulating the flow of the isolated transition metal or metal alloy from the receptor to the container of isolated transition metal or alloy using the valve.

[0430] Working Example General Procedure-System Some metal oxides are reacted with pure sodium at 900 °C to reduce the metal oxides to pure metals. The following metal oxides: Cu 2 O, NiO, Cr 2 O 3 and Fe 2 O 3 was tested.

[0431] System components:

[0432] 1.Reactor--Custom made of SS304 265mL.

[0433] 2.SiC crucible 37mL.

[0434] 3. The first induction heating system (6kw made in China), induction coil (5 turns).

[0435] 4. Second induction system(China made 3kw), induction coil(3 turns).

[0436] 5. The system was cooled with a water cooler.

[0437] 6. SS304 tube 430mL (sodium waste reactor) and flange (NW50).

[0438] 7.Parker connector for argon insertion.

[0439] 8. Thermocouples Type K (3 pcs - 1 outside 1 / 2 inch connection, 1 in reactor, 1 in crucible).

[0440] 9. Argon flow regulator company "AALBORG".

[0441] 10.3 On / Off Valves 1 / 4 inch and 1 Vacuum Valve.

[0442] 11. Bellows trap with SS wool to protect the vacuum pump.

[0443] 12. Vacuum pump.

[0444] 13. Stand.

[0445] 14. Insulating wool.

[0446] The reactor was of SS304 material construction, had a volume of 265 mL, and was connected through a 1 / 2 inch SS316 tube to a sodium waste reactor of SS304 material construction with a volume of 430 mL, in which a crucible made of SiC was placed.

[0447] Alumina block protection was used in key locations to protect the induction system and Viton o-rings in the KF flanges.

[0448] General experimental procedure In a reactor in which a crucible with 3 gr metal oxide and 3 gr pure sodium was placed, one thermocouple placed in the reactor to control the first induction system and a second thermocouple placed in the crucible to measure the reaction were connected to a data logger.

[0449] The first induction system heats the lower part of the reactor, where the crucible is located, during the experiment to 900° C. with a heating rate of 15° C. / min and an argon flow of 40 mL / min.

[0450] At the start of the reaction, the vacuum valve and the second argon exhaust valve were closed, and the argon outlet was through the first argon exhaust valve. When the temperature reached 700°C, the first argon exhaust valve was closed and the second valve was opened. Furthermore, when the first induction system reached 700°C, the second induction system was stopped to reach 200°C. 70 minutes after the start of the reaction, a gradual vacuum was started using a pump at 900°C for 30 minutes until a vacuum was reached. After 30 minutes, argon was inserted 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 closed.

[0451] Example 1: Fe2 O 3 Reduction of to Fe As detailed above in the general experimental procedure, Fe was synthesized using sodium as the reducing agent. 2 O 3 The reduction of to iron metal was carried out. The reaction peak was measured between 480 °C and 720 °C. Other reaction parameters are summarized in Table 1:

[0452] [Table 1]

[0453] Figure 12A is a graph depicting the temperature (°C) versus time (min) measured within the reactor during the reaction of Example 1. Figure 12B is an XRD pattern of the reaction product of the reaction of Example 1. Specifically, in Example 1, the predominant phase is metallic iron.

[0454] Example 2: Cu 2 Reduction of O to Cu Cu using sodium as the reducing agent as detailed above in the general experimental procedure. 2 The reduction of O to copper metal was carried out. The reaction peak was measured at 417 °C to 505 °C at 31.33 min from the start of the reaction. Other reaction parameters are summarized in Table 2:

[0455] [Table 2]

[0456] FIG. 13A is a graph depicting the temperature (° C.) versus time (min) measured in the reactor during the reaction of Example 2. FIG. 13B is an XRD pattern of the reaction product of the reaction of Example 2. Specifically, in Example 2, the main phase is ZnO with trace amounts of Cu. 2 It is metallic copper having O.

[0457] Example 3: Reduction of NiO to Ni The reduction of NiO to nickel metal using sodium as the reducing agent was carried out as detailed above in the general experimental procedure. The reaction peak was measured between 407°C and 595°C at 32 minutes into the reaction. Other reaction parameters are summarized in Table 3:

[0458] [Table 3]

[0459] Figure 14A is a graph depicting the temperature (°C) versus time (min) measured within the reactor during the reaction of Example 3. Figure 14B is an XRD pattern of the reaction product of the reaction of Example 3. Specifically, the sample measured is shown in Figure 14B and contained only metallic nickel.

[0460] Example 4: Cr 2 O 3 Reduction of to Cr Cr using sodium as the reducing agent as detailed above in the general experimental procedure. 2 O 3 The reduction of to chromium metal was carried out. The reaction peak was measured at 509 °C to 730 °C after 38 min from the start of the reaction. Other reaction parameters are summarized in Table 4:

[0461] [Table 4]

[0462] FIG 15A is a graph depicting the temperature (°C) versus time (min) measured in the reactor during the reaction of Example 4. FIG 15B is an XRD pattern of the reaction product of the reaction of Example 4. Specifically, in this sample, NaCrO 2 (87%) and chromium carbide nitride (13%).

[0463] conclusion The products from the reaction of nickel and copper oxide with sodium are high quality metals according to the XRD results. In the copper sample, the main phase is the Cr phase, with traces of Cu. 2 In the nickel sample, there is only metallic nickel.

[0464] Upon application of a vacuum of 45 torr with an argon flow of 40 mL / min for 30 minutes at 900° C., most of the sodium is discarded from the reaction mixture. Potassium, being more volatile, may give similar, if not improved, results.

[0465] While the present invention has been described in conjunction with specific embodiments thereof, it is apparent that there may be numerous alternatives, modifications, and variations that are apparent to those skilled in the art. It is to be understood that the present invention is not necessarily limited in its application to the details of construction and the arrangement of the components and / or methods described herein. Other embodiments may be implemented, and an embodiment may be carried out in various ways. Accordingly, the present invention embraces all such alternatives, modifications, and variations that fall within the scope of the appended claims.

Claims

1. A process for the reduction of a transition metal oxide, comprising: Formula (a) M Ｔ ｎ O ｍ (wherein each 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) to provide at least one transition metal oxide having the same; (b) contacting the transition metal oxide with an alkali metal (M Ａ ) in a reactor, adjusting the temperature in the reactor to a temperature T, and reaction schemes I and II: 【Chemical 1】 Inducing two reaction sequences, resulting in III which is the net reaction obtained from the two reaction sequences 【Chemical 2】 without consuming the alkali metal, and the resulting reaction mixture contains MT which is a reduced transition metal or its alloy, the alkali metal, and optionally oxygen, where M Ａ is Na or K, and the temperature T is at least 300 °C, step; and (c) Isolating the reduced transition metal or its alloy from the reaction mixture; A process comprising the above steps.

2. Step (a) includes continuously providing the at least one transition metal oxide to the reactor, such that the total transition metal oxide provided in step (a) is in molar excess over the alkali metal of step (b), and the molar excess is at least 400%. The process according to claim 1.

3. The temperature T is above the boiling point of the alkali metal, the isolation in step (c) requires evaporating the alkali metal from the reactor, and the process further includes a step (d) of recovering the isolated transition metal or its alloy. Preferably, the process further includes a step (e) of condensing the evaporated alkali metal and a step (f) of transferring the condensed alkali metal back to the reactor to recycle the alkali metal. The process according to claim 1.

4. (a) Providing the at least one transition metal oxide; (b) Combining the transition metal oxide with an alkali metal at temperature T to induce the two reaction sequences; (c) Evaporating the alkali metal from the reactor to produce an isolated transition metal or its alloy; (d) Recovering the isolated transition metal or its alloy; (e) Condensing the evaporated alkali metal; and (f) Transferring the condensed transition metal back to the reactor; A process according to claim 1, comprising: Step (e) may be performed before step (d), The process further includes repeating steps (a) to (d) for at least one additional sequence. A process.

5. M Ｔ The process according to claim 1, wherein M is a first row transition metal selected from the group consisting of Fe, Ni, Cr, Cu, Zn, and Mn.

6. M Ｔ is Fe, and M Ｔ ｎ O ｍ is Fe ２ O ３ , FeO, Fe ３ O ４ or a combination thereof, and reaction schemes I and III are: [Chemical Formula 3] Or 【Chemical Formula 4】 Or 【Chemical Formula 5】 is; Or, MT is Ni, MTnOm is NiO, and reaction schemes I and III are: 【Chemical Formula 6】 As follows; Or MT is Cr, MTnOm is Cr2O3, CrO, CrO3 or a combination thereof, and reaction schemes I and III are: [Chemical Formula 7] Or 【Chemical 8】 Or 【Chemical Formula 9】 As follows; Or MT is Cu, MTnOm is Cu2O, CuO, CuO2, or a combination thereof, and reaction schemes I and III are: 【Chemical 10】 or 【Chemical 11】 or 【Chemical 12】 ; alternatively MT is Zn, MTnOm is ZnO, and reaction schemes I and III are: 【Chemical 13】 ; alternatively MT is Mn, MTnOm is MnO, Mn3O4, Mn2O3, MnO2, Mn2O7, or a combination thereof, and reaction schemes I and III are: 【Chemical 14】 or 【Chemical 15】 or 【Chemical 16】 or 【Chemical 17】 or 【Chemical 18】 ; The process according to claim 5.

7. The process according to claim 1 for the preparation of a metal alloy, Step (a) is formula M Ｔａ ｎ Om and formula M Ｔｂ ｉ O ｊ (wherein each one of i and j is 1, 2, 3, 4, 5, 6 or 7, and each one of 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); including the step of providing at least two transition metal oxides having wherein step (b) comprises combining the transition metal oxide with the alkali metal, and reaction schemes I and III are: 【Chemical Formula 19】 ; wherein step (b) further induces reaction IV for forming an alloy: 【Chemical 20】 The process according to claim 1.

8. The process according to claim 1, wherein the alkali metal is sodium and scheme II is: 【Chemical 21】

9. The process according to claim 4, wherein step (c) comprises evaporating the alkali metal and oxygen from the reactor to produce an isolated transition metal or its alloy with a purity of at least 90% w / w, preferably, the transition metal is Fe, Co, Ni, or Cu, and its purity is at least 99% w / w.

10. The process according to claim 1, wherein the reaction mixture in step (b) substantially does not contain an additional solvent and carrier, and essentially consists of the transition metal oxide, the alkali metal, and the reduced transition metal or its alloy as the product, preferably, the two reaction sequences in step (b) are carried out in an environment protected from air and water.

11. A reactor comprising a housing defining a reaction chamber, an inlet for a transition metal oxide, an inlet for an alkali metal, an outlet for the alkali metal, and an outlet for an isolated transition metal or alloy, wherein each of the inlets and outlets is in fluid communication with the reaction chamber; An alkali metal container comprising an alkali metal inlet and an alkali metal outlet; A container for an isolated transition metal or alloy comprising an inlet for the transition metal; A condenser configured to condense the evaporated alkali metal, comprising a proximal end connected to the alkali metal outlet of the reactor and a distal end connected to the alkali metal inlet of the alkali metal container; An alkali metal transfer pipe comprising a proximal end connected to the alkali metal inlet of the reactor and a distal end connected to the alkali metal outlet of the alkali metal container; A transition metal transfer pipe comprising a proximal end connected to the transition metal outlet of the reactor and a distal end connected to the transition metal inlet of the container of the isolated transition metal or alloy; The process according to claim 4, further comprising providing a system comprising.

12. The process according to claim 11, wherein the reactor further comprises an inert gas inlet and a gas outlet, each in fluid communication with the reaction chamber, and the inert gas inlet is in fluid communication with an inert gas source.

13. (a) providing the at least one transition metal oxide to the reaction chamber through the transition metal oxide inlet; (b) combining the transition metal oxide with an alkali metal in the reaction chamber to induce the two reaction sequences; (c) evaporating the alkali metal through the alkali metal outlet of the reactor to produce an isolated transition metal or an alloy thereof; (d) transferring the isolated transition metal or an alloy thereof to the container of the isolated transition metal or alloy through the transition metal transfer pipe; (e) using the condenser to condense the evaporated alkali metal into the alkali metal container; (f) transferring the condensed alkali metal from the alkali metal container to the reactor through the alkali metal transfer pipe; comprising Step (e) may be performed before step (d). The process according to claim 11.

14. Step (b) further comprises inserting an inert gas into the reaction chamber through the inert gas inlet, thereby maintaining a reaction environment protected from air; or Step (b), step (c) or both further comprise exhausting the oxygen gas formed through the gas outlet of the reactor; The process according to claim 12.

15. The capacitor further includes a one-way valve disposed between its proximal end and its distal end, the valve being configured to regulate the flow of the alkali metal vaporized from the rector to the alkali metal container; The alkali metal transfer tube further includes a one-way valve disposed between its proximal end and its distal end, the valve being configured to regulate the flow of the condensed alkali metal from the alkali metal container to the rector; The transition metal transfer tube further includes a one-way valve disposed between its proximal end and its distal end, the valve being configured to regulate the flow of the isolated transition metal or metal alloy from the rector to the container of the isolated transition metal or alloy; The process according to claim 12.

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