A method for producing metallic titanium powder using titanium-containing oxide

Abstract

The present application relates to a kind of method for preparing metal titanium powder using titanium-containing oxide, belong to metal resource utilization technical field.The present application will flux, titanium-containing oxide and aluminum be added to reaction vessel, and carry out self-propagating reaction under oxygen-free condition, make the material in reaction vessel heat to the melting point of flux, obtain titanium-aluminum alloy and the flux rich in alumina;Under vacuum or protective gas atmosphere, dry to remove water from chloride molten salt electrolyte to obtain anhydrous molten salt electrolyte, the titanium-aluminum alloy of step (1) is placed in graphite basket, with anhydrous molten salt electrolyte as electrolyte, graphite basket as anode, metal or alloy as cathode, to form molten salt electrolysis system;In protective atmosphere, anhydrous molten salt electrolyte is uniformly heated to molten state and kept for 0.5-1h, graphite basket with titanium-aluminum alloy and cathode are completely immersed into molten state electrolyte, the current density of cathode and anode is controlled, and constant current electrolysis is carried out;The cathode product is removed, and washed by deionized water to remove residual electrolyte to obtain metal titanium powder.

Description

Technical Field

[0001] This invention relates to a method for preparing metallic titanium powder using titanium oxide, belonging to the field of metal resource utilization technology. Background Technology

[0002] Titanium is a high-performance, widely used, and rapidly developing metal. It possesses excellent properties such as high specific strength, high melting point, low density, good corrosion resistance, and good biocompatibility, making it widely used in aerospace engineering, marine engineering, petrochemicals, biomedicine, and everyday household appliances. Currently, the main method for titanium metal preparation is the magnesiothermal reduction process (The Kroll process). However, the current magnesiothermal reduction process is intermittent and energy-intensive, resulting in high output and low cost. This has led to the expectation of efficient, continuous, low-energy-consumption, and environmentally friendly alternative processes. Reported methods include Hunter, Armstrong, TIRO, CSIR, PRP, MER, HAMR, DDR, SHS, HDH, two-stage aluminothermic reduction, FFC, OS, and USTB.

[0003] Currently, methods such as Armstrong, PRP, and two-stage aluminothermic reduction are processes for producing titanium using metallothermic reduction. These methods primarily use titanium dioxide or titanium-containing compounds as the titanium source for thermal reduction, employing reducing agents such as sodium, calcium, and aluminum. This results in high raw material costs, non-recyclable waste generated during production, and high impurity content in the produced titanium, making it impossible to obtain high-purity titanium. Methods such as FFC, OS, and USTB are processes for producing titanium using molten salt electrolysis. These primarily use titanium dioxide as the titanium source for molten salt electrolysis deoxidation. However, due to the low conductivity of titanium dioxide, the current efficiency during electrolysis is low, and the electrolysis time is long, hindering large-scale industrialization. Summary of the Invention

[0004] To address the problems of high production cost, high impurity content, and long processing time in existing titanium extraction technologies, this invention proposes a method for preparing metallic titanium powder using titanium-containing oxides. Specifically, a self-propagating reaction is used to reduce the titanium-containing oxides, removing most of the oxygen and impurities to obtain a titanium-aluminum alloy. This alloy is then subjected to molten salt electrolysis using a chloride molten salt. Ti is deposited separately at the cathode, while aluminum remains in the graphite basket at the anode, achieving the purpose of refining and separating to obtain titanium powder. This invention can produce metallic titanium powder with high purity.

[0005] A method for preparing metallic titanium powder using titanium oxides, comprising the following steps:

[0006] (1) Add flux, titanium oxide and aluminum into a reaction vessel and carry out a self-propagating reaction under oxygen-free conditions to raise the temperature of the material in the reaction vessel above the melting point of the flux to obtain titanium-aluminum alloy and flux rich in alumina; the flux rich in alumina can be used for electrolytic aluminum recycling.

[0007] (2) Under vacuum or protective gas atmosphere, the chloride molten salt electrolyte is dried to remove moisture to obtain anhydrous molten salt electrolyte. The titanium-aluminum alloy of step (1) is placed in a graphite basket, with anhydrous molten salt electrolyte as electrolyte, graphite basket as anode, and metal or alloy as cathode to form a molten salt electrolysis system.

[0008] (3) Under a protective atmosphere, the anhydrous molten salt electrolyte is heated to the molten state at a constant rate and kept at the temperature for 0.5 to 1 hour. The graphite basket containing titanium-aluminum alloy and the cathode are completely immersed in the molten electrolyte. The current density of the cathode and the anode is controlled to carry out constant current electrolysis.

[0009] (4) The cathode product is removed and washed with deionized water to remove the residual electrolyte and obtain metallic titanium powder.

[0010] Preferably, the flux in step (1) is a mixture of NaF and AlF3, and the molar ratio of NaF to AlF3 is 3:1 to 2:1.

[0011] Preferably, in step (1), the mass ratio of aluminum to titanium oxide is 3:2 to 2:1, and the mass ratio of titanium oxide to flux is 1:2 to 2:5.

[0012] Preferably, the oxygen-free condition in step (1) is a protective atmosphere or a closed environment that isolates the air.

[0013] Preferably, the starting temperature of the self-propagating reaction in step (1) is 660–1050 °C;

[0014] Preferably, the cathode in step (2) is made of titanium, tungsten, molybdenum, nickel, Hastelloy, or stainless steel.

[0015] Preferably, the chloride molten salt electrolyte in step (3) is one or more of sodium chloride, potassium chloride, magnesium chloride, and lithium chloride.

[0016] Preferably, the anode current density in step (3) is 0.2–0.4 A / cm². 2 The cathode current density is 0.2–1.2 A / cm². 2 .

[0017] Preferably, the protective atmosphere is a nitrogen atmosphere or an inert gas atmosphere.

[0018] The self-propagating reaction of this invention:

[0019] 3TiO2 + 4Al = 2Al2O3 + 3Ti

[0020] Ti + 3TiO₂ = 2Ti₂O₃

[0021] 6Ti₂O₃ + 4Al = 12TiO + 2Al₂O₃

[0022] 6TiO + 4Al = 6Ti + 2Al₂O₃

[0023] Molten salt electrolysis:

[0024] Overall reaction: Ti 电 = 解 Ti

[0025] Anode reaction: Ti - 2e － =Ti 2+

[0026] Cathode reaction: Ti 2+ +2e － =Ti

[0027] This invention employs a self-propagating reaction to reduce titanium-containing oxides, thereby removing most of their oxygen and impurities to obtain a titanium-aluminum alloy. The aluminum-titanium alloy is then placed in a chloride molten salt for molten salt electrolysis, where Ti is deposited separately at the cathode while aluminum remains in the graphite basket at the anode for refining and separation to produce high-purity titanium powder.

[0028] The beneficial effects of this invention are:

[0029] (1) This invention uses a self-propagating reaction to reduce titanium oxides. The self-propagating exothermic reaction can quickly increase the furnace temperature to promote the reaction and achieve good slag-metal separation to obtain titanium-aluminum alloy and flux rich in alumina.

[0030] (2) The self-propagating reaction of the present invention occurs in a flux that easily dissolves alumina. The alumina produced is easily dissolved in the flux to form a slag phase that floats on the upper layer. The resulting upper layer material is rich in alumina and can be used for the recycling of electrolytic aluminum materials.

[0031] (3) The present invention uses chloride molten salt electrolysis of titanium-aluminum alloy to selectively separate titanium, thereby achieving a refining effect and obtaining high-quality metallic titanium.

[0032] (4) The present invention is simple to operate, fast to react, low in energy consumption, pollution-free and waste-free, and can save costs. The resulting titanium powder has low oxygen content and is easy to collect. Attached Figure Description

[0033] Figure 1 A process flow diagram for preparing metallic titanium powder using titanium oxides;

[0034] Figure 2The XRD pattern of the titanium-aluminum alloy, the product of the self-propagating reaction in Example 1;

[0035] Figure 3 The XRD pattern of alumina-rich slag from Example 1 is shown below.

[0036] Figure 4 The XRD pattern of the titanium-aluminum alloy cathode product separated in Example 1 is shown. Detailed Implementation

[0037] The present invention will be further described in detail below with reference to specific embodiments, but the scope of protection of the present invention is not limited to the content described.

[0038] Example 1: A method for preparing metallic titanium powder using titanium oxide (see Example 2) Figure 1 The specific steps are as follows:

[0039] (1) Add flux (NaF and AlF3), titanium dioxide and aluminum to a reaction vessel (graphite crucible), heat to 800°C under oxygen-free (argon atmosphere) conditions to carry out a self-propagating reaction, so that the material in the reaction vessel is heated to above the melting point of flux (NaF and AlF3) (1050°C) and held for 30 minutes, and then cooled to room temperature with the furnace to obtain a lower layer of titanium-aluminum alloy and an upper layer of flux rich in alumina. The upper layer of flux rich in alumina is recycled as raw material for electrolytic aluminum; the flux rich in alumina can be used for electrolytic aluminum recycling; wherein the molar ratio of NaF and AlF3 in the flux is 3:1, the mass ratio of aluminum and titanium dioxide is 3:2, and the mass ratio of titanium dioxide to flux is 1:2;

[0040] (2) Under vacuum conditions, the chloride molten salt electrolyte (sodium chloride and potassium chloride mixed evenly in a mass ratio of 1:1) is dried at 100°C to remove moisture and obtain anhydrous molten salt electrolyte. The titanium-aluminum alloy from step (1) is placed in a graphite basket, with anhydrous molten salt electrolyte as the electrolyte, graphite basket as the anode, and metallic titanium as the cathode to form a molten salt electrolysis system.

[0041] (3) Under an argon atmosphere, the anhydrous molten salt electrolyte is heated at a constant rate to the molten state (800℃) and held at that temperature for 30 minutes. The graphite basket containing the titanium-aluminum alloy and the cathode (metallic titanium) are then completely immersed in the molten electrolyte, and the anode current density is controlled to be 1.2 A / cm². 2 The cathode current density is 0.2 A / cm². 2 Electrolysis was performed at constant current for 3 hours, followed by uniform cooling to room temperature.

[0042] (4) Remove the cathode product and wash it with deionized water to remove the residual electrolyte to obtain metallic titanium powder separated from the anode titanium-aluminum alloy.

[0043] The XRD pattern of the titanium-aluminum alloy obtained by the self-propagating reaction in this embodiment is shown below. Figure 2 The XRD pattern of the alumina-rich slag is shown in [reference needed]. Figure 3 XRD patterns of cathode products are shown below. Figure 4 ,from Figure 2 and Figure 3 It can be seen that the self-propagating reaction reduces titanium dioxide slag and achieves significant gold separation; from Figure 4 It can be seen that the cathode products contain no impurities such as metallic aluminum other than electrolyte and metallic titanium phase, indicating that the titanium-aluminum separation effect is relatively significant.

[0044] The purity of the titanium metal produced in this embodiment is 99.86%. This method reduces titanium-containing oxides through a self-propagating reaction, separates aluminum and titanium by molten salt electrolysis, and removes the electrolyte by washing the obtained cathode product with water to obtain a relatively pure titanium metal phase.

[0045] Example 2: A method for preparing metallic titanium powder using titanium oxide (see Example 2) Figure 1 The specific steps are as follows:

[0046] (1) Add flux (NaF and AlF3), high-titanium slag and aluminum into a reaction vessel (graphite crucible), and heat to 660°C under oxygen-free (argon atmosphere) conditions to carry out a self-propagating reaction, so that the material in the reaction vessel is heated to above the melting point of flux (NaF and AlF3) (950°C) and held for 40 min. Cool to room temperature with the furnace to obtain a lower layer of titanium-aluminum alloy and an upper layer of flux rich in alumina. The upper layer of flux rich in alumina is recycled as raw material for electrolytic aluminum. The flux rich in alumina can be used for electrolytic aluminum recycling. The molar ratio of NaF to AlF3 in the flux is 2.8:1, the mass ratio of aluminum to high-titanium slag is 7:4, and the mass ratio of high-titanium slag to flux is 1:2.

[0047] (2) Under vacuum conditions, the chloride molten salt electrolyte (sodium chloride and potassium chloride are mixed evenly in a mass ratio of 2:1) is dried at 80°C to remove moisture and obtain anhydrous molten salt electrolyte. The titanium-aluminum alloy from step (1) is placed in a graphite basket, with anhydrous molten salt electrolyte as the electrolyte, graphite basket as the anode, and tungsten metal as the cathode to form a molten salt electrolysis system.

[0048] (3) Under an argon atmosphere, the anhydrous molten salt electrolyte is heated at a constant rate to the molten state (750℃) and held at that temperature for 40 minutes. The graphite basket containing the titanium-aluminum alloy and the cathode (metallic titanium) are then completely immersed in the molten electrolyte, and the anode current density is controlled to be 1.0 A / cm². 2 The cathode current density is 0.3 A / cm². 2 The mixture was subjected to constant current electrolysis for 3.5 hours and then cooled to room temperature at a uniform rate.

[0049] (4) Remove the cathode product and wash it with deionized water to remove the residual electrolyte to obtain metallic titanium powder separated from the anode titanium-aluminum alloy.

[0050] The purity of the titanium metal produced in this embodiment is 98.08%. This method reduces titanium-containing oxides through a self-propagating reaction, separates aluminum and titanium by molten salt electrolysis, and removes the electrolyte by washing the obtained cathode product with water to obtain a relatively pure titanium metal phase.

[0051] Example 3: A method for preparing metallic titanium powder using titanium oxide (see Example 4) Figure 1 The specific steps are as follows:

[0052] (1) Add flux (NaF and AlF3), titanium dioxide and aluminum to a reaction vessel (graphite crucible), heat to 900°C under oxygen-free (argon atmosphere) conditions to carry out a self-propagating reaction, so that the material in the reaction vessel is heated to above the melting point of flux (NaF and AlF3) (1150°C) and held for 35 minutes, and then cooled to room temperature with the furnace to obtain a lower layer of titanium-aluminum alloy and an upper layer of flux rich in alumina. The upper layer of flux rich in alumina is recycled as raw material for electrolytic aluminum; the flux rich in alumina can be used for electrolytic aluminum recycling; wherein the molar ratio of NaF to AlF3 in the flux is 2.6:1, the mass ratio of aluminum to titanium dioxide is 2:1, and the mass ratio of titanium dioxide to flux is 1:2;

[0053] (2) Under vacuum conditions, the chloride molten salt electrolyte (sodium chloride and magnesium chloride are mixed evenly in a mass ratio of 1:1) is dried at 90°C to remove moisture and obtain anhydrous molten salt electrolyte. The titanium-aluminum alloy in step (1) is placed in a graphite basket, with anhydrous molten salt electrolyte as the electrolyte, graphite basket as the anode, and metal molybdenum as the cathode to form a molten salt electrolysis system.

[0054] (3) Under an argon atmosphere, the anhydrous molten salt electrolyte is heated at a constant rate to the molten state (850℃) and held at that temperature for 50 min. The graphite basket containing titanium-aluminum alloy and the cathode (metallic titanium) are then completely immersed in the molten electrolyte, and the anode current density is controlled to be 0.8 A / cm. 2 The cathode current density is 0.2 A / cm². 2 Electrolysis was performed at constant current for 3 hours, followed by uniform cooling to room temperature.

[0055] (4) Remove the cathode product and wash it with deionized water to remove the residual electrolyte to obtain metallic titanium powder separated from the anode titanium-aluminum alloy.

[0056] The purity of the titanium metal produced in this embodiment is 98.57%. This method reduces titanium-containing oxides through a self-propagating reaction, separates aluminum and titanium by molten salt electrolysis, and removes the electrolyte by washing the obtained cathode product with water to obtain a relatively pure titanium metal phase.

[0057] Example 4: A method for preparing metallic titanium powder using titanium oxide (see Example 4) Figure 1 The specific steps are as follows:

[0058] (1) Add flux (NaF and AlF3), high-titanium slag and aluminum into a reaction vessel (graphite crucible), and heat to 950°C under oxygen-free (argon atmosphere) conditions to carry out a self-propagating reaction, so that the material in the reaction vessel is heated to above the melting point of flux (NaF and AlF3) (1200°C) and held for 30 minutes. Cool to room temperature with the furnace to obtain a lower layer of titanium-aluminum alloy and an upper layer of flux rich in alumina. The upper layer of flux rich in alumina is recycled as raw material for electrolytic aluminum. The flux rich in alumina can be used for electrolytic aluminum recycling. The molar ratio of NaF to AlF3 in the flux is 2.4:1, the mass ratio of aluminum to high-titanium slag is 3:2, and the mass ratio of high-titanium slag to flux is 4:9.

[0059] (2) Under vacuum conditions, the chloride molten salt electrolyte (sodium chloride and lithium chloride are mixed evenly in a mass ratio of 1:1) is dried at 100°C to remove moisture and obtain anhydrous molten salt electrolyte. The titanium-aluminum alloy from step (1) is placed in a graphite basket, with anhydrous molten salt electrolyte as the electrolyte, graphite basket as the anode, and stainless steel as the cathode to form a molten salt electrolysis system.

[0060] (3) Under an argon atmosphere, the anhydrous molten salt electrolyte is heated at a constant rate to the molten state (800℃) and held at that temperature for 35 minutes. The graphite basket containing titanium-aluminum alloy and the cathode (metallic titanium) are then completely immersed in the molten electrolyte, and the anode current density is controlled to be 1.2 A / cm². 2 The cathode current density is 0.4 A / cm². 2 Electrolysis was performed at constant current for 3 hours, followed by uniform cooling to room temperature.

[0061] (4) Remove the cathode product and wash it with deionized water to remove the residual electrolyte to obtain metallic titanium powder separated from the anode titanium-aluminum alloy.

[0062] The purity of the titanium metal produced in this embodiment is 99.01%. This method reduces titanium-containing oxides through a self-propagating reaction, separates aluminum and titanium by molten salt electrolysis, and removes the electrolyte by washing the obtained cathode product with water to obtain a relatively pure titanium metal phase.

[0063] Example 5: A method for preparing metallic titanium powder using titanium oxide (see Example 5) Figure 1 The specific steps are as follows:

[0064] (1) Add flux (NaF and AlF3), titanium dioxide and aluminum to a reaction vessel (graphite crucible), heat to 1000℃ under oxygen-free (argon atmosphere) conditions to carry out a self-propagating reaction, so that the material in the reaction vessel is heated to above the melting point of flux (NaF and AlF3) (1200℃) and held for 30 minutes, and then cooled to room temperature with the furnace to obtain a lower layer of titanium-aluminum alloy and an upper layer of flux rich in alumina. The upper layer of flux rich in alumina is recycled as raw material for electrolytic aluminum; the flux rich in alumina can be used for electrolytic aluminum recycling; wherein the molar ratio of NaF and AlF3 in the flux is 2.2:1, the mass ratio of aluminum to titanium dioxide is 3:2, and the mass ratio of titanium dioxide to flux is 2:5;

[0065] (2) Under vacuum conditions, the chloride molten salt electrolyte (magnesium chloride) is dried at 95°C to remove moisture and obtain anhydrous molten salt electrolyte. The titanium-aluminum alloy from step (1) is placed in a graphite basket, with anhydrous molten salt electrolyte as the electrolyte, graphite basket as the anode, and metallic nickel as the cathode to form a molten salt electrolysis system.

[0066] (3) Under an argon atmosphere, the anhydrous molten salt electrolyte is heated at a constant rate to the molten state (750℃) and held at that temperature for 35 minutes. The graphite basket containing titanium-aluminum alloy and the cathode (metallic titanium) are then completely immersed in the molten electrolyte, and the anode current density is controlled to be 1.2 A / cm². 2 The cathode current density is 0.2 A / cm². 2 Electrolysis was performed at constant current for 3 hours, followed by uniform cooling to room temperature.

[0067] (4) Remove the cathode product and wash it with deionized water to remove the residual electrolyte to obtain metallic titanium powder separated from the anode titanium-aluminum alloy.

[0068] The purity of the titanium metal produced in this embodiment is 99.35%. This method reduces titanium-containing oxides through a self-propagating reaction, separates aluminum and titanium by molten salt electrolysis, and removes the electrolyte by washing the obtained cathode product with water to obtain a relatively pure titanium metal phase.

[0069] Example 6: A method for preparing metallic titanium powder using titanium oxide (see Example 6) Figure 1 The specific steps are as follows:

[0070] (1) Add flux (NaF and AlF3), high-titanium slag and aluminum into a reaction vessel (graphite crucible), and heat to 1050℃ under oxygen-free (argon atmosphere) conditions to carry out a self-propagating reaction, so that the material in the reaction vessel is heated to above the melting point of flux (NaF and AlF3) (1200℃) and held for 30 minutes. Cool to room temperature with the furnace to obtain a lower layer of titanium-aluminum alloy and an upper layer of flux rich in alumina. The upper layer of flux rich in alumina is recycled as raw material for electrolytic aluminum. The flux rich in alumina can be used for electrolytic aluminum recycling. The molar ratio of NaF to AlF3 in the flux is 2:1, the mass ratio of aluminum to high-titanium slag is 2:1, and the mass ratio of high-titanium slag to flux is 2:5.

[0071] (2) Under vacuum conditions, the chloride molten salt electrolyte (lithium chloride) is dried at 100°C to remove moisture and obtain anhydrous molten salt electrolyte. The titanium-aluminum alloy from step (1) is placed in a graphite basket, with the anhydrous molten salt electrolyte as the electrolyte, the graphite basket as the anode, and Hastelloy as the cathode to form a molten salt electrolysis system.

[0072] (3) Under an argon atmosphere, the anhydrous molten salt electrolyte is heated at a constant rate to the molten state (850℃) and held at that temperature for 35 minutes. The graphite basket containing titanium-aluminum alloy and the cathode (metallic titanium) are then completely immersed in the molten electrolyte, and the anode current density is controlled to be 0.6 A / cm. 2 The cathode current density is 0.2 A / cm². 2 Electrolysis was performed at constant current for 3 hours, followed by uniform cooling to room temperature.

[0073] (4) Remove the cathode product and wash it with deionized water to remove the residual electrolyte to obtain metallic titanium powder separated from the anode titanium-aluminum alloy.

[0074] The purity of the titanium metal produced in this embodiment is 99.28%. This method reduces titanium-containing oxides through a self-propagating reaction, separates aluminum and titanium by molten salt electrolysis, and removes the electrolyte by washing the obtained cathode product with water to obtain a relatively pure titanium metal phase.

[0075] The specific embodiments of the present invention have been described in detail above. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention.

Claims

1. A method for preparing metallic titanium powder using titanium oxide, characterized in that, The specific steps are as follows: (1) Add flux, titanium dioxide and aluminum to a graphite crucible, heat to 800°C under argon atmosphere to carry out self-propagating reaction, so that the material in the graphite crucible is heated to above the melting point of flux, that is, the temperature reaches 1050°C and is held for 30 minutes, and then cooled to room temperature with the furnace to obtain a lower layer of titanium-aluminum alloy and an upper layer of flux rich in alumina. The upper layer of flux rich in alumina is recycled as raw material for electrolytic aluminum; the flux rich in alumina can be used for electrolytic aluminum recycling; wherein the flux is NaF and AlF3, the molar ratio of NaF and AlF3 in the flux is 3:1, the mass ratio of aluminum and titanium dioxide is 3:2, and the mass ratio of titanium dioxide to flux is 1:2; (2) Under vacuum conditions, the chloride molten salt electrolyte is dried at 100°C to remove moisture and obtain anhydrous molten salt electrolyte. The titanium-aluminum alloy from step (1) is placed in a graphite basket, with the anhydrous molten salt electrolyte as the electrolyte, the graphite basket as the anode, and metallic titanium as the cathode to form a molten salt electrolysis system. The chloride molten salt electrolyte is a mixture of sodium chloride and potassium chloride mixed evenly in a mass ratio of 1:

1. (3) Under an argon atmosphere, the anhydrous molten salt electrolyte is heated at a constant rate to the molten state, i.e., the temperature reaches 800℃ and is held at that temperature for 30 minutes. The graphite basket containing the titanium-aluminum alloy and the cathode are completely immersed in the molten electrolyte, and the anode current density is controlled to be 1.2 A / cm. 2 The cathode current density is 0.2 A / cm². 2 The cathode is titanium metal and subjected to constant current electrolysis for 3 hours, followed by uniform cooling to room temperature. (4) Remove the cathode product and wash it with deionized water to remove the residual electrolyte and obtain metallic titanium powder separated from the anode titanium-aluminum alloy.

2. A method for preparing metallic titanium powder using titanium oxide, characterized in that, The specific steps are as follows: (1) Add flux, high-titanium slag and aluminum to a graphite crucible, heat to 660°C under argon atmosphere to carry out self-propagating reaction, so that the material in the graphite crucible is heated to above the melting point of flux, that is, the temperature reaches 950°C and is held for 40 minutes. Cool to room temperature with the furnace to obtain a lower layer of titanium-aluminum alloy and an upper layer of flux rich in alumina. The upper layer of flux rich in alumina is recycled as raw material for electrolytic aluminum. The flux rich in alumina can be used for electrolytic aluminum recycling. The flux is NaF and AlF3, the molar ratio of NaF to AlF3 in the flux is 2.8:1, the mass ratio of aluminum to high-titanium slag is 7:4, and the mass ratio of high-titanium slag to flux is 1:

2. (2) Under vacuum conditions, the chloride molten salt electrolyte is dried at 80°C to remove moisture and obtain anhydrous molten salt electrolyte. The titanium-aluminum alloy from step (1) is placed in a graphite basket, with the anhydrous molten salt electrolyte as the electrolyte, the graphite basket as the anode, and tungsten metal as the cathode to form a molten salt electrolysis system. The chloride molten salt electrolyte is a uniform mixture of sodium chloride and potassium chloride in a mass ratio of 2:

1. (3) Under an argon atmosphere, the anhydrous molten salt electrolyte is heated at a constant rate to the molten state, i.e., the temperature reaches 750℃ and is held at that temperature for 40 minutes. The graphite basket containing the titanium-aluminum alloy and the cathode are completely immersed in the molten electrolyte, and the anode current density is controlled to be 1.0 A / cm. 2 The cathode current density is 0.3 A / cm². 2 The cathode is made of titanium and subjected to constant current electrolysis for 3.5 hours, followed by uniform cooling to room temperature. (4) Remove the cathode product and wash it with deionized water to remove the residual electrolyte and obtain metallic titanium powder separated from the anode titanium-aluminum alloy.

3. A method for preparing metallic titanium powder using titanium oxide, characterized in that: The specific steps are as follows: (1) Add flux, titanium dioxide and aluminum to a graphite crucible, heat to 900°C under argon atmosphere to carry out self-propagating reaction, so that the material in the graphite crucible is heated to above the melting point of flux, that is, the temperature reaches 1150°C and is held for 35 minutes, and then cooled to room temperature with the furnace to obtain a lower layer of titanium-aluminum alloy and an upper layer of flux rich in alumina. The upper layer of flux rich in alumina is recycled as raw material for electrolytic aluminum; the flux rich in alumina can be used for electrolytic aluminum recycling; wherein the flux is NaF and AlF3, the molar ratio of NaF and AlF3 in the flux is 2.6:1, the mass ratio of aluminum and titanium dioxide is 2:1, and the mass ratio of titanium dioxide to flux is 1:2; (2) Under vacuum conditions, the chloride molten salt electrolyte is dried at 90°C to remove moisture and obtain anhydrous molten salt electrolyte. The titanium-aluminum alloy from step (1) is placed in a graphite basket, with the anhydrous molten salt electrolyte as the electrolyte, the graphite basket as the anode, and the molybdenum metal as the cathode to form a molten salt electrolysis system. The chloride molten salt electrolyte is a uniform mixture of sodium chloride and magnesium chloride in a mass ratio of 1:

1. (3) Under an argon atmosphere, the anhydrous molten salt electrolyte is heated at a constant rate to the molten state, i.e., the temperature reaches 850℃ and is held at that temperature for 50 minutes. The graphite basket containing the titanium-aluminum alloy and the cathode are completely immersed in the molten electrolyte, and the anode current density is controlled to be 0.8A / cm. 2 The cathode current density is 0.2 A / cm². 2 The cathode is titanium metal and subjected to constant current electrolysis for 3 hours, followed by uniform cooling to room temperature. (4) Remove the cathode product and wash it with deionized water to remove the residual electrolyte and obtain metallic titanium powder separated from the anode titanium-aluminum alloy.

4. A method for preparing metallic titanium powder using titanium oxide, characterized in that, The specific steps are as follows: (1) Add flux, high-titanium slag and aluminum to a graphite crucible, and heat to 950°C under an argon atmosphere to carry out a self-propagating reaction, so that the material in the graphite crucible is heated to above the melting point of the flux, that is, the temperature reaches 1200°C and is held for 30 minutes. Cool to room temperature with the furnace to obtain a lower layer of titanium-aluminum alloy and an upper layer of flux rich in alumina. The upper layer of flux rich in alumina is recycled as raw material for electrolytic aluminum. The flux rich in alumina can be used for electrolytic aluminum recycling. The flux is NaF and AlF3, the molar ratio of NaF to AlF3 in the flux is 2.4:1, the mass ratio of aluminum to high-titanium slag is 3:2, and the mass ratio of high-titanium slag to flux is 4:

9. (2) Under vacuum conditions, the chloride molten salt electrolyte is dried at 100°C to remove moisture and obtain anhydrous molten salt electrolyte. The titanium-aluminum alloy from step (1) is placed in a graphite basket, with the anhydrous molten salt electrolyte as the electrolyte, the graphite basket as the anode, and stainless steel as the cathode to form a molten salt electrolysis system. The chloride molten salt electrolyte is a uniform mixture of sodium chloride and lithium chloride in a mass ratio of 1:

1. (3) Under an argon atmosphere, the anhydrous molten salt electrolyte is heated at a constant rate to the molten state, i.e., the temperature reaches 800℃ and is held at that temperature for 35 minutes. The graphite basket containing the titanium-aluminum alloy and the cathode are completely immersed in the molten electrolyte, and the anode current density is controlled to be 1.2 A / cm. 2 The cathode current density is 0.4 A / cm². 2 The cathode is titanium metal and subjected to constant current electrolysis for 3 hours, followed by uniform cooling to room temperature. (4) Remove the cathode product and wash it with deionized water to remove the residual electrolyte and obtain metallic titanium powder separated from the anode titanium-aluminum alloy.

5. A method for preparing metallic titanium powder using titanium oxide, characterized in that, The specific steps are as follows: (1) Add flux, titanium dioxide and aluminum to a graphite crucible, heat to 1000℃ under argon atmosphere to carry out self-propagating reaction, so that the material in the graphite crucible is heated to above the melting point of flux, that is, the temperature reaches 1200℃ and is held for 30min. Cool to room temperature with the furnace to obtain a lower layer of titanium-aluminum alloy and an upper layer of flux rich in alumina. The upper layer of flux rich in alumina is recycled as raw material for electrolytic aluminum. The flux rich in alumina can be used for electrolytic aluminum recycling. The flux is NaF and AlF3, the molar ratio of NaF to AlF3 in the flux is 2.2:1, the mass ratio of aluminum to titanium dioxide is 3:2, and the mass ratio of titanium dioxide to flux is 2:

5. (2) Under vacuum conditions, the chloride molten salt electrolyte is dried at 95°C to remove moisture and obtain anhydrous molten salt electrolyte. The titanium-aluminum alloy from step (1) is placed in a graphite basket, with the anhydrous molten salt electrolyte as the electrolyte, the graphite basket as the anode, and metallic nickel as the cathode to form a molten salt electrolysis system; the chloride molten salt electrolyte is magnesium chloride. (3) Under an argon atmosphere, the anhydrous molten salt electrolyte is heated at a constant rate to the molten state, i.e., the temperature reaches 750℃ and is held at that temperature for 35 minutes. The graphite basket containing the titanium-aluminum alloy and the cathode are completely immersed in the molten electrolyte, and the anode current density is controlled to be 1.2 A / cm. 2 The cathode current density is 0.2 A / cm². 2 The cathode is titanium metal and subjected to constant current electrolysis for 3 hours, followed by uniform cooling to room temperature. (4) Remove the cathode product and wash it with deionized water to remove the residual electrolyte and obtain metallic titanium powder separated from the anode titanium-aluminum alloy.

6. A method for preparing metallic titanium powder using titanium oxide, characterized in that, The specific steps are as follows: (1) Add flux, high-titanium slag and aluminum to a graphite crucible, heat to 1050℃ under argon atmosphere to carry out self-propagating reaction, so that the material in the graphite crucible is heated to above the melting point of flux, that is, the temperature reaches 1200℃ and is held for 30min. Cool to room temperature with the furnace to obtain a lower layer of titanium-aluminum alloy and an upper layer of flux rich in alumina. The upper layer of flux rich in alumina is recycled as raw material for electrolytic aluminum. The flux rich in alumina can be used for electrolytic aluminum recycling. The flux is NaF and AlF3, the molar ratio of NaF and AlF3 in the flux is 2:1, the mass ratio of aluminum and high-titanium slag is 2:1, and the mass ratio of high-titanium slag to flux is 2:

5. (2) Under vacuum conditions, the chloride molten salt electrolyte is dried at 100°C to remove moisture and obtain anhydrous molten salt electrolyte. The titanium-aluminum alloy from step (1) is placed in a graphite basket, with the anhydrous molten salt electrolyte as the electrolyte, the graphite basket as the anode, and Hastelloy as the cathode to form a molten salt electrolysis system; the chloride molten salt electrolyte is lithium chloride. (3) Under an argon atmosphere, the anhydrous molten salt electrolyte is heated at a constant rate to the molten state, i.e., the temperature reaches 850℃ and is held at that temperature for 35 minutes. The graphite basket containing the titanium-aluminum alloy and the cathode are completely immersed in the molten electrolyte, and the anode current density is controlled to be 0.6A / cm. 2 The cathode current density is 0.2 A / cm². 2 The cathode is titanium metal and subjected to constant current electrolysis for 3 hours, followed by uniform cooling to room temperature. (4) Remove the cathode product and wash it with deionized water to remove the residual electrolyte and obtain metallic titanium powder separated from the anode titanium-aluminum alloy.

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