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    • 专利摘要:
    extraction of liquid element by oxide electrolysis. the present invention relates to a method of electrolytic extraction that receives a target element from a compound of the oxide raw material thereof. the raw material compound is dissolved in a molten oxide in contact with a cathode and an anode of an electrolytic cell. during electrolysis the target element is deposited on the liquid cathode and coalests with it. oxygen is developed in an anode having a solid oxide layer, in contact with the molten oxide, on a metal anode substrate.
    公开号:BR112013004285B1
    申请号:R112013004285-0
    申请日:2011-08-22
    公开日:2020-02-27
    发明作者:Antoine Allanore；Donald R. Sadoway
    申请人:Massachusetts Institute Of Technology；
    IPC主号:
    专利说明:

    Invention Patent Descriptive Report for METHOD FOR EXTRACTION OF A TARGET ELEMENT FROM A RAW MATERIAL FROM THE TARGET ELEMENT, AND DEVICE.
    CROSS REFERENCE TO RELATED APPLICATION [001] The present application claims the benefit of U.S. Provisional Patent Application Serial No. 61 / 375,935, which was filed on August 23, 2010, by Antoine Allanore et al. for METHOD AND APPARATUS FOR ELECTROLYSIS OF MOLTEN OXIDES INCORPORATING METALLIC ALLOY ANODES, and also Provisional Patent Application Serial No. 61 / 489,565, which was filed on May 24, 2011, by Antoine Allanore et al, for METHOD AND APPARATUS FOR ELECTROLYSIS OF MOLTEN OXIDES INCORPORATING METALLIC ALLOY ANODES, and are hereby incorporated by reference.
    BACKGROUND OF THE INVENTION
    Field of the Invention [002] The invention relates to the extraction of elements with a high melting point from oxide ores. In particular, this invention provides electrolytic methods that incorporate metal anodes for the electro-extraction of elements from oxide castings.
    Background Information [003] The release of greenhouse gases is an intrinsic result of traditional refining methods for most metals. For example, iron produced conventionally in a blast furnace causes significant process emissions related to the production of coke and reduction of iron ore. Combustion operations still contribute to carbon emissions with auxiliary steps in the process such as ore preparation. Steel production from pig iron still leads to energy consumption, for example
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    2/22 example, in an electric arc furnace, which can be supplied by combustion of fossil fuels. Iron and steel production is expected to contribute several percentage points to global greenhouse gas emissions.
    [004] As the tolerance for greenhouse gas emissions decreases, finding replacement technologies for base metal refining operations is becoming critical. Consequently, there is a need for metal extraction techniques that work with reduced use of carbon and carbon-based fuels.
    [005] In parallel, there is a growing interest in the production of metal products containing dissolved carbon in concentrations difficult to achieve with conventional technology at an acceptable cost. Therefore, there is value to be placed on carbon-free extraction technology that can produce metal of exceptional purity. SUMMARY OF THE INVENTION [006] In a Method for extracting a target element from an oxide feed charge compound that incorporates the target element, a liquid electrolyte, at least 75% by weight of oxide, is provided. The oxide feed charge is dissolved in the liquid electrolyte. An anode that includes a metallic anode substrate is provided in contact with the electrolyte. A cathode is in contact with the electrolyte, opposite the anode. The dissolved oxide feed charge is subjected to electrolysis when electrons are conducted from oxygen precursors in the electrolyte into the metal substrate through an oxide layer on the substrate to form the gaseous oxygen. The species in the electrolyte that carry the target element are reduced to form the target element in the cathode.
    [007] In another modality, a Method for extracting a target element from an oxide feed charge that incorporates the
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    3/22 target element provides a liquid electrolyte in which the oxide feed charge is dissolved. An anode in contact with the electrolyte at an interface includes a metallic substrate for the anode. At least 50% by weight of the substrate is at least one element more reactive to oxygen than the target element at an operating temperature of the interface. A liquid cathode is in contact with the electrolyte, opposite the anode. The dissolved oxide feed charge is subjected to electrolysis when electrons are conducted from oxygen precursors in the electrolyte into the metal substrate through an oxide layer on the substrate to form the gaseous oxygen. The species in the electrolyte that carry the target element are reduced to form the target element in the cathode.
    [008] In another embodiment of a method for extracting iron from an oxide feed charge it provides a liquid electrolyte, at least 75% by weight of oxide, in which the oxide feed charge is dissolved. An anode in contact with the electrolyte includes a metallic substrate for the anode. The substrate is at least 50% by weight of chromium and at least 1% by weight of iron. A liquid cathode is in contact with the electrolyte, opposite the anode. The dissolved oxide feed charge is subjected to electrolysis when electrons are conducted from oxygen precursors in the electrolyte into the metallic substrate to form the gaseous oxygen. The species in the electrolyte that carry the target element are reduced to form the target element in the cathode.
    [009] A device comprises a liquid electrolyte, at least 75% by weight of oxide, including oxygen precursors and species carrying a target element, which originates from an oxide feed charge compound dissolved in the electrolyte. A liquid cathode is in contact with the electrolyte. The anode is in contact with the electrolyte opposite the cathode. The anode includes a substrate
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    4/22 metallic anode and a solid oxide layer that receives the electrolyte in a contact interface. The device is operated, after connecting the anode and cathode to a power source, to electrolyze the dissolved oxide feed charge compound, to conduct electrons from the oxygen precursors through the solid oxide layer in order to form gaseous oxygen and reduce the species that carry the target element to form the target element in the cathode. [0010] In another embodiment, a device includes a liquid electrolyte, at least 75% by weight of oxide, which includes the precursors of oxygen and the species that carry iron, which originate from an oxide feed charge compound dissolved in the electrolyte. A liquid cathode is in contact with the electrolyte. An anode comes into contact with the electrolyte opposite the cathode. The anode includes a metallic substrate of the anode that is at least 50% by weight of chromium and at least 1% by weight of iron. The device is operable, after connecting the anode and cathode to a power source, to electrolyze the dissolved oxide feed charge compound, conduct electrons from the oxygen precursors to form the gaseous oxygen and reduce the species that they carry iron to form iron in the cathode.
    BRIEF DESCRIPTION OF THE DRAWINGS [0011] The previous debate will be more easily understood from the following detailed description of the invention, when taken in conjunction with the accompanying drawings, in which equal reference numbers indicate identical or functionally similar elements: [0012] FIG . 1 is a vertical section showing an electrochemical device configured to extract a target element from an oxide feed compound according to the invention;
    [0013] FIG. 2 is a schematic showing the electrochemical device
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    5/22 physician of FIG. 1 configured in a circuit with a power source according to the invention;
    [0014] FIG. 3 is a vertical section showing a part of an anode in which an oxide layer has been formed on a substrate by pre-electrolysis in the electrochemical device according to the invention; and [0015] FIG. 4 is a vertical section showing a part of an anode on which a preform was formed prior to placement in the electrochemical device according to the invention.
    [0016] It will be noted that these figures are not necessarily drawn to scale.
    DETAILED DESCRIPTION OF AN ILLUSTRATIVE MODE [0017] Fused oxide electrolysis (“MOE”) requires the direct electrolysis of an oxide feed charge compound to extract a target element from it. The EOM reaches the target metal with the production of gaseous oxygen and without release, or with reduced release, of carbon dioxide or other objectionable volatile species. Since the target metal is reduced directly from the oxide, the processing of preparing parent compounds is much cleaner and simpler than conventional extraction techniques for many metals. The EOM has the potential to produce metal of exceptional purity, especially with regard to the so-called interstitial elements, that is, carbon and nitrogen. Since the EOM can produce a target element in liquid form, the difficulties associated with dendritic deposits are avoided. MOE is, moreover, energy efficient for the extraction of an element in its liquid state, in which the irreversibilities that necessarily accompany the flow of electrical current through components of an electrolytic cell also serve to keep the cellular components at the required high temperatures .
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    6/22 [0018] The target element can have a high melting temperature, illustratively above 1200 ° C or 1400 ° C. Examples include manganese (Tm = 1246 ° C), silicon (Tm = 1414 ° C), nickel (Tm = 1455 ° C), cobalt (Tm = 1495 ° C), iron (Tm = 1538 ° C), titanium (Tm = 1670 ° C), zirconium (Tm = 1855 ° C), chromium (Tm = 1907 ° C).
    [0019] Candidate feed oxide feed compounds incorporate the desired target element and oxygen. For example, possible oxide feed fillers for the extraction of titanium include, but are not limited to, for example, titanium monoxide (TiO), titanium sesquioxide (Ti2Os), titanium dioxide (TiO2). Nickel can be extracted from a nickel oxide such as NiO. Iron can be extracted from an iron oxide such as the ferric oxide (Fe2Oa) or ferrous ferric oxide (Fe3O4) feed. Chromium can be extracted from chromium oxide (Cr2O). Manganese can be extracted from a manganese oxide such as MnO, MnaO4, Mn2Oa, MnO2 or M ^ O . A mixed oxide phase such as chromite (FeCr2O4) and ilmenite (FeTiO3) as a feed filler can provide for the deposition of two elements from a single compound.
    [0020] With reference to FIG. 1 and FIG. 2, in an illustrative embodiment, an electrometallurgical cell operable to extract a target element from a feed charge compound comprises a liquid electrolyte 30, cathode 40 and anode 50. Electrolyte 30 and cathode 40 are contained by a cell structure or compartment 12.
    [0021] Cathode 40 is illustratively a liquid body that incorporates the target element. The interior of compartment 12 illustratively provides an electronically conductive cathode substrate 16 on which cathode 40 rests. The cathode substrate 16 is illustratively made of a material resistant to attack by cathode 40. For some modalities
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    7/22 de, the cathode substrate 16 may be molybdenum. The cathodic metal current collecting bars 18 incorporated in the cathode substrate 16 allow the connection of cathode 40 to an external power source 60 and serve as the negative terminal during the operation of the cell 10.
    [0022] Electrolyte 30 reaches cathode 40 on an electrolyte-electrode interface 35. Electrolyte 30 is a liquid capable of dissolving the oxide feed charge that incorporates the target element. Illustratively, electrolyte 30 is a mixture of fused oxide or fusion of oxide. The device 10 is illustratively operated under conditions that motivate a peripheral frozen electrolyte layer 32 to form between the fusion of oxide 30 and the inner sides 15 of the compartment
    12. The frozen electrolyte layer 32 protects the inner sides 15 from chemical attack by the fusion of oxide 30.
    [0023] Anode 50 disappears in the electrolyte 30 opposite the cathode
    40. Anode 50 can be a single continuous body. Illustratively, channels 56 machined through anode 50 are configured as the respective pathways between the upper surface of electrolyte 30 and the outside of cell 10. An electronically conductive metal anode substrate 54 illustratively carries a solid layer of oxide 61 constituted to limit substrate consumption 54 at an acceptable level during operation of cell 10. Anode 50 meets electrolyte 30 at a contact interface 52 at that time. The electrically conductive metal anode rods 58 incorporated into anode 50 are configured to allow connection of anode 50 to external power source 60 and serve as the positive terminal during the operation of cell 10.
    [0024] Equivalently, a plurality of substantially identical anode blocks constitute anode 50. The metallic substrate of conductive anode 54 of each of the blocks illustratively carries
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    8/22 a solid layer of oxide 61. The anode blocks are in electrical communication with a common anode collector 58, have a common electrical potential, and are arranged with spaces between them that constitute channels 56.
    [0025] The respective compositions of electrolyte 30, anode 50 and cathode 40, compartment 12 and other aspects of cell 10, are selected conjunctionally for mutual compatibility and to guarantee the practical operational parameters and the useful life of the cell 10.
    [0026] The liquid cathode 40 can be substantially identical in composition with the desired target element. Alternatively, the liquid cathode 40 additionally contains elements other than the target element produced. A molten metal host or distillation residue produced from a more noble metal than the target metal can serve as cathode 40, for example, a molten copper cathode 40 in which nickel is deposited by a cast iron cathode 40 where chromium is deposited. This situation can be consistent with the direct production of an alloy of desired composition by adding, by reducing the species in electrolyte 30 as described below, one or more elements bind the constituents already existing in cathode 40. A cathode 40 showing a composition wherein the target element produced easily binds the constituents to an environment of reduced activity of the target element relative to a mono-elementary liquid body. In this case, the voltage required to convert the oxide compound from the feed charge into the target element by the MOE in cell 10 is correspondingly reduced. A multi-element cathode can also allow the MOE cell 10 to be operated at a lower temperature than the melting temperature of the target element while producing a liquid product. In one variation, cathode 40 can be a solid body.
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    9/22 [0027] The electrolyte 30 of cell 10 is generally a solvent, one or more support compounds and other optional ingredients dissolved therein. Electrolyte 30 dissolves the oxide feed charge, providing anionic species that carry oxygen and cationic precursors to the target element to be produced.
    [0028] As used here in relation to electrolyte 30, the term oxide melting means a liquid obtained by melting one or more solid oxides, the oxides contributing at least 25%, 50%, 75%, 85% or more than electrolyte weight 30. Illustratively, the electrolyte composition meets several criteria. The composition of the oxide fusion 30 for the extraction of a high melting target element is selected for its ability to dissolve the feed charge compound that carries the target element as well as with respect to other chemical and physical properties, known to those skilled in the art. Electrolyte 30 illustratively has a lower melting temperature than the melting point of the target element (or an alloy that constitutes cathode 40), thus allowing the operation of the MOE cell 10 with suitable electrolyte fluidity. An electrolyte 30 having a density much lower than that of the target element under the operating temperature profile in the MOE cell 10 allows for separation driven by gravity of the electrolyte 30 from the target element deposited on cathode 40.
    [0029] The electrical conductivity of the electrolyte 30 is illustratively low enough that in the practical values of separation of electrodes and current density the amount of Joule heating is sufficient to maintain the desired high operating temperatures in the MOE cell 10. Illustratively the electrical conductivity of the electrolyte can be in the range of 0.5 to 1.0 or 2.0 S / cm. For a relatively small anode-cathode spacing the electrolyte conductivity can be less than 0.5 S / cm. A contribution
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    10/22 relatively low electronics for the electrical conductivity of the liquid electrolyte, that is, on the order of less than 10% of the total electrical conductivity, allows the production of an element through the MOE at a sufficiently high Faradaic efficiency. The low vapor pressure of the electrolyte constituents at temperatures within the cell 10 and the high potential for decomposition of the electrolyte constituents compared to that of the feed charge compound limit the loss of material from the electrolyte 30 and the change in its composition to the over the life of the MOE cell 10.
    [0030] The fused oxide electrolyte 30 can incorporate, for example, silica, alumina, magnesia and calcium oxide. Liquids comprising calcium oxide (CaO) can be, by virtue of their position in the electrochemical series, suitable oxide fusions. For example, liquids based on the binary magnesium oxide-calcium oxide (MgO-CaO) system, with the addition of silicon dioxide (SiO2), alumina (AbOa), or other oxides, can provide adequate oxide fusions to extract relatively non-reactive high melting metal product elements, such as nickel, iron or chromium. Electrolyte 30 may incorporate an oxide that carries one or more of beryllium, strontium, barium, thorium, uranium, hafnium, zirconium, and a rare earth metal. As used here, rare earth metals are the fifteen lanthanides plus scandium and yttrium. The mentioned electrolyte constituents can also be incorporated into anode 50 to offer advantages during electrolysis in cell 10 as described below with reference to FIG. 4.
    [0031] Illustrative anode 50 is constituted to serve mainly as an electron sink with its surface at the contact interface 52 illustratively presenting a surface capable of sustaining the evolution of oxygen gas at an acceptable voltage. Consequently, the part of anode 50 that meets
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    11/22 electrolyte 30 in cell 10 is substantially inert, constituted to be stable in a corrosive environment and at high temperatures. Thus, anode 50 may require less frequent replacement than a conventional consumable anode. The relatively stable contour at the contact interface 52 provided by the composition at the interface 52 can allow for a closer spacing between cathode 40 and anode 50. This arrangement requires a lower voltage to conduct electrolysis and, consequently, a lower cost of energy per unit of target element produced than would be a larger spacing.
    [0032] The metallic character of the substrate 54 endows anode 50 with advantages in relation to cost and ease of manufacture in large complex shapes compared to high temperature materials such as graphite, composites, or ceramics. Illustrative anode 50 in this way can operate at a considerably lower temperature than cathode 40, for example, due to the cooling induced by the evolution of gas at the interface 52.
    [0033] The metallic substrate of anode 54 includes a continuous metallic phase. The metallic phase can consist mainly of a majority of metallic elements. The word element as used here with reference to anode 50 has its normal chemical sense, which means an element in the periodic table. Candidate elements for most metallic elements on anode substrate 54 in a given cell 10 include, for example, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Y, Zr, Nb, Mo, Hf, Ta, W, one of the noble metals, or the target element to be produced in cell 10. Most metallic elements in anode substrate 54 can be more reactive to oxygen than the target element at an operating temperature of interface 52. In other words, the Gibbs energy of oxide formation for most metallic elements can be of greater magn
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    12/22 greater than that of the desired target element, or the oxide of most metallic elements is more stable than an oxide of the target element. Alternatively, most metallic elements can be the target element. Several of the candidate elements for target elements listed above and / or elements showing stable oxides can together constitute more than 50% of the anode substrate 54. The metallic phase can be nominally the mono-element, that is, of a majority of elements, except for impurities not specified at low levels, for example, up to the order of 0.01%, 0.1% or 1% by weight.
    [0034] Alternatively, the metallic phase of the substrate 54 may be an alloy that incorporates a majority of metallic elements and an additional minority of elements or a plurality of such minority elements. Most of the metallic elements can be present in the substrate 54 in a concentration by weight of 50%, 60%, 70%, 80%, 90% or more. The one or more metallic elements added to the substrate 54 may collectively be present in concentrations of at least 1%, 5%, 10%, 15%, 25%, 35% or 45% by weight of the total metallic content of the alloy. A minority of individual elements may constitute at least 0.1%, 1%, 5%, 10%, 15% or 25% by weight of the total metallic content of the alloy.
    [0035] The alloy in the substrate 54 can be graduated in a compositional way, with the concentration of most metallic elements that increases or decreases with the distance of the contact interface. In one embodiment, substrate 54, whether of constant or variable composition, substantially constitutes entire anode 50, with the exception of the oxide layer 61 overlying substrate 54. In an alternative embodiment, anode 50 comprises a continuous anodolayer coating, which is substrate 54, which covers a metal core that has a lower cost and is compatible with the alloy of substrate 54,
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    13/22 for example, melting temperature and thermal expansion properties. The transition between the substrate and the nucleus can be abrupt or achieved by compositional grading.
    [0036] A minority of elementary constituents, constituting less than 50% by weight of anode substrate 54, illustratively falls into one of the following classes: a high melting point element, listed above as a possible target element; an element for which the oxide-forming Gibbs energy is of lesser magnitude than for the desired target element at the operating temperature of interface 52 in cell 10 and which combines with most metal elements to form an alloy that melts at a satisfactorily high temperature; beryllium, strontium, barium, thorium, uranium, hafnium, zirconium, or a rare earth metal; or another element having a high melting point and forming an oxide resistant to oxidation under operating conditions in cell 10.
    [0037] The invention is not limited by any theory, a constituent element in the anode substrate 54 can be stably bonded to oxygen under the operating conditions of cell 10, the constituent forming part of the solid oxide layer 61 at interface 52. Thus any reaction in cell 10 that involves an constituent of anode substrate 54, for example, with an oxide fusion ingredient 30 or any species produced at contact interface 52, can be self-limiting. An oxide in the solid oxide layer 61 at the contact interface 52 may be more stable than an oxide feed charge compound that undergoes electrolysis to produce the target element. Thus, the solid oxide layer 61 at interface 52 can protect substrate 54 from indiscriminate consumption during the electrolysis of the feed charge compound in cell 10. The elements that originate from electrolyte 30 can also be attached to the
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    14/22 solid oxide at interface 52.
    [0038] In one approach, most of the metal elements on substrate 54 are the same element as the target element. In this case, the solid oxide layer 61 can span regions presenting the same composition as the oxide feed filler from which the target element is being extracted. Thus, adventitious electrolysis of the oxide in the solid oxide layer 61 can increase the target element deposited on cathode 40 without introducing undesirable contaminants into it. However, cell 10 can be operated to maintain oxygen saturation conditions at contact interface 52, thereby sustaining solid oxide layer 61 and consequently limiting anode 50 consumption. For example, electrolyte 30 can be saturated in with respect to the oxide feed compound of the target element. Such saturation can be maintained by supplying a sufficient amount of the oxide feed charge compound in contact with the melt 30, before beginning cellular operation. Or, saturation in fusion 30 can be established during an initial transitional period during which the anode releases material in fusion 30. Alternatively, the local saturation of fusion 30 in relation to oxygen is established by generating oxygen gas at interface 52 during electrolysis.
    [0039] In some modalities, anode 50 has chromium as the majority of metallic elements. The abundance and relatively low cost of chromium is consistent with its use in an industrial scale metal extraction process such as MOE. The physical properties of chromium facilitate anode fabrication and handling at high temperatures. In one embodiment, the chromium-based anode 50, moreover, incorporates at least one other transition or refractory metal, for example, tantalum and / or vanadium. Such an anode of the chromium group 50 can be useful in cell 10 at temperatures as
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    15/22 high when 1500 ° C or higher. In another embodiment, the refractory metal anode, in addition, incorporates iron. Iron can be present in a weight percentage greater than 5%, 10%, 15%, 20%, 25% or 30%.
    [0040] In an exemplary process sequence that produces a target element selected from an oxide feed charge compound in cell 10, anode 50 is first kept free of electrolyte 30, thus leaving the circuit including power source 60 and cell 10 incomplete. The oxide compound is introduced into electrolyte 30, the compound dissolves in electrolyte 30 and after that it is present in it in the form of the respective ionic species that carry the target element and oxygen. Power source 60 is operated in the incomplete circuit as if to release a desired current through cathode 40 and anode 50. Anode 50 is thus anodically polarized. Anode 50 is reduced in its polarized state in electrolyte 30 to form the interface 52 with it, thus completing the circuit that includes source 60 and cell 10, which allows current to flow through cell 10 and initiate electrolysis in the cell 10.
    [0041] During the operation of the power source 60, the oxygen precursors in the electrolyte 30 migrate to the contact interface 52, illustratively on the surfaces of anode 50 that line cathode 40 and the surfaces that line channels 56. The electrons are removed from the oxygen precursors, conducted through the oxide layer 61 at the contact interface 52 and through the metal substrate 54 of anode 50 through the anode rods 58. The species in electrolyte 30 are thus oxidized at the contact interface 52 to form gaseous oxygen anodically. The gas consisting mainly of oxygen is thus generated at the contact interface 52, passes through channels 56, and leaves cell 10. During electrolysis, the anode 50 po
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    16/22 to sustain the current densities, proportionally divided through the interface 52 with the electrolyte 30, on the order of or greater than, for example, 0.05 A / cm 2 , 0.5 A / cm 2 , 1 A / cm 2 , 5 A / cm 2 or 10 A / cm 2 .
    [0042] Simultaneously, energy source 60 releases electrons through the collector bars 18, cathode substrate 16, and cathode 40. At the electrolyte-electrode interface 35, electrons are transferred to the species in electrolyte 40 that carries the element -target. The species are thus reduced, with the production of the target element in liquid form. The material produced accumulates in cathode 40 and therefore functions as part of cathode 40. The target metal can constitute in the order of 80%, 90%, 95%, 99% or more by weight of material produced by reducing the cathode.
    [0043] Cell 10 can initially be configured to include at least one element in cathode 40 that is not the target element. Thus, the electrolysis outlet in cell 10 can provide the target element in a liquid alloy that constitutes cathode 40 when the operation of cell 10 continues. The target element can be periodically removed from cathode 40, for example, by extracting cell 10. Cell 10 can be operated to produce the target element continuously by continuous additions of the oxide feed charge compound. In a variation, more than one target element can be deposited on the liquid cathode 40 during the operation of the cell 10 through the simultaneous or sequential electrolysis of the species that originate from the respective distinct oxide feed charge compounds or a mixed oxide single dissolved in electrolyte 30.
    [0044] Without being bound by any theory, one or more devices may be responsible for the solid oxide layer of composition 61. The oxide can be generated on the metallic substrate of anode 54 before anode 50 is placed in cell 10 from metallic elements that originate from the metallic substrate of anode 54. In a
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    17/22 modality, anode 50 is treated with an oxidizing atmosphere at an elevated temperature to develop the oxide on the metal substrate of anode 54. FIG. 3 shows a part of anode 50 placed in electrolyte 30 after a preformed oxide layer 65 has been developed at anode 50 outside cell 10 (FIG. 1). Methods of generating an oxide layer on a metallic body are known to those skilled in the art.
    [0045] Oxide can also be generated at anode 50 after it is brought into contact with the fusion of oxide 30 in cell 10. In this case, oxygen from electrolyte 30 oxidizes the constituents of anode substrate 54 and becomes part of the anode 50. FIG. 4 shows a part of anode 50 after an in situ oxide layer 63 has been generated by the operation of external power source 60 (FIG. 2) connected through the collector bars 18 and anode rods 58. With the continuation of the reference to FIG. 2 and FIG. 4, other elemental constituents of electrolyte 30 can also be incorporated by the oxide layer in situ 63. The oxide layer in situ 63 can be initially generated during an electrolysis operation in cell 10 that does not produce the target element in cathode 40. Alternatively, the oxide layer in situ 63 can be initially generated at the beginning of the electrolysis of the dissolved oxide feed compound with the production of the target metal. The initial consumption of a relatively small portion of anode substrate 54 behind the contact interface 52 illustratively protects anode 50 from indiscriminate consumption during prolonged continuous electrolytic production of the target metal as described above. The oxide layer 63 can incorporate the spinel regions. An electronically conductive spinel at contact interface 52 can support desirable metal production rates by facilitating the transfer of electrons from contact interface 52 to metal substrate 54. Rare earth elements transferred from electrolyte 30 and
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    18/22 incorporated in the solid oxide layer 61 in concentrations around, for example, 0.1% to 1.0% can increase the stability of the oxide layer 61. The rare earth elements can still be incorporated in the metallic substrate 54, thereby increasing the stability of the interface between the metal substrate 54 and the oxide layer 61.
    [0046] With reference to FIG. 2, FIG. 3 and FIG. 4, the solid oxide layer 61 may include metal-oxygen associations formed by the pre-electrolysis process described for layer 65, the in situ process described for oxide layer 63, or both. In one embodiment, the solid oxide layer 61 is stratified, substrate 54 that carries a preformed oxide layer covered by an in situ oxide layer meets electrolyte 30 at interface 52. Alternatively, the solid oxide layer 61 at interface 52 may show the respective regions of the preformed oxide layer and the oxide layer in situ for electrolyte 30. For example, spinel can be precipitated during electrolysis at the slag intrusion sites through a layer of preformed oxide of most elements.
    [0047] As an example of a specific application of the EOM, iron extraction can be instructive in relation to the benefits and considerations relevant to the illustrative device and method. Used for the production of iron and / or steel, in a modality the EOM proceeds according to
    2Fe2 Oa (s) 4Fe3 + + 6O 2 - 4Fe (l) + 3 O2 (g), [0048] thus providing drastic mitigation of greenhouse gas emissions compared to conventional approaches to produce iron and steel. The attenuation of carbon dioxide by MOE can be achieved even when the electrolysis that produces iron in cell 10 is conducted by the electricity produced by
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    19/22 combustion of fossil fuels, for example, as in the case of natural gas.
    [0048] The MOE can accommodate a range of degrees, particle sizes and morphologies of the iron ore to be dissolved in the molten oxide mixture 30. The fine and ultrafine particles of the oxide feed material can be introduced directly into the cell of MOE. Thus, the EOM can operate without the energy consumption and other operating costs of the granulation and sintering unit conventionally applied before iron extraction. In principle, the MOE method converts iron oxide into liquid metal in a single step. It is expected that, in principle, any iron oxide phase, including magnetite and hematite, can be introduced into the slag and finally dissolved in the oxide fusion.
    [0049] In addition, the chemical selectivity of electrolysis can guarantee the absence of phosphorus or other elements of gangue from the iron deposited on cathode 40. The metal produced on cathode 40 can contain a high fraction of iron, for example, 90% , 95%, 99%, 99.9% or greater by weight. The production of iron or steel of a desired purity may therefore be possible from inferior iron ore, undesirable elements being stabilized in the ionic form in the electrolyte due to their more negative decomposition potentials. The selectivity of the MOE and the virtual absence of carbon from the components of the illustrative electrolysis cell 10, particularly anode 50, especially adjust to the iron product in cathode 40 to serve as a basis for high purity alloys or low carbon formulations, such as stainless steels.
    [0050] The liquid electrolyte of mixed oxides 30, or slag, used in an MOE device such as cell 10 to extract iron may have the desired liquid fluidity and density properties
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    20/22 for slag known in conventional iron extraction contexts. For the electrolytic extraction of pure iron through the MOE, the electrolyte 30 illustratively has a melting temperature between about 1350 ° C and 1450 ° C, with lower permissible melting temperatures when producing an alloy in cathode 40 as described above. Liquids in the CaO-MgO-AbO3-SiO2 system, with additions, for example, of yttrium, zirconia or thorium, can be suitable electrolytes for the extraction of iron.
    [0051] Another criterion for selecting the electrolyte composition refers to the mixed iron valence. For a slag in balance with atmospheric pressure and composition, iron cations octahedrally coordinated in an oxide fusion effect the formation of the iron polaron, which can allow electrons to move through the slag 30. Iron (II ) assumes octahedral coordination while iron (III) assumes a distribution over both tetrahedral and octahedral coordination geometries. It may be that highly basic slags are able to stabilize iron (III) tetrahedrally coordinated and reduce the concentration of iron (II) and iron (III) octahedrally coordinated, thus limiting the electronic conductivity in the slag. Additionally, basic slags are ionic fusions in which the electrical current is charged by a secondary alkali metal or alkaline earth metal cations. Consequently, transport phenomena and chemical reactions are relatively fast.
    [0052] Cathode 40 in an iron extraction cell 10 can be an association of nominally pure liquid iron that is increased by electrolysis during cellular operation. Ultra-high purity liquid iron can be produced as a main melt to which the addition of alloy can be carried out in a simple way. The interface 35 between electrolyte 30 and cathode 40 for the production of pure iron can
    Petition 870190063843, of 07/08/2019, p. 23/34
    21/22 be at a temperature higher than the melting temperature of the iron. Alternatively, the liquid body can be, for example, iron or molten steel, which allows the production of iron alloys of desired composition with temperatures below 1500 ° C at interface 35. For example, the MOE that adds iron to a cast iron cathode 40 can operate at an interface temperature of about 1480 ° C up to a carbon content of around 2 percent atomic.
    [0053] In a cell 10 embodiment adapted for the extraction of iron from an iron feed load, anode 50 includes a substrate 54 in which most elements are chromium. The anode can form an oxide layer containing regions of chromium oxide and electronically conductive spinel at the contact interface 52 with electrolyte 30 during electrolysis in cell 10. A substrate with most chromium 54 in an iron extraction cell 10 it can also contain vanadium or tantalum.
    [0054] Anode substrate 54 in an iron extraction cell 10 may contain iron, with chromium present in a concentration greater than 25%, 50%, 70%, 75%, 80% or 90% by weight. Iron can be present in anode substrate 54 in a concentration greater than 5%, 10%, 15%, 20% or 25% by weight. Illustratively, the Cr-Fe 54 anode substrate is preoxidized to form a preformed layer 65 (FIG. 3) of Cr2Oa prior to placement in cell 10. For example, an anode substrate based on Cr 54, illustratively 70 % Cr and 30% Fe by weight, can be treated for two hours at 1450 ° C in an argon atmosphere with 50 ppm of oxygen to create an anode 50 with an oxide ratio of 65 in it. Such anode 50 can develop an in situ oxide layer (Cr, Al, Mg, Fe, Ca), including the spinel regions, on the pre-electrolysis scale 65 during iron production by electrolysis in cell 10 with an electrolyte CaO-MgO-AhO3-SiO2. In one variation, the electron
    Petition 870190063843, of 07/08/2019, p. 24/34
    22/22 lito 30 may also include ZrÜ2 and the oxide layer in situ still incorporates Zr.
    [0055] The illustrative electrolytic device 10 is not limited to any particular method being carried or remaining at the operating temperature. During the initial assembly of the cell, a liquid constituent such as the electrolyte can initially be melted in a separate heated chamber with sufficient overheating to allow transfer into the electrolytic cell compartment. In another approach, external heaters are used before or during operation, placed, for example, on the cell compartment wall. Or, the liquids in the compartment can be self-heated during operation through applied excessive potentials or resistive heating through the DC or AC current that passes through the electrolyte 30. The practical aspects of electrometallurgical systems potentially useful for the implementation of the illustrative method and devices, such as the construction of a high temperature device to contain molten salts and liquid metals, and control of the temperature profiles in their use, are known to those skilled in the art.
    [0056] Although specific aspects are included in some modalities and designs, and not in others, it should be noted that each aspect can be combined with any or all other aspects according to the invention. It will therefore be noted that the foregoing represents a highly advantageous approach for extracting an element from an oxide, particularly for metals that melt at high temperatures. The terms and expressions used herein are used as terms of description and not of limitation, and there is no intention, in the use of such terms and expressions, to exclude any equivalents of the aspects shown and described or their parts, but it is recognized that several modifications are possible within the scope of the claimed invention.
    权利要求:
    Claims (25)
    [1]
    1. Method for extracting a target element from an oxide raw material of the target element, characterized by the fact that it comprises:
    providing a liquid oxide electrolyte (30), comprising at least 75% by weight of one or more oxide compounds, in which the oxide raw material is dissolved forming ionic ionic species and target element ionic species;
    providing an anode (50), including a metal anode substrate (54), one element constituting at least 50% by weight of metal anode substrate (54), and the one element is more reactive with respect to oxygen than the target element, the metal anode substrate (54) having an oxide layer (61) comprising one or more oxides, the metal anode substrate (54), the electrolyte (30), or combinations thereof, the anode (50) in contact with the electrolyte (30);
    providing a cathode (40) in contact with the electrolyte (30);
    conducting electrons from the ionic oxygen species, in the electrolyte (30), to the metallic substrate (54) through the oxide layer (61) in it to form gaseous oxygen; and reducing ionic species of target element, in the electrolyte (30), to form a liquid of the target element in the cathode (40), with the target element having a melting temperature above 1,200 ° C.
    [2]
    2. Method according to claim 1, characterized by the fact that it further comprises the formation of the oxide layer (61) by oxidation of the material on the metallic substrate (54) before the anode (50) contacts the electrolyte (30).
    [3]
    3. Method according to claim 1, characterized by the fact that the metal anode substrate (54) comprises at least one among scandium, titanium, vanadium, chromium, manganese, iron,
    Petition 870190063843, of 07/08/2019, p. 26/34
    2/5 cobalt, nickel, yttrium, zirconium, niobium, molybdenum, hafnium, tungsten and tantalum.
    [4]
    4. Method, according to claim 1, characterized by the fact that it also comprises the reduction of species in the electrolyte (30) presenting an additional element to form the additional element in the cathode (40) simultaneously with the formation of the target element.
    [5]
    5. Method, according to claim 1, characterized by the fact that the target element is iron, the raw material compound is an iron oxide, and the cathode (40) is liquid carbon steel.
    [6]
    6. Method according to claim 1, characterized by the fact that the target element constitutes at least 90%, by weight, of material formed by reduction in the cathode (40) during electrolysis.
    [7]
    Method according to claim 1, characterized by the fact that the oxide layer (61) comprises an electronically conductive oxide phase.
    [8]
    8. Method according to claim 1, characterized by the fact that the target element is formed at a temperature greater than 1,400 ° C in the cathode (40).
    [9]
    9. Method according to claim 1, characterized by the fact that the cathode (40) is a liquid body.
    [10]
    10. Method according to claim 1, characterized by the fact that the target metal is iron, and the anode substrate is at least 50% chromium by weight.
    [11]
    11. Method according to claim 10, characterized by the fact that the metallic substrate (54) of the anode incorporates tantalum or vanadium.
    [12]
    12. Method, according to claim 1, characterized by the fact that:
    the oxide raw material comprises an oxide of the element
    Petition 870190063843, of 07/08/2019, p. 27/34
    3/5 target selected from the group consisting of iron, titanium, nickel, manganese, cobalt, zirconium, chromium, silicon, and combinations thereof; and the metallic anode substrate (54) comprises at least 50% by weight of a metal selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, yttrium, zirconium, niobium, molybdenum, hafnium, tungsten, tantalum, and combinations thereof, the anode (50) presenting an oxide layer (61) comprising material originated in the metallic substrate.
    [13]
    13. Method according to claim 3 or 12, characterized by the fact that one of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, yttrium, zirconium, niobium, molybdenum, hafnium, tungsten and tantalum, they constitute at least 70%, by weight, of the metallic substrate (54) of the anode.
    [14]
    14. Method according to claim 3 or 12, characterized in that the target element constitutes at least 1%, by weight, of the metal anode substrate (54).
    [15]
    15. Method according to claim 3 or 12, characterized by the fact that thorium, uranium, beryllium, strontium, barium, hafnium, zirconium or yttrium, constitutes at least 0.1%, by weight, of metallic substrate (54 ) of the anode.
    [16]
    16. Method according to claim 1 or 12, characterized by the fact that the target element is one of titanium, nickel, magnesium, cobalt, zirconium, chromium and silicon.
    [17]
    17. Method according to claim 1 or 12, characterized by the fact that the target element is iron, and the compound of the raw material is an iron oxide.
    [18]
    18. Method, according to claim 1, characterized by the fact that:
    the metal anode substrate (54) comprises at least
    Petition 870190063843, of 07/08/2019, p. 28/34
    4/5 in 50% by weight of chromium and at least 1% by weight of iron in contact with the electrolyte; and reducing the ionic species of target element in the electrolyte (30) includes reducing the species with iron in the electrolyte to form iron in the cathode (40).
    [19]
    19. Method, according to claim 18, characterized by the fact that the electrolyte (30) comprises oxides of silicone, aluminum, magnesium and calcium.
    [20]
    20. Method according to claim 1, 12 or 18, characterized in that the electrolyte (30) comprises thorium, uranium, beryllium, strontium, barium, hafnium, zirconium oxide or a rare earth element.
    [21]
    21. Method, according to claim 18, characterized by the fact that the spinel phase develops over the anode (50) during electrolysis.
    [22]
    22. Method according to claim 18, characterized by the fact that the cathode (40) is a liquid iron alloy.
    [23]
    23. Method, according to claim 22, characterized by the fact that iron is formed by reduction in the cathode (40) at a temperature below 1,500 ° C.
    [24]
    24. Device (10), characterized by the fact that it comprises:
    a liquid oxide electrolyte (30) comprising at least 75% by weight of one or more oxide compounds selected from calcium oxide, magnesium oxide, aluminum oxide and silicon oxide, including ionic oxygen species and ionic species target element from an oxide raw material compound dissolved in the electrolyte (30);
    a liquid cathode (40) in contact with the electrolyte (30); and an anode (50), including a metal anode substrate
    Petition 870190063843, of 07/08/2019, p. 29/34
    5/5 (54) showing at least 50% by weight of chromium and a metal selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, yttrium, zirconium, niobium, molybdenum, hafnium, tungsten and tantalum, the anode (50) having an oxide layer (61) comprising one or more oxides of the metal anode substrate (54) or the electrolyte (30), or combinations thereof, the anode (50) in contact with the electrolyte (30) in a contact interface, said device (10) being operable by connecting the anode (50) and cathode (40) to a power source (60) to electrolyze the oxide raw material compound dissolved, conduct electrons of the ionic oxygen species through the oxide layer (61) to form gaseous oxygen and reduce the ionic species of the target element to form the target element in the cathode (40).
    [25]
    25. Device (10) according to claim 24, characterized by the fact that:
    the oxide raw material comprises an iron oxide raw material dissolved in the electrolyte (30) forming ionic oxygen species and iron ionic species, and the metallic anode substrate (54) comprises at least 50% by weight of chromium and at least 1% by weight of iron.
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    AU2011293904B2|2016-06-02|
    EP2609231A1|2013-07-03|
    US20120043220A1|2012-02-23|
    BR112013004285A2|2016-05-31|
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    RU2585904C2|2016-06-10|
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    BR112013004285A8|2018-07-10|
    ES2703715T3|2019-03-12|
    EP3533906A1|2019-09-04|
    WO2012026971A1|2012-03-01|
    CN103180487A|2013-06-26|
    US8764962B2|2014-07-01|
    CA3011682A1|2012-03-01|
    CA2809237A1|2012-03-01|
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    AU2011293904A1|2013-03-14|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-05-07| B06T| Formal requirements before examination|
    2019-12-17| B09A| Decision: intention to grant|
    2020-02-27| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/08/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
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    US37593510P| true| 2010-08-23|2010-08-23|
    US61/375,935|2010-08-23|
    US201161489565P| true| 2011-05-24|2011-05-24|
    US61/489,565|2011-05-24|
    PCT/US2011/001469|WO2012026971A1|2010-08-23|2011-08-22|Extraction of liquid element by electrolysis of oxides|
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