Carboaluminothermic reduction apparatus and method of use

Abstract

An apparatus and method for making titanium or a titanium alloy includes providing a first feed material and a carbon source material to a first reaction chamber, the first feed material comprising solid aluminum oxide. The method further includes heating the first feed material and the carbon source material to reduce the solid aluminum oxide to one or more gaseous species comprising aluminum. The method further includes providing one or more gaseous species comprising aluminum to a second reaction chamber, the second reaction chamber containing a second feed material comprising solid titanium oxide. The method further includes reducing the solid titanium oxide with the one or more gaseous species comprising aluminum to form molten titanium metal or a molten titanium alloy.

Description

[Technical Field]

[0001] Priority claims and incorporation by reference of any application claiming priority This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 280,664, entitled "CARBOALUMINOTHERMIC REDUCTION APPARTUS AND METHODS OF USING," filed November 18, 2021, which is incorporated herein by reference in its entirety. Summary of the Invention [Problem to be solved by the invention]

[0002] Aluminothermic reduction methods for producing titanium have been investigated. These methods typically involve preparing a mixture of solid aluminum metal powder and a powder containing titanium oxide material, and then heating the mixture to react the solid aluminum metal powder with the titanium oxide and reduce the titanium oxide to titanium metal. Because these methods require first producing aluminum metal powder as a reducing agent, they have proven to be very energy-intensive. Furthermore, these methods are typically configured for batch processing and therefore do not operate continuously.

[0003] Aspects of the present disclosure are best understood from the following detailed description when read in conjunction with the accompanying drawings. It should be noted that, according to standard industry practice, various features have not been drawn to scale. In fact, the dimensions of various features may be arbitrarily increased or decreased for clarity of discussion. [Brief explanation of the drawings]

[0004] [Figure 1] FIG. 1 is a schematic diagram illustrating an apparatus for aluminothermic reduction of titanium in accordance with various embodiments of the present disclosure. [Figure 2]FIG. 1 is a flow chart illustrating a method of making titanium metal in accordance with various embodiments of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0005] The following disclosure provides many different embodiments or examples for implementing various functions of the provided subject matter. Specific examples of components and arrangements are presented below to simplify the disclosure. These are, of course, examples only and are not intended to be limiting. For example, in the following description, forming a first feature above or on a second feature may include embodiments in which the first and second features are formed in direct contact, and may also include embodiments in which additional features may be formed between the first and second features such that the first and second feature functions do not directly contact. Additionally, the disclosure may repeat reference numerals and / or characters in various examples. This repetition is for purposes of brevity and clarity and does not, in itself, dictate a relationship between the various embodiments and / or configurations discussed.

[0006] Additionally, spatially relative terms such as "beneath," "below," "lower," "above," "upper," etc. may be used herein for ease of description to describe the relationship of one element or feature to another, as illustrated. Spatially relative terms are intended to encompass various orientations of the device during use or operation in addition to the orientation depicted in the figures. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative designations used herein may likewise be interpreted accordingly.

[0007] Generally, the disclosed apparatus and methods can be used to produce titanium metal. In some embodiments, the disclosed apparatus and methods can be used to produce titanium alloys. Examples of alloying elements may include, but are not limited to, aluminum, vanadium, molybdenum, tin, zirconium, and silicon.

[0008] In various embodiments, the disclosed apparatus and methods may be used for the carboaluminothermic reduction of titanium and / or the production of titanium alloys. An embodiment of the disclosed apparatus includes two reaction chambers. In the first reaction chamber, aluminum oxide in a first feed material can be reduced with a carbon reducing agent to form various gaseous aluminum species. The various gaseous aluminum species can then be fed to a second reaction chamber. A second material including solid titanium oxide can also be provided to the second reaction chamber. In the second reaction chamber, the various gaseous aluminum species can be used to reduce the solid titanium oxide and thereby form liquid metallic titanium. In various examples, compounds containing desired alloying elements can be added to the second feed to produce a titanium alloy. In other embodiments, one or more subsequent alloying steps can be performed to create the desired titanium alloy.

[0009] Advantages of the various method and apparatus embodiments discussed below include the ability to produce titanium and titanium alloys without first having to first prepare a metallic aluminum powder reductant. A further advantage is a reduction in the total amount of energy input / increased energy efficiency in the titanium reduction process. This benefit is a direct result of providing heated gaseous aluminum reductant to the second reaction chamber, thereby eliminating the powder aluminum reductant preparation step. A further advantage of the method and apparatus embodiments herein is the ability to produce metallic titanium and titanium alloy products in a continuous process rather than the traditional batch process.

[0010] 1 , an embodiment of an apparatus 100 includes a first reaction chamber 102 and a second reaction chamber 104. The first reaction chamber 102 can include a first feed inlet 106. The first feed inlet 106 can include any suitable feed mechanism, such as, but not limited to, a gravity feed mechanism, a vibratory feed, or a screw drill. A first feed material 107 can be provided to the first reaction chamber 102 via the first feed inlet 106.

[0011] In various embodiments, the first feed material 107 comprises a solid aluminum oxide, such as Al2O3. Additionally, at least one carbon-based reducing agent may be added to the first reaction chamber 102. Upon heating the first feed material 107, one or more gaseous aluminum species 110 may be formed.

[0012] In some embodiments, the carbon-based reducing agent may be a solid, such as coal, for example, anthracite, bituminous coal, subbituminous coal, lignite, or charcoal. The solid carbon-based reducing agent may be added to the solid aluminum oxide or may be added separately to the first reaction chamber 102. In alternative embodiments, the carbon-based reducing agent may be in a gaseous state, such as natural gas, methane, propane, or any other suitable carbon-based gas or gas mixture.

[0013] As discussed in more detail below, a first feed material 107 comprising solid aluminum oxide and a carbon-based reductant may be heated in the first reaction chamber 102 to a temperature high enough to reduce the aluminum oxide to one or more gaseous aluminum species 110. The one or more gaseous aluminum species 110 may comprise, for example, gaseous aluminum (Al(g)) and / or gaseous aluminum oxide (AlO(g)). As shown in FIG. 1 , the top of the first reaction chamber may include a first gas outlet 111. Additionally, as shown in FIG. 1 and discussed in more detail below, a first slug 108 may be formed at the bottom of the first chamber 102. A first tap 112 may be included at the bottom of the first reaction chamber 102 for removing excess first slag 108.

[0014] A conduit 114 connects the first reaction chamber 102 to the second reaction chamber 104. One or more gaseous aluminum species 110 may be passed from the first reaction chamber 102 to the second reaction chamber 104 via the conduit 114. In various embodiments, the conduit 114 may be connected to a manifold 118 located at the bottom of the second reaction chamber 104 to more evenly distribute the one or more gaseous aluminum species 110 within the second reaction chamber.

[0015] The second reaction chamber includes a second feed inlet 116 through which a second feed material 117 may be provided. Similar to the first feed inlet 106, the second feed inlet 116 may include any suitable feed mechanism, such as, but not limited to, a gravity feed mechanism, a vibratory feed, or a screw drill. The second reaction chamber 104 may include a water bath 124 located at the bottom of the second reaction chamber. During operation, a second slug 120 may form at the bottom of the second reaction chamber, as shown in FIG. 1 and discussed in more detail below. As further shown in FIG. 1, a layer of molten titanium or molten titanium alloy 122 may form and sink into the water bath. The molten titanium or molten titanium alloy 122 has a greater density than the second slug 120 and therefore sinks below the second slug 120.

[0016] The second reaction chamber 104 of the apparatus 100 may also include a second faucet 126 configured to remove the molten titanium or molten titanium alloy 122 from the water tank 124 in the second reaction chamber 104. Additionally, the second reaction chamber 104 may include a third faucet 128 configured to remove excess second slag 120 from the second reaction chamber 104. As illustrated in FIG. 1 , the second slag 120 is typically less dense than the molten titanium or molten titanium alloy 122 and floats on top of the molten titanium or molten titanium alloy 122. Additionally, the second reaction chamber 104 may include a second gas outlet 130, typically located at an upper portion of the second reaction chamber 104. The second gas outlet 130 may be configured to remove reactant gas from the second reaction chamber 104.

[0017] 2 is a process flow diagram illustrating a method 200 for carboaluminothermically producing titanium metal or metal alloys, according to an embodiment. Referring to FIG. 2, the method includes step 202 of providing a first feed material 107 and a carbon source material to a first reaction chamber 102. The first feed material 107 includes a solid aluminum oxide, such as Al2O3. In some embodiments, the first feed material 107 includes various non-aluminum oxides and hydroxides, such as oxides and hydroxides of iron and silicon.

[0018] Referring to step 204, the method includes heating the first feed material 107 and the carbon source material to reduce solid aluminum oxide to one or more gaseous aluminum-containing species 110. As discussed above, the one or more gaseous aluminum species 110 may include, for example, gaseous aluminum (Al(g)) and / or gaseous aluminum oxide (AlO(g)).

[0019] During the reduction of solid aluminum oxide, one or more of the following reactions may occur:

[0020] [ka]

[0021] [ka]

[0022] [ka]

[0023] [ka]

[0024] The above reaction may occur at a temperature range of 1000°C to 1800°C, such as 1100°C to 1700°C, for example 1200°C to 1600°C.

[0025] In some embodiments, the first feedstock may contain various aluminum hydroxides in addition to aluminum oxide. Upon reduction of the solid aluminum hydroxide, one or more of the following reactions may occur:

[0026] [ka]

[0027] [ka]

[0028] Additionally, naturally occurring aluminum ores, such as bauxite, may also contain iron oxide, iron hydroxide, and aluminum silicate. When the first feed material 107 is heated, a first slag 108 may form. The first slag tends to flow toward the bottom of the first chamber 102. As discussed above, a first tap 112 may be provided at the bottom of the first chamber 102 to periodically remove excess slag 108.

[0029] The following equation illustrates one reaction that leads to the formation of the first slug 108:

[0030] [ka]

[0031] Upon continued heating, one or more of the following reactions may occur within the slag:

[0032] [ka]

[0033] [ka]

[0034] [ka]

[0035] In some embodiments, one or more flux materials may be added to the first feed material to aid in slag formation, and the one or more flux materials may include, but are not limited to, salts of chlorine and fluorine.

[0036] Referring to step 206, the method includes providing one or more gaseous species 110 comprising aluminum to a second reaction chamber 104 containing a second feed material 117 comprising solid titanium oxide. In various embodiments, the second feed material 117 comprising solid titanium oxide, such as TiO, TiO, TiO, TiO, TiO, TiO, TiO, TiO, TiO, and TiO, may be provided to the second reaction chamber 104 via a second feed inlet 116. Solid titanium oxide may be found in minerals such as, but not limited to, rutile, ilmenite, and leucoxene.

[0037] Referring to step 208, the method includes reducing the solid titanium oxide with one or more gaseous species containing aluminum to form molten metallic titanium or a molten titanium alloy. In this step, the second feed material 117 and the gaseous aluminum species 110 may be heated to a temperature high enough to cause the gaseous aluminum species 110 to reduce the solid titanium oxide, such as a temperature range of 900°C to 1300°C, e.g., 1000°C to 1200°C. In various embodiments, the second feed material 117 may contain compounds of alloying elements used to produce various titanium alloys. As discussed above, alloying elements may include, but are not limited to, aluminum, vanadium, molybdenum, tin, zirconium, and silicon. Additionally, as discussed in more detail below, various flux materials may be added to the first and / or second reaction chambers 102, 104 to promote slag formation. As discussed above, flux materials may include, but are not limited to, salts of chlorine and fluorine.

[0038] During the reduction of solid titanium oxide, one or more of the following reactions may occur:

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] [ka]

[0044] In some embodiments, the second slag further comprises at least one of CaF, CaO, VO, or VO. In some embodiments, the titanium alloy comprises at least one of Al, V, Mo, Sn, Zr, or Si. In other embodiments, the method may include adding one or more alloying elements in a subsequent alloying step, which is performed in a separate alloying step after producing the titanium or titanium alloy in the apparatus discussed above. The one or more alloying elements may include at least one of Al, V, Mo, Sn, Zr, or Si.

[0045] Various embodiments of the present disclosure may provide an apparatus and method for carboaluminothermically producing titanium and / or titanium alloys.

[0046] One embodiment includes a method of making titanium or a titanium alloy, comprising providing a first feed material and a carbon source material to a first reaction chamber, the first feed material comprising solid aluminum oxide. The method further comprises heating the first feed material and the carbon source material to reduce the solid aluminum oxide to one or more gaseous species comprising aluminum. The method further comprises providing one or more gaseous species comprising aluminum to a second reaction chamber, the second reaction chamber containing a second feed material comprising solid titanium oxide. The method further comprises reducing the solid titanium oxide with the one or more gaseous species comprising aluminum to form molten metallic titanium or a molten titanium alloy.

[0047] Another embodiment includes an apparatus for making titanium or a titanium alloy, comprising a first reaction chamber and a second reaction chamber fluidly connected to the first reaction chamber, wherein the first reaction chamber is maintained at a first temperature to form one or more gaseous species comprising aluminum, the one or more gaseous species comprising aluminum may be provided from the first reaction chamber to the second reaction chamber via at least one conduit, and the second reaction chamber is maintained at a second temperature to react the one or more gaseous species comprising aluminum with titanium oxide to form molten metallic titanium or a molten titanium alloy.

[0048] The foregoing outlines features of some embodiments so that those skilled in the art may better understand aspects of the present disclosure. Those skilled in the art will appreciate that this disclosure may readily be used as a basis for designing or modifying other processes and structures to carry out the same purposes and / or obtain the same advantages as the embodiments described herein. Those skilled in the art will also recognize that such equivalent constructions do not depart from the spirit and scope of the present disclosure, and that various changes, substitutions, and alterations can be made without departing from the spirit and scope of the present disclosure. [Explanation of symbols]

[0049] 100: Equipment 102: First reaction chamber 104: Second reaction chamber 106:First supply port 107:First supply material 108: First Slug 110: one or more gaseous aluminum species 111: First gas outlet 112:First faucet 114: Conduit 116:Second supply port 117:Second supply material 118: Manifold 120: Second slug 122: Molten titanium or molten titanium alloy 124: Aquarium 126:Second faucet 128: Third faucet 130: Second gas outlet

Claims

1. 1. A method of making titanium or a titanium alloy, comprising: providing a first feedstock and a carbon source material to a first reaction chamber, the first feedstock comprising solid aluminum oxide; heating the first feedstock and the carbon source material at a temperature in the range of 1000°C to 1800°C to reduce the solid aluminum oxide to one or more gaseous species comprising aluminum; providing the one or more gaseous species comprising aluminum from an outlet in the first reaction chamber to an inlet in a second reaction chamber, the second reaction chamber containing a second feed material comprising solid titanium oxide, the first reaction chamber being fluidly connected to the second reaction chamber, and the one or more gaseous species comprising aluminum being provided at a temperature in the range of 900°C to 1300°C; reducing said solid titanium oxide with one or more gaseous species including said aluminum at a temperature range of 900°C to 1300°C to form molten titanium metal or a molten titanium alloy.

2. 10. The method of claim 1, further comprising the step of removing gaseous reaction products from the second reaction chamber through a gas outlet.

3. 10. The method of claim 1, further comprising the step of removing a first slag from the first reaction chamber through a first tap.

4. 10. The method of claim 1, further comprising the step of removing liquid titanium metal from the second reaction chamber through a second tap.

5. 5. The method of claim 4, further comprising forming a second slug in said second reaction chamber, said second slug being positioned above said liquid titanium metal.

6. 6. The method of claim 5, further comprising the step of removing the second slag from the second reaction chamber through a third tap.

7. The first slag is liquid Al ２ O ３ The method of claim 1 , comprising:

8. The method of claim 7 , wherein the first slag further comprises at least one of silicon oxide or iron oxide.

9. The second slag is TiO ２ The method of claim 5 , comprising:

10. The second slag contains CaF, CaO, V ２ O ３ , or V ２ O ５ The method of claim 9 , further comprising at least one of:

11. The method of claim 1 , wherein the titanium alloy comprises at least one of Al, V, Mo, Sn, Zr, or Si.

12. The method of claim 1 further comprising adding one or more alloying elements in a subsequent alloying stage.

13. 13. The method of claim 12, wherein the one or more alloying elements include at least one of Al, V, Mo, Sn, Zr, or Si.

14. 1. An apparatus for producing titanium or titanium alloys, comprising: a first reaction chamber having an outlet; a second reaction chamber having an inlet fluidly connected to the outlet of the first reaction chamber; the first reaction chamber is maintained at a first temperature to form one or more gaseous species comprising aluminum, the first temperature being in the range of 1000°C to 1800°C; the one or more gaseous species containing aluminum are provided from the first reaction chamber to the second reaction chamber via at least one conduit at a temperature ranging from 900°C to 1300°C; the second reaction chamber is maintained at a second temperature in the temperature range of 900°C to 1300°C to react the one or more gaseous species containing aluminum with titanium oxide to form molten titanium metal or a molten titanium alloy.

15. 15. The apparatus of claim 14, further comprising a first faucet configured to remove a first slag from the first reaction chamber.

16. 15. The apparatus of claim 14, further comprising a water bath located at the bottom of the second reaction chamber.

17. 17. The apparatus of claim 16, further comprising a second faucet configured to drain the aquarium.

18. 18. The apparatus of claim 17, further comprising a third faucet configured to remove a second slag from the second reaction chamber.

19. 15. The apparatus of claim 14, further comprising a gas outlet in the second reaction chamber configured to release gas from the second reaction chamber.

20. 15. The apparatus of claim 14, further comprising a manifold configured to provide the one or more gaseous species comprising aluminum to the second reaction chamber.

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