Method for recovering metal-containing material from composite material

Abstract

The invention relates to a method for recovering a metal-containing material from a composite material. The present invention provides a method of recovering a metal-containing product (Mproduct), the method comprising: providing a composite material comprising a matrix of oxidized reductant (Ro), a product metal (MP) dispersed in the matrix of oxidized reductant (Ro), and one or more metal compounds (MPCR) of a product metal (MP) in one or more oxidation states dispersed in a matrix of an oxidising reducing agent (Ro); and treating the composite material to at least partially remove the one or more metal compounds (MPCR) from the matrix of the oxidized reducing agent (Ro), thereby forming a metal-containing product (Mproduct).

Description

[0001] This application is a divisional application of Chinese patent application No. 201680058477.2. Field of the Invention

[0002] The present invention relates to a method for recovering metal-containing materials from composite materials. In particular, the present invention relates to a method for recovering metal-containing products (M) from novel composite materials. 产物 ), wherein the novel composite material comprises an oxidized reducing agent (R o ) matrix, dispersed in the oxidizing reducing agent (R o ) in the matrix of the product metal (M P ), and a reducing agent (R o ) in one or more oxidation states of the product metal (M P ) of one or more metal compounds (M P C R ). Background Art

[0003] International Publication No. WO 2006 / 042360 provides a method for producing titanium by reacting titanium tetrachloride with magnesium in a reactor that may contain a fluidized bed. The temperature in the reactor is above the melting point of magnesium, but below the melting point of magnesium chloride. The method produces particles containing titanium, which are removed from the reactor and processed to recover titanium particles that generally have a particle size greater than 500 μm. In line with conventional thinking, the method of WO 2006 / 042360 operates under an excess of magnesium, and the unreacted magnesium is optionally collected and recycled to the reactor. This is understood to achieve complete conversion of TiCl4 into titanium metal while avoiding the formation of subchlorides, TiCl2 and TiCl3.

[0004] Applicants have identified a method for producing a composite material from at least one metal compound, wherein an excess oxidant is fed into a reactor during the process. The composite material is typically in a subdivided form, and the method typically does not require much effort to remove by-products from the composite material. The method for producing the composite material is described in detail in a co-pending international patent application entitled "METHOD FOR THE PRODUCTION OF A COMPOSITE MATERIAL USING EXCESS OXIDANT" filed on the same day as the present application. The contents of the co-pending application are incorporated herein in their entirety.

[0005] The subject matter claimed herein is not limited to implementations that solve any disadvantages or that operate only in environments such as described above. Rather, this background is merely provided to illustrate one exemplary technology area where some implementations described herein may be practiced. SUMMARY OF THE INVENTION

[0006] As noted above, the present invention generally relates to the recovery of metal-containing products (M) from composite materials. 产物 ) method.

[0007] According to one aspect of the present invention, there is provided a method for recovering a metal-containing product (M 产物 ), comprising:

[0008] Provided is a composite material comprising an oxidized reducing agent (R o ) matrix, dispersed in the oxidizing reducing agent (R o ) in the matrix of the product metal (M P ), and a reducing agent (R o ) in one or more oxidation states of the product metal (M P ) of one or more metal compounds (M P C R );and

[0009] The composite material is treated to at least partially remove the oxidized reducing agent (R o ) to remove one or more metal compounds (M P C R ), thereby forming a metal-containing product (M 产物 ).

[0010] For convenience, the term "composite material" will be used to describe a composite material that is a metal salt composite material, an alloy salt composite material, or an intermetallic salt composite material. That is, the term "composite material" as used herein is intended to include within its scope a composite material comprising salts and the following: (i) a metallic element and a reduced metallic compound of a metallic element, (ii) two or more metallic elements and reduced metallic compounds of two or more metallic elements, and (iii) one or more metallic elements together with one or more non-metallic elements and one or more reduced metallic compounds of one or more metallic elements.

[0011] In a similar manner, the term "product metal" will be used to describe a product that is a metal, alloy, or intermetallic product. That is, the term "product metal" as used herein is intended to include within its scope products that contain (i) one metallic element, (ii) two or more metallic elements, or (iii) one or more metallic elements and one or more non-metallic elements.

[0012] As used herein, the term "removal" will be used to describe the removal of one or more metal compounds (M P C R ) from the oxidizing reducing agent (R o) is physically removed from the matrix, for example by distillation or other physical mechanisms. The term will also be used to describe metal compounds (M P C R ), for example by reduction.

[0013] Throughout the specification, unless the context requires otherwise, the word "comprise" or variations such as "include" or "comprising" will be understood to imply the inclusion of the stated steps or elements or integers or groups of steps or elements or integers, but not the exclusion of any other steps or elements or integers or groups of steps, elements or integers. Therefore, in the context of this specification, the term "comprise" is used in an inclusive sense and should therefore be understood to mean "mainly including but not necessarily only including".

[0014] According to one embodiment of the invention, the treating step comprises removing the oxidized reducing agent (R o ) in a matrix of one or more metal compounds (M P C R The distillation can further at least partially remove the oxidized reducing agent (R o In one embodiment, the treating step comprises subjecting the composite material to a reducing agent (R o ) volatilization conditions. For example, these conditions may lead to the oxidation of the reducing agent (R o )’s sublimation.

[0015] The treating step may include (i) volatilizing one or more metal compounds (M P C R ) and (ii) one or more metal compounds (M P C R ) is reduced to the product metal (M P ) at least one of.

[0016] According to one embodiment, one or more metal compounds (M) are removed from the composite material by vacuum distillation. P C R ) and optionally an oxidizing reducing agent (R o ). For example, the vacuum distillation can be carried out under inert conditions, such as under argon. If so, an inert gas (e.g., argon) is added as a barrier gas at a rate that depends on the scale of operation and the vacuum applied. According to this embodiment, the vacuum distillation can be carried out at a pressure of 0.01 to 0.015 kPa. The vacuum distillation is preferably carried out under conditions where sublimation of the oxidized reducing agent (Ro) occurs.

[0017] In a specific embodiment, the product metal (M P ) contains titanium, an oxidizing reducing agent (R o) contains magnesium chloride, vacuum distillation is carried out at a temperature of 700°C to 950°C, and the product metal (M P ) optionally comprises at least titanium.

[0018] It has been found that treating at relatively low pressures preserves the form of the product metal (MP) recovered from the composite material. For example, if the composite material is particulate and comprises a plurality of small particles, as discussed in more detail below, treating under these conditions may result in the product metal (MP) being in particulate form. P ) recycling.

[0019] In another embodiment, the treating step comprises treating the product metal (M) in the presence of a reducing agent (R) P ) of one or more metal compounds (M P C R ) is reduced to the product metal (M P The reducing agent (R) may be contained in the oxidized reducing agent (R o ) within the matrix, and / or the reducing agent (R) can be combined with the composite material before or during distillation.

[0020] In another embodiment, the treating step comprises melting at least the matrix of the composite material oxidized reducing agent and recovering the metal-containing product (M) from the melt. 产物 ). The temperature at which melting is performed will be predetermined to some extent by the components of the matrix of the oxidized reducing agent of the composite material. In certain embodiments, melting can be performed at a temperature below the individual melting temperatures of the components of the matrix by forming a composition comprising hypoeutectic and hypereutectic compositions. In a preferred embodiment, the composition of the components of the composite material can form a eutectic composition. Melting can be performed by introducing the composite material into a molten pool. The molten pool can be one of reduced melting points, such as a eutectic mixture.

[0021] In this embodiment, the metal-containing product (M) is recovered from the melt. 产物 ) may include subjecting the melt to conditions under which the product metal (M P ), one or more metal compounds (M P C R ) and the oxidizing reducing agent (R o ) to form separate layers in the melt, and to recover the product metal (M P ) layer. For example, separation may include density separation, gravity separation or centrifugation. Recovery may also include components of the composite material (e.g., one or more metal compounds (M P C R ) and the oxidizing reducing agent (R o ))dissolution.

[0022] According to this embodiment of the invention, the product metal (M P ) may not be maintained, but (M P ) can be recovered and formed into, for example, product metal (M P ) ingot.

[0023] The reducing agent (R) may be a solid, solid particles, liquid or vapor. In certain embodiments, the reducing agent (R) is selected from the group consisting of Mg, Na, K, Li, Ba, Ca, Be and Al, although it is contemplated that other options may also be suitable. In certain embodiments, there may be two or more reducing agents (R), which may include one or more metal reducing agents (M R ). In other embodiments, it is contemplated that the reducing agent (R) may suitably comprise a multi-component reducing agent, such as an alloy, such as a Mg-Al or Mg-Pd alloy. Typically, the composite material comprises up to 20 wt%, preferably up to 3 wt% of the reducing agent (R).

[0024] In certain embodiments, the product metal (M) in one or more oxidation states P ) of one or more metal compounds (M P C R ) contains product metal (M P ) of one or more metal halides (M P X). For example, the product metal (M P ) of one or more metal compounds (M P C R ) may comprise a metal halide selected from the group consisting of titanium, aluminum, vanadium, chromium, niobium, molybdenum, zirconium, silicon, boron, tin, hafnium, yttrium, iron, copper, nickel, bismuth, manganese, palladium, tungsten, cadmium, zinc, silver, cobalt, tantalum, scandium, ruthenium and a rare earth element halide or a combination of any two or more thereof. The product metal (M) in one or more oxidation states P ) of one or more metal compounds (M P C R ) may contain at least two metal halides. If so, the metal halides may preferably be selected from halides of titanium, aluminum and vanadium.

[0025] In certain embodiments, the oxidized reducing agent (R o ) contains metal halides (M R X). For example, metal halides (M R X) can be selected from the group consisting of MgCl2, NaCl, KCl, LiCl, BaCl2, CaCl2, BeCl2, AlCl3 and any combination thereof.

[0026] The composite material may further comprise one or more metals (M). For example, additional metals incorporated into the composite material during the preparation of the composite material. The metal (M) may be selected from the group consisting of titanium, aluminum, vanadium, chromium, niobium, molybdenum, zirconium, silicon, boron, tin, hafnium, yttrium, iron, copper, nickel, bismuth, manganese, palladium, tungsten, cadmium, zinc, silver, cobalt, tantalum, scandium, ruthenium and rare earth elements or any combination of two or more thereof. For example, the other metal (i.e., metal element) may be solid or liquid aluminum metal.

[0027] In a preferred embodiment, the composite material is in the form of particles. The particles may generally be spherical. They may also be of regular or irregular shape. Preferably, the particles have an average particle size of up to 500 μm, more preferably 20-300 μm.

[0028] The metal component (M P ) typically has a particle size of up to about 1 micron. The metal component (M P ) The surface area to volume ratio in the protective matrix is ​​preferably greater than 6 m 2 / mL.

[0029] In this regard, for example, when a composite material is formed by contacting Mg with an excess of TiCl4 in a fluidized bed reactor to form Ti metal dispersed in a MgCl2 matrix, it is believed that at the extreme lower limit of particle size, one TiCl4 molecule can react with one Mg atom to form MgCl2 and TiCl2. Thereafter, another Mg atom reacts with TiCl2 to form a second MgCl2 and a single Ti atom. Thus, at its extreme, it is conceivable that the finely divided metal component (M P ) can be present at the atomic level in the MgCl2 protective matrix. Such an example would represent the metal component (M P ) is the real "primary particle". In fact, the metal component (M P) inherently desires nucleation or agglomeration (and possibly sintering), particularly at nascent sites and in the presence of some localized heating, mixing, possible electron transfer through partially molten salts, and the like. Thus, it is thought that there may be many atoms agglomerated together to form more viable "primary particles" that will be observed in the analysis. These particles may be very small, for example on the nanometer scale. However, at some point, further aggregation is not possible because, at least according to this embodiment, the MgCl2 is "frozen," encapsulating the Ti in its current agglomerated state, resulting in a frozen sea of ​​MgCl2 with uniformly dispersed titanium particles. Thus, in this particular embodiment, the ultra-high surface area metal without an oxide barrier is completely protected from forming larger particles or otherwise reacting unless the MgCl2 is removed. However, when the protective matrix (in this case MgCl2) is removed (e.g., by melting), the titanium particles are free to move around and further aggregate to form larger structures, such as shells of Ti. These structures can be considered "secondary particles." It should be understood that these comments are equally relevant to the metal component (M) in the protective matrix. P )’s surface area to volume ratio.

[0030] The metal components (M) of these preferred embodiments of the present invention P Another advantageous feature of these embodiments is the lack of a protective oxide layer. P ) particles do not have an activation barrier, which is different from the metal component (M P ) is associated with a lower activation energy (increased reactivity) of the particles. In addition to the above advantages, small particles are generally highly pyrophoric. The composite materials of the preferred embodiments of the present invention are relatively not. For conventional metal powders of approximately <10 um, pyrophoric becomes a major problem, but even at significantly larger sizes (>100 um) pyrophoric can be severe under certain conditions. The protective matrix of the composite materials of the present invention advantageously overcomes this problem.

[0031] The method of the present invention may further comprise combining the composite material with additional components before or during the treatment step. The additional components may be selected from the group consisting of: (i) a reducing agent (R oThe invention also provides a composite material of a matrix of (i) a quartz crystal (e.g., a metal halide) and one or more metal elements dispersed in the matrix, (ii) a metal element or compound, (iii) a non-metal element or compound, (iv) a metalloid element or compound, and (v) any combination of two or more of these. For example, the composite material can be combined with any one or more of the following: beryllium, boron, carbon, nitrogen, oxygen, aluminum, silicon, phosphorus, sulfur, scandium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, lead, bismuth, rare earth elements and their compounds.

[0032] Metal-containing products (M 产物 ) can be composed of the product metal (M P ) and the method may include recovering the product metal (M) from the composite material P The method may further include recovering the product metal (M P ) for post-processing. For example, post-processing includes crushing, grinding, coating, pressing, heat treatment (e.g., aging, annealing, quenching, tempering), rolling, forming, casting, hot or cold isostatic pressing (HIPing or CIP), molding, melting, sintering, mixing, extruding, drawing, forging, turning, welding, atomizing and / or spraying.

[0033] The method may further include pre-treating the composite material prior to the treating step. For example, the pre-treating may include at least one of compacting, crushing and grinding the composite material.

[0034] According to another aspect of the present invention, there is provided a metal-containing product (M) produced by the above method. 产物 ).

[0035] The metal-containing product (M) formed according to the present invention 产物 ) may comprise particulate metal having a particle size of less than 500 μm, preferably 20-300 μm, or may comprise product metal (M P ) ingot.

[0036] In certain embodiments, the product metal (M P ) is an alloy, such as an alloy of two or more of titanium, vanadium and aluminum. For example, the alloy may be close to Ti64.

[0037] In this regard, it is understood that Ti64 alloy generally refers to an alloy having a chemical composition of 6% aluminum, 4% vanadium, 0.25% (max) iron, 0.2% (max) oxygen and the remainder titanium. Ti64 is also commonly referred to as grade 5 titanium.

[0038] In another embodiment, palladium can be incorporated into the composite material to facilitate the recovery of grade 7 titanium. In this regard, grade 7 titanium contains 0.12-0.25% palladium. Small amounts of palladium provide enhanced resistance to crevice corrosion at low temperatures and high pH.

[0039] It is believed that the particulate metal may be suitable for use in many powder metallurgy processes. In this regard, as described above, it is contemplated that the recovered product metal (M P ) is that the desired shape and particle size for the particles can be predicted by manipulating the recycling method and the manufacturing method of the composite material. That is, the size and shape of the particles can be manipulated to obtain suitable particles for a specific powder metallurgy process.

[0040] The present invention consists of a combination of features and parts hereinafter fully described and illustrated in the drawings, it being understood that various changes in detail may be made without departing from the scope of the invention or sacrificing any of its advantages. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] In order to further clarify various aspects of some embodiments of the present invention, a more specific description of the present invention will be presented by reference to specific embodiments illustrated in the accompanying drawings. It should be understood that these drawings only depict typical embodiments of the present invention and should not be considered to limit its scope. The present invention will be described and explained with more specificity and detail through the accompanying drawings, in which:

[0042] Figure 1 A method for recovering metal-containing products (M) from composite materials is shown. 产物 ) is a flow chart of a method of manufacturing a composite material, which also illustrates an exemplary method for obtaining a composite material.

[0043] Figure 2 The weight loss of a titanium composite according to Example 4 that was rapidly heated to 500°C and held at that temperature for a period of time is shown.

[0044] Figure 3 Shown are the total titanium and magnesium contents determined by XRF of the feed material of Example 5 and several subsequent recycled material samples.

[0045] Figure 4 Shows the Figure 3 Similar graph, but showing the individual contents of titanium and magnesium, respectively.

[0046] Detailed description of preferred embodiments

[0047] Hereinafter, this specification will describe the present invention according to the preferred embodiment. It should be understood that limiting the description to the preferred embodiment of the present invention is only for the convenience of discussing the present invention and is contemplated without departing from the scope of the appended claims.

[0048] refer to Figure 1 , showing the recovery of metal-containing products (M 产物 For convenience and without any limitation on the recovery methods of the present invention, an exemplary method 100 for producing a suitable composite material comprising one or more product metals (M) in one or more oxidation states is also shown. P ) of one or more metal compounds (M P C R ). We provide the following non-limiting discussion of an exemplary method 100, followed by a more detailed discussion of the method 200 of the present invention.

[0049] According to the method 100 for recycling composite materials, the product metal (M p ) of metal compounds (M P C) 110 and capable of reducing the product metal (M P ) of metal compounds (M P The reducing agent (R) 120 of the reactor 130 is supplied to the reactor 130. The metal compound (M P C) 110 (including any recycled metal compounds (M P C) 140) is in excess relative to the amount of reducing agent 120 supplied to reactor 130. Composite material 150 is recovered from reactor 130. The composite material comprises oxidized reducing agent (R o ) matrix, dispersed in the oxidizing reducing agent (R o ) in the matrix of the product metal (M P ), and a reducing agent (R o ) in one or more oxidation states of the product metal (M P ) of one or more metal compounds (M P C R ). The composite material may further comprise a reducing agent (R).

[0050] Reference Figure 1 The reactor 130 discussed in the form of a fluidized bed reactor is below the reducing agent (R o ) and generally above the melting point of the reducing agent (R) 120, which may form part of the composite material 150. The temperature in the reactor 130 is between the melting point of the reducing agent (R) 120 and the oxidized reducing agent (R o) (e.g., its oxidized salt), the reaction of the reducing agent (R) 120 with the oxidizing agent results in the formation of a composite material 150 that contains mostly or completely solid characteristics. This "frozen" reaction advantageously has the effect of producing finely separated and high purity reaction products. Although not wishing to be bound by theory, it is believed that the particle size of the composite material 150 is such that the finely separated elements contained therein are small enough that they interact with visible light differently than their bulk counterparts do with visible light. For example, they can appear black or dark. The finely divided structure of the composite material 150 has advantages over composite materials of similar nominal composition that do not have the same finely divided structure. These advantages will be explained in more detail below.

[0051] When the reductant (R) 120 is fed into the reactor 130 as a solid or solid particles, the conditions prevailing in the reactor 130 ensure melting of the reductant 120 in a sufficient time. The time required for the solid reductant 120 to melt depends on many factors, including the feeding mechanism, whether the reductant 120 is fed with other materials, the temperature of the reactor 130, the intensity of the reaction per unit volume of the reactor 130, the particle density of the reductant 120 at any single location, and if other reductants or reagents or inert streams have entered or are entering the reactor, the proximity of the reductant 120 to these components and their respective temperatures when these components collide with the particles of the reductant 120.

[0052] The interaction of the reductant (R) 120 when it contacts other surfaces in the reactor 130 will depend on its phase at that time. If the reductant 120 particle is solid, the reductant 120 particle may collide and rebound. It will then continue to interact with other surfaces in the reactor 130 and the environment.

[0053] If the reductant 120 particle has a molten outer surface and a solid inner surface, the particle can attach to any surface it strikes, forming a composite of the two objects. The particle will then continue to interact with other surfaces and the environment in the reactor 130.

[0054] If the reducing agent 120 particles are molten when they interact with other surfaces, they can wet the surface. Depending on the characteristics of the solid-liquid interaction, the thickness of the layer formed will vary. It is believed that this can be manipulated by varying the strength of the interaction, the density of the reducing agent 120 feed, temperature and time, etc.

[0055] Regardless of the final location of the molten reducing agent in the reactor 130, whether as a separate species, wetted on a surface, or combined with other surfaces, at some point it will interact and react with the oxidant. At this point, the thickness or wetted layer or size of the molten material or particles is believed to be of some importance in determining the extent of reaction of the reducing agent (R) 120 and the morphology of the final composite material 150.

[0056] If the particles or the wetting layer are large enough or not completely melted at this time, the frozen nature of the reaction as described above can cause a certain proportion of the reducing agent (R) to be encapsulated by the composite material 150. In the case where the surface exposed to the oxidant reacts to form a solid, the surface can form a barrier (i.e., a shell) that can limit or eliminate the remaining reducing agent from participating in further reduction. If the particles are small enough or the wetting layer is thin enough, for example, if the thickness of the reaction layer is equal to the radius of the particle or the thickness of the wetting layer, the process can consume most (if not all) of the reducing agent (R).

[0057] The amount of oxidant relative to the reductant (R) in the reactor will be an important factor in determining the likelihood of the above interactions. The weighting of one form of interaction over other forms of interaction can be manipulated by changing the operating conditions, feed form, etc. The nature of the surfaces available for interaction in the reactor, the possibility of sequential ordering, and the form of contact between the reductant and the oxidant can lead to the formation of composite materials with various characteristics. These may include, but are not limited to, excess or fully consumed reductant, composite material layers, composite material layers with magnesium interstitial layers. It is believed that novel structured materials can be formed by sequentially stacking different layers of specified composition.

[0058] Once the composite material is recovered 150, it can be stored under suitable conditions for later use.

[0059] The present invention relates to a method for recovering a metal-containing product (M) from a composite material 150. 产物 In certain embodiments, the method includes recovering the product metal (M) directly from the composite material 210. P ), or may include in the process of combining the composite material with other product metals (M P ,) 220 and / or other compounding materials (C M ) 230 after the combination. Therefore, it is conceivable that various products can be recovered, including but not limited to metal-containing products (M 产物 )240, alloy or mixture containing metal products (M 产物 / M 产物 ,) 250, and mixtures or composites containing metal products (M 产物 / C M) 260. In any of these recovery processes, it is also desirable to recover the reducing agent (R). Once the desired composite material is formulated (ie, with or without additional materials), it is processed 270 to recover the metal-containing product 240, 250, 260.

[0060] The purpose of treating 270 the composite material is to at least partially remove the oxidized reducing agent (R o ) to remove one or more metal compounds (M P C R ), thereby forming a metal-containing product (M 产物 ). Generally, the purpose of treatment step 270 is to remove the oxidized reducing agent (R o ) is substantially completely removed from the matrix of one or more metal compounds (M P C R ).

[0061] Two treatment methods are currently envisioned 270 for the reduction agent (R o ) to remove one or more metal compounds (M P C R ) are particularly useful. These methods include distillation, especially vacuum distillation, and the presence of a reducing agent to reduce one or more metal compounds (M P C R ) is reduced to the product metal (M P ). These two options may be performed independently or in combination. However, it should be understood that other suitable options may be used. For example, the processing step 270 may suitably include melting the composite material and then separating the one or more metal compounds (M P C R ).

[0062] The treatment step 270 may also result in the removal of the oxidized reducing agent (R o As an example, one or more metal compounds (M) can be removed from the composite material by vacuum distillation. P C R ) and the oxidizing reducing agent (R o ). Treatment 270 may further result in the removal of the reducing agent (R), if present, which may be recycled to the reducing agent feed 120 or recovered in other ways. In these cases, the metal-containing products 240, 250, 260 may be composed of the product metal (M P )240, alloy or mixture of product metals (M P / M P’ )250 and mixtures or composites (M P / C M )260.

[0063] In addition to the different compositional inputs to the recycling process as described above, the finely characterized product metal (MP) in the composite material 150 is packaged in a material that is chemically inert to itself based on its grade characteristics. Product metals with similar compositional characteristics but without the same physical characteristics resulting from the packaging process will not respond to the same recycling process with similar results. That is, the surface does not have any protective or passivating layers, which means that it will react differently to physical interactions than its macroscopic bulk counterpart.

[0064] The individual components of the product metal surrounded by the inert material provide building blocks that may or may not combine to varying degrees through different driving forces in the recovery process to produce the product metal (M P ). Therefore, the product metal (M P )The conditions of release from the composite matrix and the conditions throughout the recovery process have a significant deterministic influence on the way in which each separate product metal building block interacts with other materials and ultimately on the way in which they can or cannot combine and the morphology and microstructure of the recovered product metal. Example

[0065] The following examples are provided for illustration only and are not to be construed as limiting the present invention in any manner.

[0066] Example 1 - Recovery of CP2 Titanium from a Primary MgCl2 Matrix

[0067] 30 g of a black composite material in the form of spherical particles comprising a magnesium chloride matrix, titanium metal, magnesium and a certain amount of titanium subhalide (TiCl2 and TiCl3) is placed in a container made of stainless steel. The container is placed under a vacuum with a pressure of about 0.01 kPa. Argon purge is provided at a rate of 10 mg / min. The container is then heated from the outside to a temperature of 900°C at a heating rate of 31°C per minute. The container is then placed at a temperature of 900°C for 1 hour and then cooled to room temperature.

[0068] The container was purged with air and the remaining material was recovered from the container, which contained about 5 g of titanium metal. The metal was in the form of loosely sintered spheres, approximately half the size of the particles of the composite material fed into the container.

[0069] This recycling process produces commercially pure Grade 2 titanium.

[0070] Implementation 2 - Combination of Composite Materials

[0071] 15 g of a black composite material in the form of spherical particles comprising a magnesium chloride matrix, titanium metal, aluminum metal, magnesium and a certain amount of titanium subhalides (TiCl2 and TiCl3) is combined with 15 g of a black composite material in the form of spherical particles comprising a magnesium chloride matrix, titanium metal, vanadium metal, magnesium and a certain amount of titanium subhalides (TiCl2 and TiCl3) and possibly vanadium subhalides.

[0072] A total of 30 g of the composite material was ground under inert conditions to form a uniform composition and then placed in a container made of stainless steel. The degree of grinding can be adjusted for different levels of uniformity. The container was placed under a vacuum with a pressure of about 0.01 kPa. An argon purge was provided at a rate of 10 mg / min. The container was then heated from the outside to a temperature of 900°C at a heating rate of 31°C per minute. The container was then placed at a temperature of 900°C for 1 hour and then cooled to room temperature.

[0073] The vessel is purged with air and the remaining material is recovered from the vessel, which contains about 5 g of metals containing titanium, aluminum and vanadium in proportion to the total amount of product metals input into the composite material. The metals are in the form of closely packed sintered particles of irregular shape.

[0074] Example 3 - Release of product metals from a primary MgCl2 matrix under atmospheric conditions

[0075] 30 g of a black composite material in the form of spherical particles comprising a magnesium chloride matrix, titanium metal, magnesium and a certain amount of titanium subhalides (TiCl2 and TiCl3) were ground under inert conditions and then placed in a container made of stainless steel. The degree of grinding or screening can be adjusted for different sizes and morphologies of the initial particle size of the composite material. The container was purged with argon at atmospheric pressure and then heated from the outside to a temperature of 900°C at a heating rate of 31°C per minute. The container was then placed at a temperature of 900°C for 1 hour and then cooled to room temperature.

[0076] The contents of the vessel were recovered and found to be a white and silvery substance composed of titanium metal and magnesium chloride. No green or purple color was present, which would indicate the presence of titanium subhalides in the salt phase.

[0077] The material was broken up, ground into powder, and returned to the stainless steel container. The container was placed under a vacuum at a pressure of about 0.01 kPa. An argon purge was provided at a rate of 10 mg / min. The container was then heated from the outside to a temperature of 900°C at a heating rate of 31°C per minute. The container was then placed at a temperature of 900°C for 1 hour and then cooled to room temperature.

[0078] The container was purged with air, and the remaining material, which contained about 5 g of titanium metal, was recovered from the container.

[0079] In atmospheric processes, the product metals are released from the protective matrix and can be consolidated to some extent by sintering. Similarly, melting of the matrix provides an opportunity for partially reduced or oxidized compounds to be released from the matrix structure and significantly enhance the opportunity to interact and react with other compounds in the matrix, or to be removed by boiling.

[0080] Example 4 - Recovery of a Metal-Containing Product Having Reduced Subhalide Content

[0081] 50 mg of a black composite material in the form of angular particles comprising a magnesium chloride matrix, titanium metal, magnesium and a certain amount of titanium subhalides (TiCl2 and TiCl3) is placed in an open alumina cup. The cup is placed in a vacuum furnace at a pressure of about 0.01 kPa. An argon purge is provided at a rate of 2 mg / min. The furnace is then heated to 500°C at a heating rate of 100°C per minute, which is sufficient to remove titanium and promote the disproportionation of titanium subhalides under vacuum. The container is then placed at a temperature of 500°C for 1 hour and then cooled to room temperature.

[0082] Figure 2 The weight loss of the material over time during the process is shown. It can be seen that the weight stabilizes after a short time.

[0083] The remaining material is recovered from the container, which contains about 30 mg of a metal-containing composite material having a significantly reduced subhalide content. This composite material can be passed through further recovery processes, where the effects of significant volatile subhalide content will be reduced or eliminated. These effects may include a significant increase in total volatile content, difficulty in controlling the conversion of subhalides to metals or removal of subhalides.

[0084] Example 5 - Recovery of a Metal-Containing Product Having Reduced Subhalide Content

[0085] Titanium composites with significant subhalide content were passed through vacuum at 600°C with a residence time of 2 hours. The feed composite contained uniform black spheres with a particle size of <2 mm.

[0086] After leaving the heating zone, the composite material became lighter in color, indicating that some form of chemical processing had occurred.

[0087] Figure 3 Shown are the total titanium and magnesium contents determined by XRF of the feed material and several subsequent recycled material samples. Figure 4 A similar graph is shown, but showing the individual contents of titanium and magnesium, respectively.

[0088] like Figure 3 As shown, the increase in total metal ion content between the feed and recycled materials indicates that the metal components of the composite have been concentrated in the process. Figure 4The titanium content of the recycled material is shown to decrease after treatment, which, when combined with the increase in total metal content, suggests that the titanium halide phase has been removed by the treatment and has not affected the remaining composite components.

[0089] Significantly, the process reduces the mass ratio of titanium to magnesium from 1.12 substantially towards the theoretical ratio of 0.985 for a two-phase mixture of titanium metal and magnesium chloride. As a result, the stability and predictability of the recovered composite material for subsequent processing will increase.

[0090] Example 6 - Recycling of composite materials by changing the melting point of the encapsulating salt

[0091] 2 g of a black composite material in the form of angular particles comprising a magnesium chloride matrix, titanium metal, magnesium and a certain amount of titanium subhalides (TiCl2 and TiCl3), 7.83 g of lithium chloride and 10.01 g of potassium chloride were ground together to form a uniform grey powder.

[0092] 50 mg of the grey composite material was placed in an open alumina cup. The cup was placed in a furnace under an argon atmosphere. The furnace was then heated to a temperature of 500°C at a heating rate of 10°C per minute. The material was kept at this temperature for 20 minutes and then cooled. The composite material exhibited an endotherm at around 350°C, indicating that the composite material had melted. This is in contrast to the melting point of the original composite material of about 715°C.

[0093] The cup was then placed in a vacuum furnace at a pressure of about 0.01 kPa. An argon purge was provided at a rate of 2 mg / min. The furnace was then heated to a temperature of 1100°C at a heating rate of 10°C per minute. The sample was shown to melt again at about 350°C. Surprisingly, all volatiles were removed below 700°C, leaving titanium metal. This represents a significant reduction in the temperature required to recover the metal component based on the original composite composition.

[0094] Example 7 - Recovery of Metals from Composite Materials Containing Aluminum

[0095] 50 mg of a gray composite material in the form of angular particles comprising a magnesium chloride matrix, titanium metal, aluminum and a certain amount of titanium subhalides (TiCl2 and TiCl3) was placed in an open alumina cup. The cup was placed in a furnace under an argon atmosphere. The furnace was then heated to a temperature of 900°C at a heating rate of 10°C per minute. The material was kept at this temperature for 20 minutes and then cooled. The composite material exhibited an endotherm at around 650°C, indicating that the aluminum metal melted. The composite material also showed an exotherm above and below 650°C, which was equivalent to the formation of titanium aluminide. The weight loss of the sample was shown to be more than 10% at around 500°C, consistent with the removal of TiCl3. The weight loss was shown to be more than 10% at around above 850°C, which was equivalent to the removal of TiCl2.

[0096] SEM examination showed that the recovered metal comprised a titanium-aluminum composition with a low residual chloride content.

[0097] Although the above examples mainly use magnesium chloride as the oxidizing reducing agent (R o ), but those skilled in the art will appreciate that other metals (including but not limited to other magnesium halides and halides of sodium, potassium, lithium and barium) are expected to achieve similar results due to similar properties.

[0098] Unless the context requires otherwise or specifically stated to the contrary, integers, steps or elements of the invention recited herein as a single integer, step or element expressly encompass both the singular and the plural form of the integer, step or element.

[0099] It should be understood that the foregoing description is given by way of illustrative examples of the invention and that all such modifications and variations as would be apparent to one skilled in the art are considered to fall within the broad scope and range of the invention as described herein.

Claims

1. A method for recovering a metal-containing product (M 产物 ), comprising: Provided is a particulate composite material having an average particle size of at most 500 μm, the composite material comprising an oxidized reducing agent (R) o ) matrix, dispersed in the oxidizing reducing agent (R o ) in the matrix of the product metal (M P ), and a reducing agent (R o ) in one or more oxidation states of the product metal (M P ) of one or more metal compounds (M P C R ), and a reducing agent (R), the composite material comprising up to 3 wt % of the reducing agent (R), the particle composite material being below the oxidized reducing agent (R o ) and above the melting point of the reducing agent (R); and Treating the composite material to at least partially remove the oxidized reducing agent (R o ) in a matrix to remove the one or more metal compounds (M P C R ), thereby forming the metal-containing product (M 产物 ), wherein the treatment is selected from distillation, reduction or melting, wherein the reducing agent (R) is selected from the group consisting of Mg, Na, K, Li, Ba, Ca, Be, Al, and any combination thereof, and the product metal (M) in one or more oxidation states P ) of one or more metal compounds (M P C R ) is a metal halide selected from the group consisting of halides of titanium, aluminum, vanadium, chromium, niobium, molybdenum, zirconium, tin, hafnium, iron, copper, nickel, bismuth, manganese, palladium, tungsten, cadmium, zinc, silver, cobalt, tantalum, ruthenium and rare earth elements or a combination of any two or more thereof.

2. The method according to claim 1, characterized in that The treating step comprises removing the oxidized reducing agent (R o ) in a matrix of P C R ).

3. The method according to claim 2, characterized in that The distillation at least partially removes the oxidized reducing agent (R o ).

4. The method according to claim 2 or 3, characterized in that The distillation results in at least one of (i) and (ii): (i) the one or more metal compounds (M P C R ) volatilizes, (ii) the one or more metal compounds (M P C R ) is reduced to the product metal (M) in the presence of a reducing agent (R) P ).

5. The method according to any one of claims 2 to 4, characterized in that: The one or more metal compounds (M) are removed from the composite material by vacuum distillation. P C R ) and optionally the oxidizing reducing agent (R o ).

6. The method according to claim 5, characterized in that The vacuum distillation is performed under inert conditions, such as under argon.

7. The method according to claim 6, characterized in that The argon is added as a barrier gas at a rate that depends on the scale of the operation and the vacuum applied.

8. The method according to any one of claims 5 to 7, characterized in that The vacuum distillation is carried out at a pressure of 0.01-0.015 kPa.

9. The method according to any one of claims 5 to 8, characterized in that The vacuum distillation is carried out in the oxidation reducing agent (R o ) is carried out under conditions where sublimation occurs.

10. The method according to claim 9, characterized in that The oxidizing reducing agent (R o ) contains magnesium chloride, the vacuum distillation is carried out at a temperature of 700°C to 950°C, and the product metal (M P ) optionally comprises at least titanium.

11. The method according to claim 1, characterized in that The treating step comprises treating the product metal (M) in the presence of a reducing agent (R) P ) of the one or more metal compounds (M P C R ) is reduced to the product metal (M P ).

12. The method according to claim 11, characterized in that The reducing agent (R) is contained in the oxidized reducing agent (R o ) within the matrix.

13. The method according to claim 11, characterized in that The reducing agent (R) is combined with the composite material before or during the distillation.

14. The method according to any one of claims 11 to 13, characterized in that The reducing agent (R) is solid, solid particles, liquid or vapor.

15. The method according to any one of claims 11 to 14, characterized in that The reducing agent (R) is selected from the group consisting of Mg, Na, K, Li, Ba, Ca, Be and Al.

16. The method according to claim 1, wherein: The processing step comprises melting the composite material and recovering a metal-containing product (M) from the melt. 产物 ).

17. The method according to claim 16, characterized in that Melting occurs at a temperature below the individual melting temperatures of the components of the matrix by forming a hypoeutectic or hypereutectic composition, preferably a eutectic composition.

18. The method according to claim 16 or 17, characterized in that Melting is performed by introducing the composite material into a melt pool.

19. The method according to claim 18, characterized in that The melt pool is one of reduced melting point, such as a eutectic mixture.

20. The method according to any one of claims 16 to 19, characterized in that Recovery of metal-containing products (M) from the melt 产物 ) comprises subjecting the melt to a product metal (M P ), one or more metal compounds (M P C R ) and the oxidizing reducing agent (R o ) to form separate layers in the melt, and to recover the product metal (M P )layer.

21. The method of claim 20, wherein: The formation of the separated layers is achieved by density separation, gravity separation or centrifugation.

22. The method according to any one of claims 16 to 19, characterized in that Recovery of metal-containing products (M) from the melt 产物 ) includes dissolution of components of the composite material, such as one or more metal compounds (M P C R ) and the oxidizing reducing agent (R o ).

23. A method as claimed in any one of the preceding claims, characterised in that The product metal (M) in one or more oxidation states P ) of the one or more metal compounds (M P C R ) contains the product metal (M P ) of one or more metal halides (M P X).

24. The method of claim 23, wherein: The product metal (M) in one or more oxidation states P ) of one or more metal compounds (M P C R ) comprises a metal halide selected from the group consisting of halides of titanium, aluminum, vanadium, chromium, niobium, molybdenum, zirconium, silicon, boron, tin, hafnium, yttrium, iron, copper, nickel, bismuth, manganese, palladium, tungsten, cadmium, zinc, silver, cobalt, tantalum, scandium, ruthenium and rare earth elements, or combinations of any two or more thereof.

25. The method according to claim 23 or 24, characterized in that The product metal (M) in one or more oxidation states P ) of one or more metal compounds (M P C R ) comprises at least two metal halides.

26. The method of claim 25, wherein: The metal halide is selected from the group consisting of halides of titanium, aluminum and vanadium.

27. A method as claimed in any one of the preceding claims, characterised in that The oxidizing reducing agent (R o ) contains metal halides (M R X).

28. The method of claim 27, wherein: The metal halide (M R X) is selected from the group consisting of MgCl2, NaCl, KCl, LiCl, BaCl2, CaCl2, AlCl3 and BeCl2.

29. A method as claimed in any one of the preceding claims, characterised in that The composite material further comprises one or more metals (M).

30. The method of claim 29, wherein: The metal (M) is selected from the group consisting of titanium, aluminum, vanadium, chromium, niobium, molybdenum, zirconium, silicon, boron, tantalum, tin, hafnium, yttrium, iron, copper, nickel, lithium, bismuth, manganese, palladium and rare earth elements or a combination of any two or more thereof.

31. A method as claimed in any one of the preceding claims, characterised in that The composite material is in the form of spherical particles.

32. The method according to any one of claims 1 to 30, characterized in that The particulate composite material is in the form of regularly or irregularly shaped particles.

33. A method as claimed in any one of the preceding claims, characterised in that The average particle size of the particles is 20-300 μm.

34. A method as claimed in any one of the preceding claims, characterised in that The method further comprises combining the composite material with additional components prior to or during the treating step.

35. The method of claim 34, wherein: The additional component is selected from the group consisting of: (i) a reducing agent (R o ) and a composite material of one or more metal elements dispersed in the matrix, the oxidizing reducing agent (R o ) such as metal halides; (ii) metal elements or compounds; (iii) non-metal elements or compounds; (iv) metalloid elements or compounds; and (v) any combination of two or more of these.

36. The method of claim 35, wherein: For example, the additional component is selected from the group consisting of beryllium, boron, carbon, nitrogen, oxygen, aluminum, silicon, phosphorus, sulfur, scandium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, lead, bismuth, rare earth elements, compounds thereof, and any combination thereof.

37. A method as claimed in any one of the preceding claims, characterised in that The metal-containing product (M 产物 ) is composed of the product metal (M P ), the method comprising recovering the product metal (M P ).

38. The method of claim 37, wherein: The method further comprises treating the recovered product metal (M P ) for post-processing.

39. The method of claim 38, wherein: The post-processing includes crushing, grinding, coating, pressing, heat treatment (such as aging, annealing, quenching, tempering), rolling, forming, casting, hot or cold isostatic pressing (HIPing or CIP), molding, melting, sintering, mixing, extruding, drawing, forging, turning, welding, atomizing and / or spraying.

40. A method as claimed in any one of the preceding claims, characterised in that The method further comprises pre-treating the composite material prior to the treating step.

41. The method of claim 40, wherein: The pre-treatment includes at least one of compacting, crushing and grinding the composite material.

42. The method according to any one of claims 1 to 30, characterized in that The metal-containing product (M 产物 ) contains a particulate product metal (M) having a particle size of less than 500 μm, preferably 20-300 μm P ), or comprising the product metal (M P ) ingot.

43. A method as claimed in any one of the preceding claims, characterised in that The metal-containing product (M 产物 ) is an alloy, such as an alloy of two or more of titanium, vanadium and aluminum.

44. The method of claim 43, wherein: The alloy is close to Ti64.

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