METHOD OF CONTROLLABLY REDUCING OXYGEN CONTENT, AND PREPARING TITANIUM METAL POWDER AND Ti6A14V ALLOY POWDER

Abstract

Provided are a method of controllably reducing an oxygen content, a method of preparing titanium metal powder, and a method of preparing Ti6Al4V alloy powder. The method of controllably reducing an oxygen content can accurately control the removal amount of oxygen in titanium oxide or vanadium aluminum alloy by introducing a calcium-containing substance into titanium source and/or vanadium source and using aluminum powder in combination as a reductant, and a simple wet treatment is performed on a reduced material obtained after reduction treatment to achieve separation of a reduction by-product and a first reduction powder to obtain high-purity titanium oxide or high-purity vanadium aluminum alloy, thereby providing theoretical and practical bases for preparing a low-valent titanium oxide having a specific oxygen content, a titanium metal powder having a low oxygen content, a vanadium aluminum alloy having a low oxygen content, and a Ti6Al4V alloy having a low oxygen content.

Claims

1. A method of controllably reducing an oxygen content, comprising the following steps: (1) mixing a raw material, a calcium source, a first reductant and a first adjuvant, and performing first reduction to obtain a reduced material; wherein the raw material is a vanadium oxide or a titanium source, and the first reductant comprises aluminum; and (2) performing a first wet treatment on the reduced material to obtain a first reduced powder; wherein when the raw material is the titanium source, the first reduced powder is TiO.sub.x, wherein a value range of x in TiO.sub.x is 0.167x1; or when the raw material is the vanadium oxide, the first reduced powder is a VAl.sub.y alloy, wherein a value range of y is 0.20y5.80.

2. The method according to claim 1, wherein a temperature of the first reduction is 700 C. to 1400 C.; preferably, a time of the first reduction is 0.25 h to 24 h; preferably, an atmosphere of the first reduction comprises vacuum or a protective atmosphere; preferably, the protective atmosphere comprises any one or a combination of at least two of argon, hydrogen or helium; preferably, the first adjuvant comprises any one or a combination of at least two of anhydrous CaCl.sub.2, a CaCl.sub.2KCl eutectic salt, a CaCl.sub.2NaCl eutectic salt or a CaCl.sub.2AlCl.sub.3 eutectic salt; preferably, the first wet treatment comprises: performing first slurrying on the reduced material with water to obtain a first slurry; performing first pH adjustment on a pH of the first slurry with a hydrochloric acid, and performing solid-liquid separation to obtain a first liquid phase solution and a first solid phase; performing second slurrying on the first solid phase with water and/or an acid liquid to obtain a second slurry; performing second pH adjustment on a pH of the second slurry with a hydrochloric acid, and performing solid-liquid separation to obtain a second liquid phase and a second solid phase; and washing and drying the second solid phase to obtain the first reduced powder; or the first wet treatment comprises: performing third slurrying on the reduced material with water and/or an acid liquid to obtain a third slurry, performing third pH adjustment on a pH of the third slurry, performing solid-liquid separation to obtain a third solid phase, and washing and drying the third solid phase to obtain the first reduced powder; preferably, (NH.sub.4).sub.2CO.sub.3 and the first liquid phase solution are mixed and react, or NH.sub.4HCO.sub.3, ammonia and the first liquid phase solution are mixed and react, and solid-liquid separation is performed after reacting to obtain a CaCO.sub.3 solid and a NH.sub.4Cl solution; preferably, CaCO.sub.3 is returned and used in step (1) as a calcium source for the first reduction; preferably, a liquid-to-solid ratio of the first slurrying is 2:1 mL/g to 20:1 mL/g; preferably, the first pH adjustment is performed with the hydrochloric acid to adjust the pH to 5.0 to 6.0; preferably, the second pH adjustment is performed with the hydrochloric acid to adjust the pH to 1.0 to 3.0; preferably, a temperature of the washing is 0 C. to 60 C.; preferably, a temperature of the drying is less than or equal to 60 C.; preferably, the second liquid phase is a mixed solution of AlCl.sub.3CaCl.sub.2; preferably, the mixed solution of AlCl.sub.3CaCl.sub.2 is used for preparing a polyaluminium chloride product; preferably, the pH of the third slurry is controlled to be greater than or equal to 0.8 during the third pH adjustment; preferably, the pH of the third slurry after the third pH adjustment is 1.5 to 3.0.

3. The method according to claim 1, wherein when the raw material is the titanium source, the mixing in step (1) comprises: performing first mixing on the titanium source and the calcium source to obtain a calcium-containing titanium source, and performing second mixing on the calcium-containing titanium source, the first reductant and the first adjuvant; preferably, a molar ratio of calcium in the calcium-containing titanium source to the first reductant is 0.6:1 to 2:1; preferably, a molar ratio of the first reductant to titanium in the calcium-containing titanium source is 0.67:1 to 1.33:1; preferably, a mass ratio of the first adjuvant to titanium in the titanium source based on TiO.sub.2 is 0.05:1 to 3:1.

4. The method according to claim 1, wherein the vanadium oxide in step (1) comprises V.sub.2O.sub.3 and/or V.sub.2O.sub.5; preferably, when the raw material is the vanadium oxide, a molar ratio of the first reductant to the vanadium oxide is (2ay+2by+10b/3+2a):(a+b), wherein y is a value of y in the VAl.sub.y alloy, a/(a+b) is a molar ratio of V.sub.2O.sub.3 in the vanadium oxide, and b/(a+b) is a molar ratio of V.sub.2O.sub.5 in the vanadium oxide; preferably, the calcium source is a calcium oxide; preferably, a molar ratio of the calcium oxide to the first reductant is 0.6:1 to 2:1; preferably, a mass ratio of the first adjuvant to the vanadium oxide is 0.05:1 to 3:1; preferably, when the raw material is the vanadium oxide, the method further comprises: (3) performing first deoxidization on the VAl.sub.y alloy with a first deoxidizer to obtain a first deoxidized material, wherein the first deoxidizer comprises calcium; and (4) performing a wet treatment on the first deoxidized material to obtain a VAl.sub.y alloy with a low oxygen content.

5. A method of preparing a titanium metal powder by reduction, comprising the method of controllably reducing an oxygen content according to claim 1.

6. The method of preparing a titanium metal powder by reduction according to claim 5, wherein the method comprises four independent schemes, and a method in a first scheme comprises: performing deep deoxidization and a deep deoxidization wet treatment on a first reduced powder with a deep deoxidizer to obtain a titanium metal powder, wherein the deep deoxidizer comprises magnesium and/or calcium, the first reduced powder is TiO.sub.x, wherein, x is 0.167x0.5; or, a method in a second scheme comprises: performing second reduction on a first reduced powder with a second reductant, and performing a second wet treatment to obtain a second reduced powder having an oxygen content less than or equal to 2 wt %, wherein the second reductant comprises magnesium; and performing deep deoxidization and a deep deoxidization wet treatment on the second reduced powder with a deep deoxidizer to obtain a titanium metal powder, wherein the deep deoxidizer comprises magnesium and/or calcium, the first reduced powder is TiO.sub.x, wherein, x is 0.167x1; or, a method in a third scheme comprises: mixing a first reduced powder and a titanium metal powder partially returned to obtain a mixed material, performing first sintering on the mixed material to obtain a titanium-oxygen solid solution having an oxygen content less than or equal to 8 wt %, and performing deep deoxidization and a deep deoxidization wet treatment on the titanium-oxygen solid solution with a deep deoxidizer to obtain a titanium metal powder, wherein the deep deoxidizer comprises magnesium and/or calcium, the first reduced powder is TiO.sub.x, wherein, x is 0.333x0.5; or, a method in a fourth scheme comprises: performing second reduction on titanium dioxide with a second reductant, and performing a second wet treatment to obtain a second reduced powder having an oxygen content less than or equal to 3 wt %; mixing the second reduced powder and a first reduced powder, and performing second sintering to obtain a titanium-oxygen solid solution having an oxygen content less than or equal to 8 wt %; and performing deep deoxidization and a deep deoxidization wet treatment on the titanium-oxygen solid solution with a deep deoxidizer to obtain a titanium metal powder, wherein the deep deoxidizer comprises magnesium and/or calcium, the first reduced powder is TiO.sub.x, wherein, x is 0.333x0.5; preferably, a mass ratio of the second reductant to the first reduced powder in the second scheme is 0.09:1 to 0.56:1; or a molar ratio of the second reductant to titanium dioxide in the fourth scheme is 2:1 to 4:1; preferably, a second adjuvant is added in the second reduction; preferably, the second adjuvant comprises any one or a combination of at least two of anhydrous MgCl.sub.2, a MgCl.sub.2CaCl.sub.2 eutectic salt, a MgCl.sub.2NaCl eutectic salt or a MgCl.sub.2KCl eutectic salt; preferably, a mass ratio of the second adjuvant to the first reduced powder or titanium dioxide is 0.05:1 to 3:1; preferably, a temperature of the second reduction in the second scheme is 650 C. to 900 C.; or a temperature of the second reduction in the fourth scheme is 600 C. to 900 C.; preferably, a time of the second reduction and the deep deoxidization is each independently 0.25 h to 48 h; preferably, a protective atmosphere of the second reduction comprises any one or a combination of at least two of argon, hydrogen or helium; preferably, a deep deoxidization adjuvant is added in the deep deoxidization; preferably, a mass ratio of the deep deoxidization adjuvant to the titanium-oxygen solid solution, the first reduced powder or the second reduced powder is 0.05:1 to 3:1; preferably, when the deep deoxidizer contains magnesium, a mass ratio of magnesium to the first reduced powder in the first scheme is 0.08:1 to 0.64:1, a mass ratio of magnesium to the second reduced powder in the second scheme is 0.03:1 to 0.2:1, a mass ratio of magnesium to the titanium-oxygen solid solution in the third scheme is 0.05:1 to 3:1, or a mass ratio of magnesium to the titanium-oxygen solid solution in the fourth scheme is 0.033:1 to 0.6:1; preferably, when the deep deoxidizer contains magnesium, the deep deoxidization adjuvant comprises any one or a combination of at least two of anhydrous MgCl.sub.2, a MgCl.sub.2CaCl.sub.2 eutectic salt, a MgCl.sub.2NaCl eutectic salt or a MgCl.sub.2KCl eutectic salt; preferably, when the deep deoxidizer contains magnesium, a temperature of the deep deoxidization is 650 C. to 900 C.; preferably, when the deep deoxidizer contains magnesium, an atmosphere of the deep deoxidization comprises a hydrogen-argon mixed atmosphere or a pure hydrogen atmosphere; preferably, a volume fraction of hydrogen in the hydrogen-argon mixed atmosphere is 5% to 100%; preferably, when the deep deoxidizer contains calcium, a mass ratio of calcium to the first reduced powder in the first scheme is 0.13:1 to 1:1, a mass ratio of calcium to the second reduced powder in the second scheme is 0.05:1 to 0.4:1, a mass ratio of calcium to the titanium-oxygen solid solution in the third scheme is 0.05:1 to 3:1, or a mass ratio of calcium to the titanium-oxygen solid solution in the fourth scheme is 0.033:1 to 0.8:1; preferably, when the deep deoxidizer contains calcium, the deep deoxidization adjuvant comprises any one or a combination of at least two of anhydrous CaCl.sub.2, a CaCl.sub.2MgCl.sub.2 eutectic salt, a CaCl.sub.2NaCl eutectic salt or a CaCl.sub.2KCl eutectic salt; preferably, when the deep deoxidizer contains calcium, a temperature of the deep deoxidization is 700 C. to 1100 C.; preferably, when the deep deoxidizer contains calcium, an atmosphere of the deep deoxidization comprises vacuum or a protective atmosphere.

7. The method of preparing a titanium metal powder by reduction according to claim 6, further comprising: performing third sintering or a melting solidification treatment on the first reduced powder between the first wet treatment and the deep deoxidization in the first scheme; preferably, a temperature of the third sintering is 1000 C. to 1500 C.; preferably, a time of the third sintering is 0.25 h to 24 h; preferably, a manner of the melting solidification treatment comprises electromagnetic induction smelting; preferably, the method in the second scheme further comprises: performing a heat treatment on the second reduced powder between the second wet treatment and the deep deoxidization; preferably, a temperature of the heat treatment is 750 C. to 1100 C.; preferably, a time of the heat treatment is 0.167 h to 24 h; preferably, a mass ratio of the first reduced powder to the titanium metal powder mixed in the third scheme is 1:0.25 to 1:10; preferably, a mass ratio of the first reduced powder to the second reduced powder mixed in the fourth scheme is 1:0.267 to 1:10; preferably, temperatures of the first sintering and the second sintering are each independently 800 C. to 1200 C.; preferably, times of the first sintering and the second sintering are each independently 0.25 h to 24 h; preferably, atmospheres of the first sintering, the second sintering, the third sintering and the heat treatment are each independently vacuum or a protective atmosphere; preferably, protective atmospheres of the first sintering, the second sintering, the third sintering and the heat treatment each independently comprise any one or a combination of at least two of argon, hydrogen or helium;

8. The method of preparing a titanium metal powder by reduction according to claim 6, wherein the second wet treatment and the deep deoxidization wet treatment each independently comprise: performing fourth slurrying on a product obtained after the second reduction or the deep deoxidization with water and/or an acid liquid to obtain a fourth slurry; performing fourth pH adjustment on a pH of the fourth slurry, and performing solid-liquid separation to obtain a fourth solid phase; and washing and drying the fourth solid phase to obtain a product; preferably, a pH of the acid liquid in the second wet treatment and the deep deoxidization wet treatment is each independently greater than or equal to 0.5; preferably, an acid used in the fourth pH adjustment in the second wet treatment and the deep deoxidization wet treatment is a hydrochloric acid; preferably, a pH of a slurry in the fourth pH adjustment in the second wet treatment and the deep deoxidization wet treatment is controlled to be greater than or equal to 0.8; preferably, the pH of the fourth slurry after the fourth pH adjustment in the second wet treatment and the deep deoxidization wet treatment is 1.5 to 3.0; preferably, a temperature of the washing in the second wet treatment and the deep deoxidization wet treatment is 0 C. to 60 C.; and preferably, a temperature of the drying in the second wet treatment and the deep deoxidization wet treatment is less than or equal to 60 C.

9. A method of preparing a Ti6Al4V alloy powder, comprising the method of controllably reducing an oxygen content according to claim 1.

10. The method of preparing a Ti6Al4V alloy powder according to claim 9, comprising the following steps: (1) performing first reduction on a mixture of a vanadium oxide and a calcium oxide with a first reductant and a first adjuvant to obtain a first reduced material, and performing a first wet treatment on the first reduced material to obtain a 6Al4V alloy powder, wherein a mass ratio of vanadium to aluminum in the 6Al4V alloy powder is (3.5 to 4.5):(5.5 to 6.75), and the first reductant comprises aluminum; and performing third reduction on titanium dioxide with a third reductant to obtain a third reduced material, and performing a third wet treatment on the third reduced material to obtain a third reduced powder, wherein the third reduced powder is TiO.sub.x, and x is less than or equal to 0.5; and (2) mixing the 6Al4V alloy powder and the third reduced powder, performing fourth sintering to obtain an oxygen-containing Ti6Al4V alloy powder, and performing second deoxidization and a fourth wet treatment on the oxygen-containing Ti6Al4V alloy powder to obtain a Ti6Al4V alloy powder; preferably, a third adjuvant is added in the third reduction; preferably, a mass ratio of the third adjuvant to titanium dioxide is 0.05:1 to 3:1; preferably, a time of the third reduction is 0.25 h to 24 h; preferably, an atmosphere of the third reduction is vacuum or a protective atmosphere; preferably, when the third reductant is aluminum, a molar ratio of the third reductant to titanium dioxide is 1:1 to 1.33:1; preferably, when the third reductant is aluminum, a calcium oxide is added in the third reduction; preferably, when the third reductant is aluminum, a molar ratio of the calcium oxide to the third reductant is 0.6:1 to 2:1; preferably, when the third reductant is aluminum, the third adjuvant comprises any one or a combination of at least two of anhydrous CaCl.sub.2, a CaCl.sub.2KCl eutectic salt, a CaCl.sub.2NaCl eutectic salt or a CaCl.sub.2AlCl.sub.3 eutectic salt; preferably, when the third reductant is aluminum, a temperature of the third reduction is 700 C. to 1400 C.; preferably, when the third reductant is magnesium, a molar ratio of the third reductant to titanium dioxide is 2:1 to 4:1; preferably, when the third reductant is magnesium, the third adjuvant comprises any one or a combination of at least two of anhydrous MgCl.sub.2, a MgCl.sub.2KCl eutectic salt, a MgCl.sub.2NaCl eutectic salt or a MgCl.sub.2CaCl.sub.2 eutectic salt; preferably, when the third reductant is magnesium, a temperature of the third reduction is 600 C. to 900 C.; preferably, a temperature of the fourth sintering is 900 C. to 1400 C.; preferably, a time of the fourth sintering is 0.25 h to 24 h; preferably, an atmosphere of the fourth sintering is vacuum or a protective atmosphere; preferably, a fourth adjuvant is added in the second deoxidization; preferably, when a second deoxidizer contains magnesium, a mass ratio of the oxygen-containing Ti6Al4V alloy powder to the second deoxidizer is 1:0.05 to 1:0.6; and preferably, when the second deoxidizer contains calcium, a mass ratio of the oxygen-containing Ti6Al4V alloy powder to the second deoxidizer is 1:0.1 to 1:1.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0197] FIG. 1 is a flowchart of a method of preparing a low-valent titanium oxide compound TiO.sub.x having a controllable oxygen content according to embodiment one of the present disclosure.

[0198] FIG. 2 is a flowchart of a method of preparing a vanadium-aluminum alloy having a controllable vanadium-aluminum molar ratio according to embodiment two of the present disclosure.

[0199] FIG. 3 is a flowchart of a method of preparing a titanium metal powder by reduction according to embodiment three of the present disclosure.

[0200] FIG. 4 is a flowchart of a method of preparing a titanium metal powder by three-stage reduction of titanium dioxide according to embodiment four of the present disclosure.

[0201] FIG. 5 is a flowchart of a method of preparing a titanium metal powder by reduction of titanium dioxide according to embodiment five of the present disclosure.

[0202] FIG. 6 is a flowchart of a method of preparing a low-oxygen titanium metal powder according to embodiment six of the present disclosure.

[0203] FIG. 7 is a flowchart of a method of preparing a Ti6Al4V alloy powder according to embodiment seven of the present disclosure.

[0204] FIG. 8 is a scanning electron microscopy (SEM) diagram of a Ti6Al4V alloy powder prepared by first reduction according to embodiment G1 of the present disclosure.

[0205] FIG. 9 is an element content analysis diagram of FIG. 8 by spot scanning.

DETAILED DESCRIPTION

[0206] Technical solutions of the present disclosure are further described hereinafter in conjunction with the drawings and the embodiments.

[0207] The present disclosure is further described in detail below. Embodiments set forth below are merely simple examples of the present disclosure and are not intended to represent or limit the protection scope of the present disclosure. The protection scope of the present disclosure is defined by the claims.

[0208] The first wet treatment performed after the first reduction treatment in the following Examples and Comparative Examples may be replaced as follows: performing first slurrying on the reduced material with water to obtain a first slurry, wherein a liquid-to-solid ratio of the first slurrying is 2:1 mL/g to 20:1 mL/g; performing first pH adjustment with a hydrochloric acid to adjust a pH of the first slurry to 5.0 to 6.0, and performing solid-liquid separation to obtain a first liquid phase solution and a first solid phase; mixing (NH.sub.4).sub.2CO.sub.3 and the first liquid phase solution or mixing NH.sub.4HCO.sub.3, ammonia and the first liquid phase solution, performing a reaction, and performing solid-liquid separation after the reaction to obtain a CaCO.sub.3 solid and a NH.sub.4Cl solution, wherein the CaCO.sub.3 solid is returned and used in first reduction as a calcium source; performing second slurrying on the first solid phase with water and/or an acid liquid to obtain a second slurry; performing second pH adjustment with a hydrochloric acid to adjust a pH of the second slurry to 1.0 to 3.0, and performing solid-liquid separation to obtain a second liquid phase and a second solid phase, wherein the second liquid phase is a mixed solution of AlCl.sub.3CaCl.sub.2, and the mixed solution of AlCl.sub.3CaCl.sub.2 is used for preparing a polyaluminium chloride product; and washing the second solid phase at 0 C. to 60 C., and drying the second solid phase at a temperature less than or equal to 60 C. to obtain a first reduced powder. Any regulation and control of each of the preceding process parameters can achieve the preparation of the first reduced powder. To save space, the details are not repeated here. With the replacement by the preceding process flow, the calcium resources can be recycled.

[0209] The test methods are as follows: in the following Examples and Comparative Examples, the value of x in the TiO.sub.x intermediate powder is measured by a difference method and X-ray diffraction analysis after the contents of other elements are measured by inductively coupled plasma atomic emission spectroscopy, the oxygen content of the final titanium metal powder is measured by an ONH analyzer, and the cost of the reductant consumed per ton of titanium metal powder is calculated based on the market average price of magnesium at 40000 CNY per ton, aluminum at 20000 CNY per ton, and calcium at 45000 CNY per ton. The oxygen content of the Ti6Al4V alloy powder is measured by an ONH analyzer, the purity of the Ti6Al4V alloy powder is measured by an ICP-OES analyzer, the particle size of the Ti6Al4V alloy powder is measured by a particle size distribution analyzer, and the contents of elements in the first reduced powder TiO.sub.x and the 6Al4V alloy powder are measured by ICP-OES and EDS methods.

[0210] Embodiment one: A method of preparing a low-valent titanium oxide compound TiO.sub.x having a controllable oxygen content is provided. As shown in FIG. 1, the preparation method includes the following steps.

[0211] (1) A raw material, a calcium source, a first reductant and a first adjuvant are mixed, and first reduction is performed on the resulting mixture to obtain a reduced material; wherein the raw material is a vanadium oxide or a titanium source; the first reductant includes aluminum; the mixing includes: performing first mixing on the titanium source and the calcium source to obtain a calcium-containing titanium source, and performing second mixing on the calcium-containing titanium source, the first reductant and the first adjuvant; the calcium-containing titanium source includes any one or a combination of at least two of a first titanium source, a second titanium source, a third titanium source or a fourth titanium source; the first titanium source is a mixture of titanium dioxide and a calcium oxide; the second titanium source is a mixture of a calcium oxide and calcined titanium dioxide; the third titanium source is a mixture of a calcium oxide and a calcined product obtained after the calcination of a calcium oxide and titanium dioxide mixed based on CaTiO.sub.3; the fourth titanium source is a mixture of a calcium oxide and titanium dioxide which are weighted in a ratio exceeding the ratio based on CaTiO.sub.3, mixed and calcined.

[0212] (2) A first wet treatment is performed on the reduced material to obtain a first reduced powder, wherein the first reduced powder is TiO.sub.x, and the value of x in TiO.sub.x is 0.167x1.

Example A1

[0213] This example provides a method of preparing a low-valent titanium oxide compound TiO.sub.x having a controllable oxygen content. The preparation method includes the following steps.

[0214] (1) A calcium-containing titanium source (a mixture of titanium dioxide and a calcium oxide), an aluminum powder and a CaCl.sub.2NaCl eutectic salt were mixed, and reduction was performed on the resulting mixture at 1200 C. under an argon atmosphere for 2 h to obtain a first reduced material.

[0215] (2) Third slurrying was performed on the reduced material with water to obtain a third slurry, wherein the liquid-to-solid ratio of the third slurrying was 50:1 mL/g; third pH adjustment was performed on the pH of the third slurry with a hydrochloric acid until the pH of the third slurry was adjusted to 2.0, wherein the pH of the third slurry was controlled to be greater than or equal to 0.8 during the third pH adjustment; the third slurry was filtered to obtain a solid phase; and the solid phase was washed at 25 C. with water and dried at 55 C. to obtain TiO.sub.x.

[0216] The value of x in TiO.sub.x may be controlled to be 0.167x1 according to the amounts of the calcium oxide, aluminum powder and CaCl.sub.2NaCl eutectic salt added.

[0217] The specific amounts of the calcium oxide, aluminum powder and CaCl.sub.2NaCl eutectic salt added in this example, the corresponding final value of x, and experimental results are shown in Table 1.

TABLE-US-00001 TABLE 1 Molar ratio Mass ratio Molar ratio of aluminum of the first of calcium in powder to adjuvant to the titanium titanium in titanium in the source to the the titanium titanium source Value first reductant source based on TiO.sub.2 of x Note Example 0.6:1 0.67:1 1.5:1 0.99 A1-1 Example 1.0:1 1.11:1 1.5:1 0.51 A1-2 Example 2.0:1 1.11:1 1.5:1 0.50 A1-3 Example 1.0:1 1.22:1 1.5:1 0.33 A1-4 Example 1.5:1 1.33:1 1.5:1 0.167 A1-5 Example 0.4:1 0.67:1 1.5:1 / Weak acid- A1-6 insoluble by- products are generated. Example 3.0:1 1.11:1 1.5:1 0.51 Excess CaO is A1-7 ineffectively consumed. Example 1.0:1 0.3:1 1.5:1 1.86 A1-8 Example 1.0:1 1.8:1 1.5:1 / Ti.sub.3Al as the A1-9 main phase, with a small amount of Ti.sub.6O.

Example A2

[0218] This example provides a method of preparing a low-valent titanium oxide compound TiO.sub.x having a controllable oxygen content. The preparation method includes the following steps.

[0219] (1) A calcium-containing titanium source (a mixture of a calcium oxide and titanium dioxide which was calcined at 1300 C. for 3 h), an aluminum powder and a CaCl.sub.2NaCl eutectic salt were mixed, and reduction was performed on the resulting mixture at 700 C. under vacuum (with an absolute vacuum degree of 80 kPa) for 24 h to obtain a first reduced material.

[0220] (2) Third slurrying was performed on the first reduced material with a hydrochloric acid whose pH was 1.2 to obtain a third slurry, wherein the liquid-to-solid ratio of the third slurrying was 10:1 mL/g; third pH adjustment was performed on the pH of the third slurry with a hydrochloric acid until the pH of the third slurry was adjusted to 2.0, wherein the pH of the third slurry was controlled to be greater than or equal to 0.8 during the third pH adjustment; the third slurry was filtered to obtain a solid phase; and the solid phase was washed at 25 C. with water and dried at 60 C. to obtain TiO.sub.x.

[0221] The value of x in TiO.sub.x may be controlled to be 0.167x1 according to the amounts of the calcium oxide, aluminum powder and CaCl.sub.2NaCl eutectic salt as the first adjuvant added.

[0222] The specific amounts of the calcium oxide, aluminum powder and CaCl.sub.2NaCl eutectic salt added in this example and the corresponding final value of x are shown in Table 2.

TABLE-US-00002 TABLE 2 Molar ratio Mass ratio Molar ratio of aluminum of the first of calcium in powder to adjuvant to the titanium titanium in titanium in the source to the the titanium titanium source Value first reductant source based on TiO.sub.2 of x Example A2-1 1.5:1 0.67:1 2.0:1 1.0 Example A2-2 1.5:1 0.9:1 2.0:1 0.67 Example A2-3 1.5:1 1.11:1 2.0:1 0.49

Example A3

[0223] This example provides a method of preparing a low-valent titanium oxide compound TiO.sub.x having a controllable oxygen content. The preparation method includes the following steps.

[0224] (1) A calcium-containing titanium source (a product obtained after a calcium oxide and titanium dioxide which were weighted in a ratio exceeding the stoichiometric ratio based on CaTiO.sub.3, mixed and calcined at 1200 C. for 8 h), an aluminum powder and a CaCl.sub.2KCl eutectic salt were mixed, and reduction was performed on the resulting mixture at 1000 C. under a hydrogen-argon mixed atmosphere (where the volume ratio of hydrogen to argon was 1:1) for 8 h to obtain a first reduced material.

[0225] (2) Third slurrying was performed on the first reduced material with a hydrochloric acid whose pH was 1.0 to obtain a third slurry, wherein the liquid-to-solid ratio of the third slurrying was 5:1 mL/g; third pH adjustment was performed on the pH of the third slurry with a hydrochloric acid until the pH of the third slurry was adjusted to 2.5, wherein the pH of the third slurry was controlled to be greater than or equal to 0.8 during the third pH adjustment; the third slurry was filtered to obtain a solid phase; and the solid phase was washed at 0 C. with water and dried at 45 C. to obtain TiO.sub.x.

[0226] The value of x in TiO.sub.x may be controlled to be 0.167x1 according to the amounts of the calcium oxide, aluminum powder and CaCl.sub.2KCl eutectic salt as the first adjuvant added.

[0227] The specific amounts of the calcium oxide, aluminum powder and CaCl.sub.2KCl eutectic salt added in this example and the corresponding final value of x are shown in Table 3.

TABLE-US-00003 TABLE 3 Mass ratio Molar ratio Molar ratio of the first of calcium in of aluminum adjuvant to the titanium powder to titanium in source to titanium in the titanium the first the titanium source based Value reductant source on TiO.sub.2 of x Note Example 1.0:1 0.9:1 3.0:1 0.67 A3-1 Example 1.0:1 1.17:1 3.0:1 0.40 A3-2 Example 1.0:1 1.28:1 3.0:1 0.22 A3-3 Example 1.0:1 2.33:1 2.5:1 / Ti.sub.3Al and A3-4 TiAl phases are generated.

Example A4

[0228] The preparation method of this example is the same as the preparation method of Example A1 except that the first adjuvant was replaced with NaCl, and the results are shown in Table 4.

TABLE-US-00004 TABLE 4 Mass ratio Molar ratio of the first Molar ratio of aluminum adjuvant to of calcium in powder to titanium in the titanium titanium in thetitanium source to the the titanium source based Value first reductant source on TiO.sub.2 of x Example A4-1 0.6:1 0.67:1 1.5:1 1.19 Example A4-2 1.0:1 1.11:1 1.5:1 0.64 Example A4-3 2.0:1 1.11:1 1.5:1 0.68 Example A4-4 1.0:1 1.22:1 1.5:1 0.42 Example A4-5 1.5:1 1.33:1 1.5:1 0.19

Comparative Example A1

[0229] The preparation method of this comparative example is the same as the preparation method of Example A1 except that the aluminum powder was replaced with an equal molar ratio of a magnesium powder, and the results are shown in Table 5.

TABLE-US-00005 TABLE 5 Molar ratio Mass ratio Molar ratio of magnesium of the first of calcium in powder to adjuvant to the titanium titanium in titanium in the source to the the titanium titanium source first reductant source based on TiO.sub.2 Note Comparative 0.6:1 0.67:1 1.5:1 When Mg is Example A1-1 used as the Comparative 1.0:1 1.11:1 1.5:1 reductant, the Example A1-2 CaO additive Comparative 2.0:1 1.11:1 1.5:1 has no effect in Example A1-3 the system and Comparative 1.5:1 1.33:1 1.5:1 is an ineffective Example A1-4 additive, and a Comparative 1.0 1.22:1 1.5:1 composite Example A1-5 material of MgO and low- valent titanium oxide is generated.

Comparative Example A2

[0230] The preparation method of this comparative example is the same as the preparation method ofExample A2 except that the titanium source did not contain calcium, and the results are shown in Table 6.

TABLE-US-00006 TABLE 6 Molar ratio Mass ratio of aluminum of the first powder to adjuvant to titanium in titanium in the the titanium titanium source source based on TiO.sub.2 Note Comparative 0.67:1 2.0:1 The reduction by- Example A2-1 products cannot be Comparative 0.9:1 2.0:1 effectively Example A2-2 separated from Comparative 1.11:1 2.0:1 TiOx by wet Example A2-3 separation.

Comparative Example A3

[0231] This comparative example provides a method of preparing a low-valent titanium oxide compound TiO.sub.x having a controllable oxygen content. The preparation method is performed by a self-propagating method. The specific method includes: TiO.sub.2, a reductant Al powder, a combustion improver KClO.sub.4 and an adjuvant CaO were thoroughly mixed in a certain ratio for half an hour and then placed in a stainless steel cup (where Al/TiO.sub.2=1.33); the steel cup was placed in a high-pressure vessel filled with argon, and a self-propagating reaction was triggered by a nickel-chromium filament on the upper surface of the cup; a large amount of heat was rapidly released from the reaction to cause a sharp increase in the system temperature, the reaction product was melted, and slag and metal titanium were automatically separated to finally obtain a TiO.sub.x titanium oxide compound ingot with x equal to 0.35.

[0232] Taking the methods of Example A1-1, Example A1-4, Example A1-5, Example A1-7, Example A1-8, Example A4-2, Example A5-1 and Comparative Example A3 as examples, the stability of the components of the products obtained in different methods was detected, that is, each method was repeated five times, and the value of x in the final product was calculated according to the oxygen content in the low-valent titanium oxide compound TiO.sub.x product. The results are shown in Table 7.

TABLE-US-00007 TABLE 7 First Second Third Fourth Fifth Mean time time time time time square x x x x x Average deviation Range Example A1-1 0.99 0.99 1.01 1.0 1.0 0.998 0.0084 0.02 Example A1-4 0.33 0.34 0.33 0.33 0.32 0.33 0.0071 0.02 Example A1-5 0.167 0.17 0.16 0.167 0.17 0.167 0.0041 0.01 Example A1-7 0.51 0.50 0.51 0.49 0.51 0.504 0.0089 0.02 Example A1-8 1.86 1.84 1.87 1.86 1.85 1.856 0.0114 0.03 Example A4-2 0.40 0.39 0.40 0.41 0.41 0.402 0.0084 0.02 Example A5-1 1.19 1.17 1.21 1.23 1.19 1.198 0.0228 0.06 Comparative 0.35 0.38 0.40 0.32 0.35 0.36 0.0308 0.08 Example A3

[0233] In Tables 1 to 7, / indicates that there is no related data.

[0234] The following conclusions can be drawn from Tables 1 to 7.

[0235] (1) As can be seen from Examples A1 to A3, the method of preparing a low-valent titanium oxide compound TiO.sub.x having a controllable oxygen content provided by the present disclosure can better control the oxygen content of the first reduced powder, that is, the oxygen content of the low-valent titanium oxide compound TiO.sub.x. Within the preferable range, the mean square deviation of multiple replicates is in the range of 0.0084, and the range of x is less than or equal to 0.03. Furthermore, the x can be effectively controlled between 0.167 and 1 according to Al+TiO.sub.2.fwdarw.TiO.sub.x+Al.sub.2O.sub.3, thereby achieving the accurate control of the oxygen content in the low-valent titanium oxide.

[0236] (2) As can be seen from Example A1-1 and Example A5-1, in a case where the CaCl.sub.2NaCl eutectic salt is used as the first adjuvant in Example A1-1 and NaCl is used as the first adjuvant in Example A5-1, with the same ratio, the value of x in Example A1-1 is only 0.99; in Example A5-1, the value of x is as high as 1.19, the mean square deviation is as high as 0.0228, and the range is as high as 0.06, indicating that the control effect on the oxygen content is reduced. Therefore, in the present disclosure, by preferably selecting the first adjuvant containing calcium, the reduction can be better promoted, thereby improving the reduction effect and the control effect on the oxygen content.

[0237] (3) As can be seen from Example A1 and Comparative Example A1, Example A1 uses aluminum to perform reduction, and with the same amount of the first reduced agent added, the value x in Example A1-5 can be as low as 0.167; Comparative Example A1 uses magnesium to perform reduction, a composite material of MgO and low-valent titanium oxide was generated, and the titanium oxide compound TiO.sub.x cannot be obtained. Therefore, in the present disclosure, by preferably selecting aluminum to perform reduction, the value of x in TiO.sub.x can be better controlled, and the wet separation can be more easily performed.

[0238] (4) As can be seen from Example A1, Comparative Example A2 and Comparative Example A3, the reduction with aluminum is performed under the condition of adding a calcium oxide in Example A1, no calcium oxide is added in Comparative Example A2, and reduction is performed by self-propagating in Comparative Example A3; by comparison, the reduced product in Example A1 can be separated by wet method, thereby achieving the accurate control of the oxygen content, with the mean square deviation of only 0.0084 and the ranged of only 0.02; although a reduction method similar to the reduction method of Example A1 is adopted, the wet separation cannot be performed in Comparative Example A2; the slag-metal separation is performed in Comparative Example A3 after self-propagating, the oxygen content is difficult to control, the mean square deviation of five replicates is as high as 0.0308, and the range is as high as 0.08. Therefore, in the present disclosure, under the action of the calcium-containing substance and the first adjuvant, the by-product Al.sub.2O.sub.3 obtained during the process of reducing TiO.sub.2 with aluminum can be converted into a calcium-aluminum-containing compound which is easy to dissolve by a wet method, and the low-valent titanium oxide can be obtained by wet separation, thereby enabling the oxygen content to be more controllable and significantly reducing the cost of the first reductant.

[0239] Embodiment two: The present disclosure provides a method of preparing a vanadium-aluminum alloy having a controllable vanadium-aluminum molar ratio. As shown in FIG. 2, the preparation method includes the following steps.

[0240] (1) A vanadium oxide, a calcium source, a first reductant and a first adjuvant are mixed, and first reduction is performed on the resulting mixture to obtain a reduced material, wherein the first reductant includes aluminum.

[0241] (2) A first wet treatment is performed on the reduced material to obtain a first reduced powder, wherein the first reduced powder is a VAl.sub.y alloy, and the value of y is 0.20y5.80.

[0242] Optionally, the preparation method further includes the following steps: (3) first deoxidization is performed on the VAl.sub.y alloy with a first deoxidizer and a first deoxidization adjuvant to obtain a first deoxidized material, wherein the first deoxidizer includes calcium; and (4) a wet treatment is performed on the first deoxidized material after the first deoxidization to obtain a VAl.sub.y alloy having a low oxygen content.

Example B1

[0243] This example provides a method of preparing a vanadium-aluminum alloy having a controllable vanadium-aluminum molar ratio. The preparation method includes the following steps.

[0244] (1) A vanadium oxide, a CaO powder, an Al powder and a CaCl.sub.2NaCl eutectic salt were mixed, wherein the molar ratio of the Al powder to the vanadium oxide was (2ay+2by+10b/3+2a):(a+b), y was the value of y in the VAl.sub.y alloy, a/(a+b) was the molar ratio of V.sub.2O.sub.3 in the vanadium oxide, b/(a+b) was the molar ratio of V.sub.2O.sub.5 in the vanadium oxide; and first reduction was performed on the resulting mixture at 1300 C. under vacuum or a protective atmosphere (whether the atmosphere was vacuum or a protective atmosphere did not affect the result) for 10 h to obtain a first reduced material.

[0245] (2) Third slurrying was performed on the first reduced material with a hydrochloric acid liquid whose pH was 1.5 to obtain a third slurry; third pH adjustment was performed on the pH of the third slurry, wherein the pH of the third slurry was controlled to be greater than or equal to 0.8 during the third pH adjustment, and the pH of the third slurry after the third pH adjustment was stabilized to 2.2; the third slurry was filtered to obtain a solid phase; and the solid phase was washed at 45 C. with water and dried at 55 C. under vacuum to obtain a VAl.sub.y alloy, wherein the value of y was greater than or equal to 0.20 and less than or equal to 5.80.

[0246] The specific molar ratio b:a of V.sub.2O.sub.5 to V.sub.2O.sub.3 in the vanadium oxide, the specific amounts of the calcium oxide, aluminum powder and CaCl.sub.2NaCl eutectic salt added in this example and the corresponding final value of y are shown in Table 8.

TABLE-US-00008 TABLE 8 VAl.sub.y Molar ratio Molar Mass ratio of alloy VAl.sub.y of Al to ratio of CaCl.sub.2NaCl oxygen alloy vanadium CaO to eutectic salt to Value content purity a b oxide Al vanadium oxide of y wt % (wt %) Example 0 1 3.74:1 1.0:1 1.5:1 0.2 0.23 99.9 B1-1 Example 0.5 1 .sup.8.83:1.5 1.0:1 0.6:1 1.5 0.18 99.5 B1-2 Example 1 1 13.3:2 1.0:1 1.5:1 2 0.15 99.9 B1-3 Example 2 1 31.3:3 0.6:1 2.0:1 4 0.12 99.8 B1-4 Example 1 0 13.6:1 1.5:1 1.5:1 5.8 0.08 99.9 B1-5 Example 1 1 13.3:2 0.4:1 1.5:1 The aluminum oxide-rich B1-6 by-product phase cannot be completely dissolved in dilute acids. Example 1 1 13.3:2 2.0:1 1.5:1 2 0.15 99.9% B1-7 Example 1 1 13.3:2 1.0:1 3.0:1 2 0.15 99.9% B1-8 Example 1 1 13.3:2 1.0:1 0.02:1 The aluminum oxide-rich B1-9 by-product phase cannot be completely dissolved in dilute acids.

[0247] The following conclusions can be drawn from Table 8.

[0248] (1) As can be seen from Examples B1-3, B1-6 and B1-7, in Example B1-6, when the amount of the calcium oxide added is too low, the aluminum oxide-rich by-product is difficult to be dissolved in dilute acids, and the phase of the acid washing product includes the VAl.sub.y alloy and acid-insoluble calcium aluminate; in Example B1-7, when too much calcium oxide is added, the calcium oxide is excessively consumed. Therefore, in the present disclosure, by controlling the molar ratio of the calcium oxide to aluminum to be within a specific range, the product purity can be improved, and the consumption of the calcium oxide can be reduced.

[0249] (2) As can be seen from Examples B1-3, B1-8 and B1-9, in Example B1-9, when the amount of the first adjuvant added is too low, the acid-soluble aluminum-calcium by-product phase is difficult to be fully generated, and the phase of the acid washing product includes the VAl.sub.y alloy and acid-insoluble calcium aluminate; in Example B1-8, the salt consumption is high. Therefore, in the present disclosure, by controlling the mass ratio of the first adjuvant to the vanadium oxide to be within a specific range, the product purity can be improved, and the consumption of the first adjuvant can be reduced.

Example B2

[0250] This example provides a method of preparing a vanadium-aluminum alloy having a controllable vanadium-aluminum molar ratio. The preparation method includes the following steps.

[0251] (1) Avanadium oxide, a CaO powder, an Al powder and anhydrous CaCl.sub.2 were mixed, wherein the molar ratio of the Al powder to the vanadium oxide was (2ay+2by+10b/3+2a):(a+b), y was the value of y in the VAl.sub.y alloy, a/(a+b) was the molar ratio of V.sub.2O.sub.3 in the vanadium oxide, b/(a+b) was the molar ratio of V.sub.2O.sub.5 in the vanadium oxide; and first reduction was performed on the resulting mixture at 1400 C. under vacuum or a protective atmosphere for 0.25 h to obtain a first reduced material.

[0252] (2) Third slurrying was performed on the first reduced material with a hydrochloric acid liquid whose pH was 0.5 to obtain a third slurry; third pH adjustment was performed on the pH of the third slurry, wherein the pH of the third slurry was controlled to be greater than or equal to 1.0 during the third pH adjustment, and the pH of the third slurry after the third pH adjustment was stabilized to 3.0; the third slurry was filtered to obtain a solid phase; and the solid phase was washed at 0 C. with water and dried at 60 C. under vacuum to obtain a VAl.sub.y alloy, wherein the value of y was 0.20y5.80.

[0253] (3) First deoxidization was performed on the VAl.sub.y alloy with calcium as a first deoxidizer and anhydrous CaCl.sub.2 at 1100 C. under vacuum for 0.25 h to obtain a deoxidized material, wherein the mass ratio of the VAl.sub.y alloy to the first deoxidizer was 1:0.05, and the mass ratio of anhydrous CaCl.sub.2 to the VAl.sub.y alloy was 0.2:1.

[0254] (4) Third slurrying was performed on the deoxidized material with water to obtain a third slurry; third pH adjustment was performed on the pH of the third slurry, wherein the pH of the third slurry was controlled to be greater than or equal to 0.8 during the third pH adjustment, and the pH of the third slurry after the third pH adjustment was stabilized to 2.0; the third slurry was filtered to obtain a solid phase; and the solid phase was washed at 20 C. and dried at 45 C. to obtain a VAl.sub.y alloy having a low oxygen content.

[0255] The specific molar ratio b:a of V.sub.2O.sub.5 to V.sub.2O.sub.3 in the vanadium oxide, the specific amounts of the calcium oxide, aluminum powder and anhydrous CaCl.sub.2 added in this example and the corresponding final value of y are shown in Table 9.

TABLE-US-00009 TABLE 9 VAl.sub.y Molar ratio Molar Mass ratio of alloy VAl.sub.y of Al to the ratio of anhydrous oxygen alloy vanadium CaO to CaCl.sub.2 to Value content purity a b oxide Al vanadium oxide of y wt % (wt %) Example 0 1 3.93:1.sup. 1.2:1 1.0:1 0.3 0.19 99.9 B2-1 Example 0.5 1 9.73:1.5 0.8:1 0.8:1 1.8 0.17 99.8 B2-2 Example 1 3 40:4 1.0:1 1.5:1 3.5 0.13 99.9 B2-3 Example 1 0 13.6:1.sup. 1.2:1 1.2:1 5.8 0.09 99.9 B2-4

Example B3

[0256] This example provides a method of preparing a vanadium-aluminum alloy having a controllable vanadium-aluminum molar ratio. The preparation method includes the following steps.

[0257] (1) A vanadium oxide, a CaO powder, an Al powder and a CaCl.sub.2KCl eutectic salt were mixed, wherein the molar ratio of the Al powder to the vanadium oxide was (2ay+2by+10b/3+2a):(a+b), y was the value of y in the VAl.sub.y alloy, a/(a+b) was the molar ratio of V.sub.2O.sub.3 in the vanadium oxide, b/(a+b) was the molar ratio of V.sub.2O.sub.5 in the vanadium oxide; and first reduction was performed on the resulting mixture at 700 C. under vacuum or a protective atmosphere for 24 h to obtain a first reduced material.

[0258] (2) Third slurrying was performed on the first reduced material with a hydrochloric acid liquid whose pH was 1.0 to obtain a third slurry; third pH adjustment was performed on the pH of the third slurry, wherein the pH of the third slurry was controlled to be greater than or equal to 0.8 during the third pH adjustment, and the pH of the third slurry after the third pH adjustment was stabilized to 1.5; the third slurry was filtered to obtain a solid phase; and the solid phase was washed at 60 C. with water and dried at 45 C. under vacuum to obtain a VAl.sub.y alloy, wherein the value of y was 0.20y5.80.

[0259] (3) First deoxidization was performed on the VAl.sub.y alloy with calcium as a first deoxidizer and a CaCl.sub.2KCl eutectic salt at 700 C. under a helium atmosphere for 48 h to obtain a deoxidized material, wherein the mass ratio of the VAl.sub.y alloy to the first deoxidizer was 1:0.5, and the mass ratio of the CaCl.sub.2KCl eutectic salt to the VAl.sub.y alloy was 3:1.

[0260] (4) Third slurrying was performed on the deoxidized material with water to obtain a third slurry; third pH adjustment was performed on the pH of the third slurry, wherein the pH of the third slurry was controlled to be greater than or equal to 0.8 during the third pH adjustment, and the pH of the third slurry after the third pH adjustment was stabilized to 3.0; the third slurry was filtered to obtain a solid phase; and the solid phase was washed at 10 C. and dried at 40 C. to obtain a VAl.sub.y alloy having a low oxygen content.

[0261] The specific molar ratio b:a of V.sub.2O.sub.5 to V.sub.2O.sub.3 in the vanadium oxide, the specific amounts of the calcium oxide, aluminum powder and anhydrous CaCl.sub.2 added in this example and the corresponding final value of y are shown in Table 10.

TABLE-US-00010 TABLE 10 Mass ratio of anhydrous VAl.sub.y Molar ratio Molar CaCl.sub.2 eutectic alloy VAl.sub.y of Al to the ratio of salt to oxygen alloy vanadium CaO to vanadium Value content purity a b oxide Al oxide of y wt % (wt %) Example 1 1 6.53:2.sup. 1.1:1 1.0:1 0.3 0.20 99.9 B3-1 Example 0.2 1 7.33:1.2 0.9:1 0.8:1 1.5 0.18 99.8 B3-2 Example 1 2 20.67:3 1.2:1 1.2:1 2.0 0.14 99.9 B3-3 Example 1 3 52:4 1.2:1 1.2:1 5.0 0.10 99.9 B3-4

Example B4

[0262] The preparation method of this example is the same as the preparation method of Example B1-1 except that first deoxidization and a post-deoxidization wet treatment were performed after step (2).

[0263] Specifically, the preparation method further includes the following steps.

[0264] (3) First deoxidization was performed on the VAl.sub.y alloy with calcium as a first deoxidizer and a CaCl.sub.2KCl eutectic salt at 1000 C. under a helium atmosphere for 20 h to obtain a deoxidized material, wherein the mass ratio of the VAl.sub.y alloy to the first deoxidizer was 1:0.3, and the mass ratio of the CaCl.sub.2KCl eutectic salt to the VAl.sub.y alloy was 0.4:1.

[0265] (4) Third slurrying was performed on the deoxidized material with a hydrochloric acid liquid whose pH was 0.8 to obtain a third slurry; third pH adjustment was performed on the pH of the third slurry, wherein the pH of the third slurry was controlled to be greater than or equal to 0.8 during the third pH adjustment, and the pH of the third slurry after the third pH adjustment was stabilized to 2.5; the third slurry was filtered to obtain a solid phase; and the solid phase was washed at 15 C. and dried at 45 C. under vacuum to obtain a VAl.sub.y alloy having an oxygen content as low as 0.07%.

Example B5

[0266] The preparation method of this example is the same as the preparation method of Example B1 except that the first adjuvant CaCl.sub.2KCl eutectic salt was replaced with MgCl.sub.2, and the results are shown in Table 11.

TABLE-US-00011 TABLE 11 Molar ratio Molar Mass ratio of of Al to the ratio of MgCl.sub.2 slat to Product obtained after vanadium CaO to vanadium first reduction and acid a b oxide Al oxide washing Example B1-1 0 1 3.74:1 1.0:1 1.5:1 Due to the replacement Example B1-2 0.5 1 .sup.8.83:1.5 1.0:1 0.6:1 reaction between MgCl.sub.2 Example B1-3 1 1 13.3:2 1.0:1 1.5:1 and CaO, the generated Example B1-4 2 1 31.3:3 0.6:1 2.0:1 MgO reacts with part of Example B1-5 1 0 13.6:1 1.5:1 1.5:1 the first reduction product Al.sub.2O.sub.3 to form dilute acid-insoluble magnesia-alumina spinel, and the mixture of magnesia-alumina spinel and a vandium- aluminum alloy is obtained, where the mass proportion of the vanadium-aluminum alloy cannot exceed 80%.

Comparative Example B1

[0267] The preparation method of this comparative example is the same as the preparation method of Example B1-1 except that the aluminum powder was replaced with an equal molar ratio of a magnesium powder. Since no aluminum source was used in this comparative example, no vanadium-aluminum alloy was obtained after the first reduction.

Comparative Example B2

[0268] The preparation method of this comparative example is the same as the preparation method of Example B1-1 except that no calcium oxide was added. Since the aluminum oxide-rich by-product phase in the obtained first reduction product cannot be completely dissolved in dilute acids, the vanadium aluminum alloy with high purity cannot be obtained.

[0269] As can be seen from Example B1-1, Comparative Example B1 and Comparative Example B2, a calcium oxide and a first adjuvant are added in the first reduction with aluminum in the present disclosure, magnesium is used as the first reductant in Comparative Example B1, and no calcium oxide is added in Comparative Example B2; in this manner, the VAl.sub.y alloy wherein the value of y is 0.2 can be accurately prepared in Example B1-1, the vanadium-aluminum alloy cannot be formed in Comparative Example Bi, and although the vanadium-aluminum alloy can be obtained in Comparative Example B2, since the aluminum oxide-rich by-product phase in the first reduction product is mainly a corundum phase which cannot be dissolved in dilute acids, the mixed phase of the vanadium-aluminum alloy and aluminum oxide is obtained after acid washing.

[0270] Taking Example B1-1, Example B1-4, Example B2-1 and Example B3-3 as examples, the stability of the components of the products obtained in the methods of the present disclosure was detected, that is, each Example B was repeated five times, and the value of y in the final product was calculated by an ICP-OES chemical component analytical method. The results are shown in Table 12.

TABLE-US-00012 TABLE 12 First Second Third Fourth Fifth time time time time time Standard y y y y y Average deviation Example B1-1 0.200 0.202 0.199 0.199 0.201 0.200 0.0013 Example B1-4 4.000 4.005 4.007 3.992 3.996 4.000 0.0062 Example B2-1 0.301 0.308 0.293 0.299 0.302 0.301 0.0054 Example B3-3 2.000 2.004 1.995 2.001 1.998 2.000 0.0034

[0271] As can be seen from Table 12, the method of preparing a vanadium-aluminum alloy provided by the present disclosure can reliably and stably prepare VAl.sub.y alloys having desired values of y, and the standard deviation of the value of y of five replicates is less than or equal to 0.0062, indicating that the stability is high.

[0272] Embodiment three: The present disclosure provides a first scheme of preparing a titanium metal powder, that is, the present disclosure provides a method of preparing a titanium metal powder by reduction of titanium dioxide. As shown in FIG. 3, the preparation method includes the following steps.

[0273] (1) A calcium-containing titanium source, a first reductant and a first adjuvant are mixed, and first reduction is performed on resulting mixture to obtain a reduced material, wherein the first reductant includes aluminum; and a first wet treatment is performed on the reduced material to obtain a first reduced powder, wherein the first reduced powder is TiO.sub.x, and x is 0.167x0.5.

[0274] (2) Deep deoxidization and a deep deoxidization wet treatment are performed on the first reduced powder with a deep deoxidizer to obtain a titanium metal powder, wherein the deep deoxidizer includes magnesium and/or calcium.

[0275] Optionally, third sintering or electromagnetic induction smelting may be performed on the first reduced powder between the first wet treatment and the deep deoxidization.

[0276] Optionally, when the deep deoxidizer contains magnesium, a dehydrogenation treatment is performed on the product obtained after the deep deoxidization wet treatment to obtain a titanium metal powder.

Example C1

[0277] This example provides a method of preparing a titanium metal powder by reduction of titanium dioxide. The preparation method includes the following steps.

[0278] (1) A calcium-containing titanium source (a mixture of a calcium oxide and calcined titanium dioxide), an aluminum powder and a CaCl.sub.2KCl eutectic salt were mixed, wherein the molar ratio of calcium in the calcium-containing titanium source to the aluminum powder was 1.0:1, the molar ratio of the aluminum powder to titanium in the calcium-containing titanium source was 1.11:1, and the mass ratio of the CaCl.sub.2KCl eutectic salt to titanium in the calcium-containing titanium source based on TiO.sub.2 was 1.5:1; and first reduction was performed on the resulting mixture at 1200 C. under a helium atmosphere for 2 h to obtain a first reduction product.

[0279] Slurrying was performed on the first reduction product with a hydrochloric acid whose pH was 1.0 to obtain a slurry, wherein the liquid-to-solid ratio was 50:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 2.2; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 50 C. with water and dried at 45 C. to obtain a TiO.sub.x intermediate powder.

[0280] (2) The TiO.sub.x intermediate powder was sintered at 1400 C. under vacuum for 1 h, and deep deoxidization was performed with a magnesium powder and a MgCl.sub.2 molten salt on the sintered TiO.sub.x intermediate powder at 850 C. under a pure hydrogen atmosphere for 2 h to obtain a deep deoxidization product, wherein the mass ratio of the magnesium powder to the TiO.sub.x intermediate powder was 0.3:1, and the mass ratio of the MgCl.sub.2 molten salt to the TiO.sub.x intermediate powder was 2.0:1.

[0281] Slurrying was performed on the deep deoxidization product with a hydrochloric acid liquid whose pH was 1.5 to obtain a slurry, wherein the liquid-to-solid ratio was 3:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 1.5; the slurry was filtered to obtain a solid phase; the solid phase was washed at 40 C. with water and dried at 40 C. to obtain a dried product; and a dehydrogenation treatment was performed on the dried product at 800 C. under an argon atmosphere to obtain a titanium metal powder.

Example C2

[0282] This example provides a method of preparing a titanium metal powder by reduction of titanium dioxide. The preparation method includes the following steps.

[0283] (1) A calcium-containing titanium source (a mixture of a calcium oxide and a calcined product obtained after the calcination of a calcium oxide and titanium dioxide mixed based on CaTiO.sub.3), an aluminum powder and a CaCl.sub.2NaCl eutectic salt were mixed, wherein the molar ratio of calcium in the calcium-containing titanium source to the aluminum powder was 0.6:1, the molar ratio of the aluminum powder to titanium in the calcium-containing titanium source was 1.33:1, and the mass ratio of the CaCl.sub.2NaCl eutectic salt to titanium in the calcium-containing titanium source based on TiO.sub.2 was 3.0:1; and first reduction was performed on the resulting mixture at 1100 C. under a helium atmosphere for 4 h to obtain a first reduction product.

[0284] Slurrying was performed on the first reduction product with a hydrochloric acid whose pH was 1.0 to obtain a slurry, wherein the liquid-to-solid ratio was 20:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 1.2 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 2.5; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 20 C. with water and dried at 60 C. to obtain a TiO.sub.x intermediate powder.

[0285] (2) The TiO.sub.x intermediate powder was sintered at 1200 C. under a hydrogen atmosphere for 12 h, and deep deoxidization was performed with calcium particles and anhydrous CaCl.sub.2 on the sintered TiO.sub.x intermediate powder at 800 C. under a hydrogen-argon mixed atmosphere (where the volume fraction of hydrogen was 50%) for 12 h to obtain a deep deoxidization product, wherein the mass ratio of the calcium particles to the TiO.sub.x intermediate powder was 0.14:1, and the mass ratio of anhydrous CaCl.sub.2 to the TiO.sub.x intermediate powder was 3.0:1.

[0286] Slurrying was performed on the deep deoxidization product with a hydrochloric acid liquid whose pH was 1.0 to obtain a slurry, wherein the liquid-to-solid ratio was 80:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 1.0 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 2.5; the slurry was filtered to obtain a solid phase; the solid phase was washed at 45 C. with water and dried at 40 C. to obtain a dried product; and a dehydrogenation treatment was performed on the dried product at 500 C. under vacuum to obtain a titanium metal powder.

Example C3

[0287] The preparation method of this example is the same as the preparation method of Example C1 except that the MgCl.sub.2 molten salt in step (2) was replaced with a CaCl.sub.2 molten salt.

Example C4

[0288] The preparation method of this example is the same as the preparation method of Example C1 except that the pure hydrogen atmosphere in step (2) was replaced with a helium atmosphere.

Example C5

[0289] The preparation method of this example is the same as the preparation method of Example C1 except that the sintering step in step (2) was not performed, that is, deep deoxidization was directly performed on the TiO.sub.x intermediate powder, wherein the parameters and conditions of the deep deoxidization were the same as those in Example C1.

[0290] The calculation results are shown in Tables 13 and 14.

TABLE-US-00013 TABLE 13 Value Oxygen Aluminum Magnesium Reductant of x content of consumed or calcium cost of in TiO.sub.x titanium per ton of consumed per per ton of inter- metal titanium ton of titanium mediate powder metal titanium metal powder (wt %) powder metal powder powder Example 0.5 0.28 0.6244 0.35 26,488 C1 CNY Example 0.167 0.15 0.7481 0.1477 21,608 C2 CNY

TABLE-US-00014 TABLE 14 Product obtained after washing, Oxygen content of filtration and drying are performed titanium metal on the first reduction product powder (wt %) Example C3 Ti.sub.2O, i.e., x = 0.5 0.88 Example C4 Ti.sub.2O, i.e., x = 0.5 2.45 Example C5 Ti.sub.2O, i.e., x = 0.5 1.75

[0291] / in the preceding tables indicates that there is no related data.

[0292] The following conclusions can be drawn from Tables 13 and 14.

[0293] (1) As can be seen from Examples C1 to C2, the method of preparing a titanium metal powder provided by the present disclosure can prepare a titanium metal powder having an oxygen content less than or equal to 0.28%, and the total cost of the reductant can be reduced to 21,608 CNY per ton of titanium metal powder and is significantly reduced compared with the total cost of the reductant in the magnesium reduction process.

[0294] (2) As can be seen from Example C1, Example C3 and Example C4, the magnesium reduction in Example C1 is performed using a magnesium-containing second adjuvant under a hydrogen-containing atmosphere, a CaCl.sub.2 molten salt is adopted as the second adjuvant in Example C3, and a hydrogen-free atmosphere is adopted in Example C4. In this manner, the oxygen content of the final titanium metal powder in Example C1 is only 0.28 wt %, and the oxygen contents in Examples C3 and C4 are as high as 0.88 wt % and 2.45 wt %, respectively. Therefore, in the present disclosure, by performing the magnesium reduction steps under a hydrogen-containing atmosphere with a magnesium-containing second adjuvant, the reduction effect is improved, and the oxygen content of the titanium metal powder is reduced.

[0295] (3) As can be seen from Example C1 and Example C5, in Example C5, no sintering is performed, a dense structure thus cannot be formed, and the oxygen content of the final titanium metal powder is as high as 1.75 wt %. Therefore, in the present disclosure, by preferably performing sintering or electromagnetic induction smelting, the oxygen content of the titanium metal powder can be further reduced.

[0296] Embodiment four: The present disclosure provides a second scheme of preparing a titanium metal powder, that is, the present disclosure provides a method of preparing a titanium metal powder by three-stage reduction of titanium dioxide. As shown in FIG. 4, the preparation method includes the following steps.

[0297] (1) A calcium-containing titanium source, a first reductant and a first adjuvant are mixed, and first reduction is performed to obtain a reduced material, wherein the first reductant includes aluminum; and a first wet treatment is performed on the reduced material to obtain a first reduced powder, wherein the first reduced powder is TiO.sub.x, and x is 0.167x1.

[0298] (2) Second reduction is performed on the first reduced powder with a second reductant, and a second wet treatment is performed to obtain a second reduced powder having an oxygen content less than or equal to 2 wt %, wherein the second reductant includes magnesium.

[0299] Deep deoxidization and a deep deoxidization wet treatment are performed on the second reduced powder with a deep deoxidizer to obtain a titanium metal powder, wherein the deep deoxidizer includes magnesium and/or calcium.

[0300] Optionally, a heat treatment may be performed on the second reduced powder between the second wet treatment and the deep deoxidization.

[0301] Optionally, when the deep deoxidizer contains magnesium, a dehydrogenation treatment is performed on the product obtained after the deep deoxidization wet treatment to obtain a titanium metal powder.

Example D1

[0302] This example provides a method of preparing a titanium metal powder by three-stage reduction of titanium dioxide. The preparation method includes the following steps.

[0303] (1) A calcium-containing titanium source (a mixture of a calcium oxide and calcined titanium dioxide), an aluminum powder and a CaCl.sub.2KCl eutectic salt were mixed, wherein the molar ratio of calcium in the calcium-containing titanium source to the aluminum powder was 1.5:1, the molar ratio of the aluminum powder to titanium in the calcium-containing titanium source was 1.11:1, and the mass ratio of the CaCl.sub.2KCl eutectic salt to titanium in the calcium-containing titanium source based on TiO.sub.2 was 2.0:1; and first reduction was performed on the resulting mixture at 1000 C. under a helium atmosphere for 6 h to obtain a first reduction product.

[0304] Slurrying was performed on the first reduction product with a hydrochloric acid liquid whose pH was 1.5 to obtain a slurry, wherein the liquid-to-solid ratio was 50:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 2.0; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 42 C. with water and dried at 50 C. to obtain a TiO.sub.x intermediate powder.

[0305] (2) Second reduction was performed on the TiO.sub.x intermediate powder with a magnesium powder and a MgCl.sub.2KCl eutectic salt at 800 C. under a helium atmosphere for 4 h to obtain a second reduction product, wherein the mass ratio of the magnesium powder to the TiO.sub.x intermediate powder was 0.15:1, and the mass ratio of the MgCl.sub.2KCl eutectic salt to the TiO.sub.x intermediate powder was 2.0:1.

[0306] Slurrying was performed on the second reduction product with water to obtain a slurry, wherein the liquid-to-solid ratio was 80:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 2.5; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 55 C. with water and dried at 55 C. to obtain a second reduced powder.

[0307] (3) A heat treatment was performed on the second reduced powder at 1000 C. under vacuum for 4 h, and deep deoxidization was performed with a magnesium powder and a MgCl.sub.2KCl eutectic salt at 800 C. under a pure hydrogen atmosphere for 4 h to obtain a deep deoxidization product, wherein the mass ratio of the magnesium powder to the second reduced powder was 0.08:1, and the mass ratio of the MgCl.sub.2KCl eutectic salt to the second reduced powder was 2.0:1.

[0308] Slurrying was performed on the deep deoxidization product with a hydrochloric acid liquid whose pH was 0.5 to obtain a slurry, wherein the liquid-to-solid ratio was 20:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 1.8; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 50 C. with water and dried at 50 C. to obtain a titanium metal powder.

[0309] A dehydrogenation treatment was performed on the titanium metal powder at 800 C. under an argon atmosphere to obtain a final titanium metal powder.

Example D2

[0310] This example provides a method of preparing a titanium metal powder by three-stage reduction of titanium dioxide. The preparation method includes the following steps.

[0311] (1) A calcium-containing titanium source (a mixture of a calcium oxide and calcined titanium dioxide), an aluminum powder and a CaCl.sub.2NaCl eutectic salt were mixed, wherein the molar ratio of calcium in the calcium-containing titanium source to the aluminum powder was 1.5:1, the molar ratio of the aluminum powder to titanium in the calcium-containing titanium source was 1.22:1, and the mass ratio of the CaCl.sub.2NaCl eutectic salt to titanium in the calcium-containing titanium source based on TiO.sub.2 was 2.5:1; and first reduction was performed on the resulting mixture at 900 C. under a helium atmosphere for 12 h to obtain a first reduction product.

[0312] Slurrying was performed on the first reduction product with a hydrochloric acid whose pH was 0.5 to obtain a slurry, wherein the liquid-to-solid ratio was 10:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 2.0; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 50 C. with water and dried at 50 C. to obtain a TiO.sub.x intermediate powder.

[0313] (2) Second reduction was performed on the TiO.sub.x intermediate powder with a magnesium powder and a MgCl.sub.2NaCl eutectic salt at 700 C. under a helium atmosphere for 10 h to obtain a second reduction product, wherein the mass ratio of the magnesium powder to the TiO.sub.x intermediate powder was 0.15:1, and the mass ratio of the MgCl.sub.2NaCl eutectic salt to the TiO.sub.x intermediate powder was 2.0:1.

[0314] Slurrying was performed on the second reduction product with a hydrochloric acid whose pH was 1.0 to obtain a slurry, wherein the liquid-to-solid ratio was 30:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.9 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 2.5; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 30 C. with water and dried at 55 C. to obtain a second reduced powder.

[0315] (3) A heat treatment was performed on the second reduced powder at 900 C. under an argon atmosphere for 18 h, and deep deoxidization was performed with a magnesium powder and anhydrous MgCl.sub.2 at 650 C. under a hydrogen-argon mixed atmosphere (where the volume fraction of hydrogen was 85%) for 48 h to obtain a deep deoxidization product, wherein the mass ratio of the magnesium powder to the second reduced powder was 0.05:1, and the mass ratio of anhydrous MgCl.sub.2 to the second reduced powder was 0.5:1.

[0316] Slurrying was performed on the deep deoxidization product with a hydrochloric acid liquid whose pH was 1.5 to obtain a slurry, wherein the liquid-to-solid ratio was 30:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 3.0; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 55 C. with water and dried at 55 C. to obtain a titanium metal powder.

[0317] A dehydrogenation treatment was performed on the titanium metal powder at 1000 C. under an argon atmosphere to obtain a final titanium metal powder.

Example D3

[0318] This example provides a method of preparing a titanium metal powder by three-stage reduction of titanium dioxide. The preparation method includes the following steps.

[0319] (1) A calcium-containing titanium source (a mixture of a calcium oxide and a calcined product obtained after the calcination of calcium oxide and titanium dioxide mixed based on the stoichiometric ratio of calcium titanate), an aluminum powder and anhydrous CaCl.sub.2 were mixed, wherein the molar ratio of calcium in the calcium-containing titanium source to the aluminum powder was 0.6:1, the molar ratio of the aluminum powder to titanium in the calcium-containing titanium source was 0.67:1, and the mass ratio of anhydrous CaCl.sub.2 to titanium in the calcium-containing titanium source based on TiO.sub.2 was 1.0:1; and first reduction was performed on the resulting mixture at 1100 C. under vacuum for 4 h to obtain a first reduction product.

[0320] Slurrying was performed on the first reduction product with a hydrochloric acid liquid whose pH was 0.5 to obtain a slurry, wherein the liquid-to-solid ratio was 10:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 1.5; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 0 C. with water and dried at 45 C. to obtain a TiO.sub.x intermediate powder.

[0321] (2) Second reduction was performed on the TiO.sub.x intermediate powder with a magnesium powder and a MgCl.sub.2CaCl.sub.2 eutectic salt at 900 C. under an argon atmosphere for 0.25 h to obtain a second reduction product, wherein the mass ratio of the magnesium powder to the TiO.sub.x intermediate powder was 0.35:1, and the mass ratio of the MgCl.sub.2CaCl.sub.2 eutectic salt to the TiO.sub.x intermediate powder was 1.0:1.

[0322] Slurrying was performed on the second reduction product with a hydrochloric acid whose pH was 1.0 to obtain a slurry, wherein the liquid-to-solid ratio was 15:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 1.0 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 1.5; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 25 C. with water and dried at 40 C. to obtain a second reduced powder.

[0323] (3) A heat treatment was performed on the second reduced powder at 1100 C. under vacuum for 2 h, and deep deoxidization was performed with a magnesium powder and anhydrous CaCl.sub.2 at 1100 C. under an argon atmosphere for 2 h to obtain a deep deoxidization product, wherein the mass ratio of the magnesium powder to the second reduced powder was 0.15:1, and the mass ratio of anhydrous CaCl.sub.2 to the second reduced powder was 2.0:1.

[0324] Slurrying was performed on the deep deoxidization product with a hydrochloric acid liquid whose pH was 1.0 to obtain a slurry, wherein the liquid-to-solid ratio was 10:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 3.0; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 30 C. with water and dried at 60 C. to obtain a titanium metal powder.

Example D4

[0325] This example provides a method of preparing a titanium metal powder by three-stage reduction of titanium dioxide. The preparation method includes the following steps.

[0326] (1) A calcium-containing titanium source (a mixture of a calcium oxide and calcined titanium dioxide), an aluminum powder and a CaCl.sub.2KCl eutectic salt were mixed, wherein the molar ratio of calcium in the calcium-containing titanium source to the aluminum powder was 2.0:1, the molar ratio of the aluminum powder to titanium in the calcium-containing titanium source was 1.22:1, and the mass ratio of the CaCl.sub.2KCl eutectic salt to titanium in the calcium-containing titanium source based on TiO.sub.2 was 1.5:1; and first reduction was performed on the resulting mixture at 700 C. under a helium atmosphere for 24 h to obtain a first reduction product.

[0327] Slurrying was performed on the first reduction product with water to obtain a slurry, wherein the liquid-to-solid ratio was 100:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 3.0; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 60 C. with water and dried at 60 C. to obtain a TiO.sub.x intermediate powder.

[0328] (2) Second reduction was performed on the TiO.sub.x intermediate powder with a magnesium powder and a MgCl.sub.2KCl eutectic salt at 650 C. under a hydrogen atmosphere for 48 h to obtain a second reduction product, wherein the mass ratio of the magnesium powder to the TiO.sub.x intermediate powder was 0.2:1, and the mass ratio of the MgCl.sub.2KCl eutectic salt to the TiO.sub.x intermediate powder was 3.0:1.

[0329] Slurrying was performed on the second reduction product with a hydrochloric acid whose pH was 2.0 to obtain a slurry, wherein the liquid-to-solid ratio was 100:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 1.0 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 3.0; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 15 C. with water and dried at 60 C. to obtain a second reduced powder.

[0330] (3) A heat treatment was performed on the second reduced powder at 800 C. under an argon atmosphere for 24 h, and deep deoxidization was performed with a magnesium powder and a CaCl.sub.2LiCl eutectic salt at 900 C. under a helium atmosphere for 16 h to obtain a deep deoxidization product, wherein the mass ratio of the magnesium powder to the second reduced powder was 0.03:1, and the mass ratio of the CaCl.sub.2LiCl eutectic salt to the second reduced powder was 1.0:1.

[0331] Slurrying was performed on the deep deoxidization product with a hydrochloric acid liquid whose pH was 1.5 to obtain a slurry, wherein the liquid-to-solid ratio was 40:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 1.0 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 1.5; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 40 C. with water and dried at 45 C. to obtain a titanium metal powder.

Example D5

[0332] The preparation method of this example is the same as the preparation method of Example D1 except that the MgCl.sub.2KCl eutectic salt in step (2) was replaced with a CaCl.sub.2KCl eutectic salt.

Example D6

[0333] The preparation method of this example is the same as the preparation method of Example D1 except that the pure hydrogen atmosphere in the deep deoxidization in step (3) was replaced with a helium atmosphere.

Example D7

[0334] The preparation method of this example is the same as the preparation method of Example D1 except that no heat treatment was performed on the second reduced powder in step (3).

[0335] The measurement and calculation results of the preceding examples are shown in Table 15.

TABLE-US-00015 TABLE 15 Oxygen Oxygen Aluminum Calcium Magnesium Reductant content of content of consumed consumed consumed cost of Value of second titanium per ton of per ton of per ton of per ton of x in TiO.sub.x reduced metal titanium titanium titanium titanium intermediate powder/ powder/ metal metal metal metal powder wt % wt % powder powder powder powder Example 0.5 4.99 0.18 0.6244 / 0.2592 22,856 CNY D1 Example 0.33 2.0 0.15 0.6863 / 0.2177 22,434 CNY D2 Example 1.0 4.01 0.12 0.3769 0.1563 0.4667 33,240 CNY D3 Example 0.33 0.49 0.08 0.6863 0.0302 0.2222 23,973 CNY D4

TABLE-US-00016 TABLE 16 Product obtained after Oxygen content Oxygen content the first wet treatment of second of titanium is performed on the reduced powder metal powder first reduction product (wt %) (wt %) Example D5 Ti.sub.2O, i.e., x = 0.5 5.51 0.29 Example D6 Ti.sub.2O, i.e., x = 0.5 4.99 2.42 Example D7 Ti.sub.2O, i.e., x = 0.5 4.99 1.78

[0336] / in the preceding tables indicates that there is no related data.

[0337] The following conclusions can be drawn from Tables 15 and 16.

[0338] (1) As can be seen from Examples D1 to D4, the method of preparing a titanium metal powder provided by the present disclosure can prepare a titanium metal powder having an oxygen content less than or equal to 0.2%, and the cost of the reductant can be reduced to 22,434 CNY per ton of titanium metal powder and is only 56% of the cost of the reductant in the magnesium reduction.

[0339] (2) As can be seen from Example D1 and Example D5, the magnesium reduction in Example D1 adopts a magnesium-containing second adjuvant, and a CaCl.sub.2KCl eutectic salt is adopted as the second adjuvant in Example D5. In this manner, the oxygen content of the second reduced powder in Example D1 is 4.99 wt %, and the oxygen content in Example D5 is as high as 5.51 wt %. Therefore, in the present disclosure, by performing the magnesium reduction steps with a magnesium-containing second adjuvant, the reduction effect is improved.

[0340] (3) As can be seen from Example D1 and Example D6, in Example D6, magnesium is used as the deoxidizer, a hydrogen-free atmosphere is adopted, and thus the oxygen content of the final titanium metal powder is as high as 2.42 wt %. Therefore, in the present disclosure, by preferably adopting magnesium and a hydrogen-containing atmosphere to perform deep deoxidization, the deep deoxidization can be significantly improved, and the oxygen content of the titanium metal powder can be further reduced.

[0341] (4) As can be seen from Example D1 and Example D7, in Example D7, no heat treatment is performed, a dense structure thus cannot be formed, and the oxygen content of the final titanium metal powder is as high as 1.78 wt %. Therefore, in the present disclosure, by preferably performing heat treatment, the oxygen content of the titanium metal powder can be further reduced.

Embodiment five: The present disclosure provides a third scheme of preparing a

[0342] titanium metal powder, that is, the present disclosure provides a method of preparing a titanium metal powder by reduction of titanium dioxide. As shown in FIG. 5, the preparation method includes the following steps.

[0343] (1) A calcium-containing titanium source, a first reductant and a first adjuvant are mixed, and first reduction is performed to obtain a reduced material, wherein the first reductant includes aluminum; and a first wet treatment is performed on the reduced material to obtain a first reduced powder, wherein the first reduced powder is TiO.sub.x, and x is 0.333x0.5.

[0344] (2) A first reduced powder and a titanium metal powder partially returned are mixed to obtain a mixed material, first sintering is performed on the mixed material to obtain a titanium-oxygen solid solution having an oxygen content less than or equal to 8 wt %, and deep deoxidization and a deep deoxidization wet treatment are performed on the titanium-oxygen solid solution with a deep deoxidizer to obtain a titanium metal powder, wherein the deep deoxidizer includes magnesium and/or calcium.

[0345] Optionally, when the deep deoxidizer is magnesium, a dehydrogenation treatment is performed on the product obtained after the deep deoxidization wet treatment to obtain a titanium metal powder. Part of the titanium metal powder is outputted, and part is returned to be mixed with the first reduced powder.

Example E1

[0346] This example provides a method of preparing a titanium metal powder by reduction of titanium dioxide. The preparation method includes the following steps.

[0347] (1) A calcium-containing titanium source (a mixture of a calcium oxide and calcined titanium dioxide), an aluminum powder and a CaCl.sub.2NaCl eutectic salt were mixed, wherein the molar ratio of calcium in the calcium-containing titanium source to the aluminum powder was 1.3:1, the molar ratio of the aluminum powder to titanium in the calcium-containing titanium source was 1.0:1, and the mass ratio of the CaCl.sub.2NaCl eutectic salt to titanium in the calcium-containing titanium source based on TiO.sub.2 was 1.5:1; and first reduction was performed on the resulting mixture at 790 C. under a helium atmosphere for 10 h to obtain a first reduction product.

[0348] Slurrying was performed on the first reduction product with a hydrochloric acid liquid whose pH was 0.5 to obtain a slurry, wherein the liquid-to-solid ratio was 40:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 1.8; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 45 C. with water and dried at 55 C. to obtain a TiO.sub.x intermediate powder.

[0349] (2) The TiO.sub.x intermediate powder and the titanium metal powder returned in step (3) were directly dry mixed by tumble at a mass ratio of 1:0.8 to obtain a mixed material, and the mixed material was sintered at 1200 C. under an argon atmosphere for 6 h to obtain a titanium-oxygen solid solution.

[0350] (3) Deep deoxidization was performed on the titanium-oxygen solid solution with a magnesium powder and a MgCl.sub.2KCl eutectic salt at 850 C. under a hydrogen-argon mixed atmosphere (where the volume fraction of hydrogen was 70%) for 2 h to obtain a deep deoxidization product, wherein the mass ratio of the magnesium powder to the titanium-oxygen solid solution was 0.3:1, and the mass ratio of the MgCl.sub.2KCl eutectic salt to the titanium-oxygen solid solution was 2:1.

[0351] Slurrying was performed on the deep deoxidization product with water to obtain a slurry, wherein the liquid-to-solid ratio was 5:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 1.6; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 50 C. with water and dried at 40 C. to obtain a titanium metal powder.

Example E2

[0352] This example provides a method of preparing a titanium metal powder by reduction of titanium dioxide. The preparation method includes the following steps.

[0353] (1) A calcium-containing titanium source (a mixture of a calcium oxide and a calcined product obtained after the calcination of a calcium oxide and titanium dioxide mixed based on the stoichiometric ratio of CaTiO.sub.3), an aluminum powder and anhydrous CaCl.sub.2 were mixed, wherein the molar ratio of calcium in the calcium-containing titanium source to the aluminum powder was 0.6:1, the molar ratio of the aluminum powder to titanium in the calcium-containing titanium source was 1.22:1, and the mass ratio of anhydrous CaCl.sub.2 to titanium in the calcium-containing titanium source based on TiO.sub.2 was 3:1; and first reduction was performed on the resulting mixture at 1200 C. under an argon atmosphere for 0.25 h to obtain a first reduction product.

[0354] Slurrying was performed on the first reduction product with a hydrochloric acid liquid whose pH was 1.5 to obtain a slurry, wherein the liquid-to-solid ratio was 100:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 1.5; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 40 C. with water and dried at 0 C. to obtain a TiO.sub.x intermediate powder.

[0355] (2) The TiO.sub.x intermediate powder was ground into a slurry until the particle size of the TiO.sub.x intermediate powder in the slurry was 10 m or less, the slurry and the titanium metal powder returned in step (3) were mixed, and the resulting mixture was stirred and dried to obtain a mixed material, wherein the mass ratio of the TiO.sub.x intermediate powder to the titanium metal powder was 1:4; and the mixed material was sintered at 800 C. under vacuum for 24 h to obtain a titanium-oxygen solid solution.

[0356] (3) Deep deoxidization was performed on the titanium-oxygen solid solution with calcium particles and anhydrous CaCl.sub.2 at 900 C. under a hydrogen-argon mixed atmosphere (where the volume fraction of hydrogen was 30%) for 1 h to obtain a deep deoxidization product, wherein the mass ratio of the calcium particles to the titanium-oxygen solid solution was 0.08:1, and the mass ratio of anhydrous CaCl.sub.2 to the titanium-oxygen solid solution was 0.05:1.

[0357] Slurrying was performed on the deep deoxidization product with a hydrochloric acid liquid whose pH was 1.0 to obtain a slurry, wherein the liquid-to-solid ratio was 20:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 3.0; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 20 C. with water and dried at 45 C. to obtain a titanium metal powder.

Example E3

[0358] The preparation method of this example is the same as the preparation method of Example E1 except that the direct drying power mixing step in step (2) was replaced with the following steps: the TiO.sub.x intermediate powder and the titanium metal powder were mixed, crushed by ball milling, spray pelletized and sintered to obtain a nearly spherical titanium-oxygen solid solution.

[0359] The measurement and calculation results as well as the effects of the preceding examples and comparative examples are shown in Table 17 and Table 18.

TABLE-US-00017 TABLE 17 Magnesium Oxygen Aluminum or calcium content of consumed consumed Value of x Oxygen content titanium per ton of per ton of Reductant cost in TiO.sub.x of the titanium- metal titanium titanium of per ton of intermediate oxygen solid powder metal metal titanium metal powder solution (wt %) (wt %) powder powder powder Example 0.5 7.94 0.18 0.5625 0.6300 36,450 CNY E1 Example 0.17 1.193 0.15 0.6863 0.4167 32,480 CNY E2

TABLE-US-00018 TABLE 18 Oxygen content Product obtained after of the titanium- Oxygen content the first wet treatment oxygen solid of titanium is performed on the solution metal powder first reduction product (wt %) (wt %) Example Ti.sub.2O, i.e., x = 0.5 7.94 0.12 E3

[0360] / in the preceding tables indicates that there is no related data.

[0361] The following conclusions can be drawn from Tables 17 and 18.

[0362] (1) As can be seen from Examples E1 and E2, the method of preparing a titanium metal powder by reduction of titanium dioxide provided by the present disclosure can prepare a titanium metal powder having an oxygen content less than 0.3%, and the cost of the reductant can be reduced to 32,480 CNY per ton of titanium metal powder and is only 55% of the cost of the reductant in the magnesium reduction process.

[0363] (2) As can be seen from Examples E1 and E3, the manner of spray pelletizing and sintering is adopted in Example E3, and the oxygen content of the titanium metal powder can be further reduced compared with the oxygen content in Example E1.

Embodiment six: The present disclosure provides a fourth scheme of preparing a

[0364] titanium metal powder, that is, the present disclosure provides a method of preparing a low-oxygen titanium metal powder. As shown in FIG. 6, the preparation method includes the following steps.

[0365] (1) A calcium-containing titanium source, a first reductant and a first adjuvant are mixed, and first reduction is performed to obtain a reduced material, wherein the first reductant includes aluminum; and a first wet treatment is performed on the reduced material to obtain a first reduced powder, wherein the first reduced powder is TiO.sub.x, and x is 0.333x0.5.

[0366] (2) Second reduction is performed on titanium dioxide with a second reductant, and a second wet treatment is performed to obtain a second reduced powder having an oxygen content less than or equal to 3 wt %.

[0367] (3) The second reduced powder and a first reduced powder are mixed, and second sintering is performed to obtain a titanium-oxygen solid solution having an oxygen content less than or equal to 8 wt %; and deep deoxidization and a deep deoxidization wet treatment are performed on the titanium-oxygen solid solution with a deep deoxidizer to obtain a titanium metal powder, wherein the deep deoxidizer includes magnesium and/or calcium.

Example F1

[0368] This example provides a method of preparing a low-oxygen titanium metal powder.

[0369] The preparation method includes the following steps.

[0370] (1) A calcium-containing titanium source (a mixture of a calcium oxide and calcined titanium dioxide), an aluminum powder and a CaCl.sub.2KCl eutectic salt were mixed, wherein the molar ratio of calcium in the calcium-containing titanium source to the aluminum powder was 1.5:1, the molar ratio of the aluminum powder to titanium in the calcium-containing titanium source was 1.1:1, and the mass ratio of the CaCl.sub.2KCl eutectic salt to titanium in the calcium-containing titanium source based on TiO.sub.2 was 0.5:1; and first reduction was performed on the resulting mixture at 1000 C. under a helium atmosphere for 6 h to obtain a first reduction product.

[0371] Slurrying was performed on the first reduction product with water to obtain a slurry, wherein the liquid-to-solid ratio was 70:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 2.0; the slurry was filtered to obtain a solid phase; and the solid phase was washed at room temperature and dried at 40 C. to obtain a first reduced powder.

[0372] Second reduction was performed on titanium dioxide with a magnesium powder and a MgCl.sub.2KCl eutectic salt at 700 C. under a helium atmosphere for 24 h to obtain a second reduction product, wherein the mass ratio of the magnesium powder to the titanium dioxide was 2.0:1, and the mass ratio of the MgCl.sub.2KCl eutectic salt to the titanium dioxide was 2.5:1.

[0373] Slurrying was performed on the second reduction product with water to obtain a slurry, wherein the liquid-to-solid ratio was 20:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 1.2; the slurry was filtered to obtain a solid phase; and the solid phase was washed at room temperature and dried at 48 C. to obtain a second reduced powder.

[0374] (2) The first reduced powder and the second reduced powder were mixed in a mass ratio of 1:1 and sintered at 1000 C. under vacuum for 12 h to obtain a titanium-oxygen solid solution.

[0375] (3) Deep deoxidization was performed on the titanium-oxygen solid solution with a magnesium powder and a MgCl.sub.2KCl eutectic salt at 650 C. under a hydrogen-argon mixed atmosphere (where the volume fraction of hydrogen was 95%) for 18 h to obtain a deep deoxidization product, wherein the mass ratio of the magnesium powder to the titanium-oxygen solid solution was 0.15:1, and the mass ratio of the MgCl.sub.2KCl eutectic salt to the titanium-oxygen solid solution was 2.0:1.

[0376] Slurrying was performed on the deep deoxidization product with a hydrochloric acid liquid whose pH was 0.5 to obtain a slurry, wherein the liquid-to-solid ratio was 25:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 2.5; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 25 C. and dried at 40 C. to obtain a low-oxygen titanium metal powder.

Example F2

[0377] This example provides a method of preparing a low-oxygen titanium metal powder. The preparation method includes the following steps.

[0378] (1) A calcium-containing titanium source (a mixture of a calcium oxide and a calcined product obtained after the calcination of a calcium oxide and titanium dioxide mixed based on the stoichiometric ratio of CaTiO.sub.3), an aluminum powder and anhydrous CaCl.sub.2 were mixed, wherein the molar ratio of calcium in the calcium-containing titanium source to the aluminum powder was 0.6:1, the molar ratio of the aluminum powder to titanium in the calcium-containing titanium source was 1.0:1, and the mass ratio of anhydrous CaCl.sub.2 to titanium in the calcium-containing titanium source based on TiO.sub.2 was 3:1; and first reduction was performed on the resulting mixture at 1200 C. under vacuum for 24 h to obtain a first reduction product.

[0379] Slurrying was performed on the first reduction product with a hydrochloric acid liquid whose pH was 2.5 to obtain a slurry, wherein the liquid-to-solid ratio was 100:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 1.0 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 1.5; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 45 C. and dried at 60 C. to obtain a first reduced powder.

[0380] Second reduction was performed on titanium dioxide with a magnesium powder and a MgCl.sub.2CaCl.sub.2 eutectic salt at 600 C. under an argon atmosphere for 48 h to obtain a second reduction product, wherein the mass ratio of the magnesium powder to the titanium dioxide was 2:1, and the mass ratio of the MgCl.sub.2CaCl.sub.2 eutectic salt to the titanium dioxide was 3:1.

[0381] Slurrying was performed on the second reduction product with a hydrochloric acid liquid whose pH was 0.5 to obtain a slurry, wherein the liquid-to-solid ratio was 100:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 1.5; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 0 C. and dried at 30 C. to obtain a second reduced powder.

[0382] (2) The first reduced powder and the second reduced powder were mixed in a mass ratio of 1:10 and sintered at 800 C. under an argon atmosphere for 24 h to obtain a titanium-oxygen solid solution.

[0383] (3) Deep deoxidization was performed on the titanium-oxygen solid solution with a calcium powder and anhydrous CaCl.sub.2 at 1000 C. under an argon atmosphere for 24 h to obtain a deep deoxidization product, wherein the mass ratio of the calcium powder to the titanium-oxygen solid solution was 0.09:1, and the mass ratio of anhydrous CaCl.sub.2 to the titanium-oxygen solid solution was 0.05:1.

[0384] Slurrying was performed on the deep deoxidization product with water to obtain a slurry, wherein the liquid-to-solid ratio was 100:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 3.0; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 0 C. with water and dried at 45 C. to obtain a low-oxygen titanium metal powder.

Example F3

[0385] This example provides a method of preparing a low-oxygen titanium metal powder. The preparation method includes the following steps.

[0386] (1) A calcium-containing titanium source (a mixture of a calcium oxide and calcined titanium dioxide), an aluminum powder and a CaCl.sub.2LiCl eutectic salt were mixed, wherein the molar ratio of calcium in the calcium-containing titanium source to the aluminum powder was 2.0:1, the molar ratio of the aluminum powder to titanium in the calcium-containing titanium source was 1.22:1, and the mass ratio of the CaCl.sub.2LiCl eutectic salt to titanium in the calcium-containing titanium source based on TiO.sub.2 was 0.05:1; and first reduction was performed on the resulting mixture at 800 C. under a helium atmosphere for 12 h to obtain a first reduction product.

[0387] Slurrying was performed on the first reduction product with a hydrochloric acid liquid whose pH was 1.0 to obtain a slurry, wherein the liquid-to-solid ratio was 80:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 1.0 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 3.0; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 10 C. and dried at 50 C. to obtain a first reduced powder.

[0388] Second reduction was performed on titanium dioxide with a magnesium powder and a MgCl.sub.2KCl eutectic salt at 900 C. under a hydrogen atmosphere for 0.25 h to obtain a second reduction product, wherein the mass ratio of the magnesium powder to the titanium dioxide was 2.05:1, and the mass ratio of the MgCl.sub.2KCl eutectic salt to the titanium dioxide was 0.05:1.

[0389] Slurrying was performed on the second reduction product with a hydrochloric acid liquid whose pH was 0.8 to obtain a slurry, wherein the liquid-to-solid ratio was 20:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 2.5; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 15 C. and dried at 20 C. to obtain a second reduced powder.

[0390] (2) The first reduced powder and the second reduced powder were mixed in a mass ratio of 1:0.267 and sintered at 1200 C. under a helium atmosphere for 0.25 h to obtain a titanium-oxygen solid solution.

[0391] (3) Deep deoxidization was performed on the titanium-oxygen solid solution with a calcium powder and a CaCl.sub.2MgCl.sub.2 eutectic salt at 700 C. under a hydrogen atmosphere for 48 h to obtain a deep deoxidization product, wherein the mass ratio of the calcium powder to the titanium-oxygen solid solution was 0.25:1, and the mass ratio of the CaCl.sub.2MgCl.sub.2 eutectic salt to the titanium-oxygen solid solution was 3:1.

[0392] Slurrying was performed on the deep deoxidization product with a hydrochloric acid liquid of water to obtain a slurry, wherein the liquid-to-solid ratio was 80:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 1.5; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 0 C. and dried at 30 C. to obtain a low-oxygen titanium metal powder.

Example F4

[0393] This example provides a method of preparing a low-oxygen titanium metal powder. The preparation method includes the following steps.

[0394] (1) A calcium-containing titanium source (a mixture of a calcium oxide and titanium dioxide which were weighted in a ratio exceeding the stoichiometric ratio based on CaTiO.sub.3, mixed and calcined), an aluminum powder and a CaCl.sub.2KCl eutectic salt were mixed, wherein the molar ratio of calcium in the calcium-containing titanium source to the aluminum powder was 1.5:1, the molar ratio of the aluminum powder to titanium in the calcium-containing titanium source was 1.15:1, and the mass ratio of the CaCl.sub.2KCl eutectic salt to titanium in the calcium-containing titanium source based on TiO.sub.2 was 2.2:1; and first reduction was performed on the resulting mixture at 1000 C. under vacuum for 20 h to obtain a first reduction product.

[0395] Slurrying was performed on the first reduction product with a hydrochloric acid liquid whose pH was 1.0 to obtain a slurry, wherein the liquid-to-solid ratio was 40:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 1.0 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 2.5; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 20 C. and dried at 45 C. to obtain a first reduced powder.

[0396] Second reduction was performed on titanium dioxide with a magnesium powder and a MgCl.sub.2KCl eutectic salt at 700 C. under a hydrogen atmosphere for 3 h to obtain a second reduction product, wherein the mass ratio of the magnesium powder to the titanium dioxide was 2.1:1, and the mass ratio of the MgCl.sub.2KCl eutectic salt to the titanium dioxide was 1.5:1.

[0397] Slurrying was performed on the second reduction product with a hydrochloric acid liquid whose pH was 1.0 to obtain a slurry, wherein the liquid-to-solid ratio was 15:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 2.8; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 25 C. and dried at 20 C. to obtain a second reduced powder.

[0398] (2) The first reduced powder and the second reduced powder were mixed in a mass ratio of 1:3 and sintered at 900 C. under an argon atmosphere for 12 h to obtain a titanium-oxygen solid solution.

[0399] (3) Deep deoxidization was performed on the titanium-oxygen solid solution with a magnesium powder and a MgCl.sub.2KCl eutectic salt at 900 C. under a pure hydrogen atmosphere for 3 h to obtain a deep deoxidization product, wherein the mass ratio of the magnesium powder to the titanium-oxygen solid solution was 0.1:1, and the mass ratio of the MgCl.sub.2KCl eutectic salt to the titanium-oxygen solid solution was 3:1.

[0400] Slurrying was performed on the deep deoxidization product with a hydrochloric acid liquid of water to obtain a slurry, wherein the liquid-to-solid ratio was 80:1 mL/g; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 2.0; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 0 C. and dried at 55 C. to obtain a low-oxygen titanium metal powder.

Example F5

[0401] The preparation method of this example is the same as the preparation method of Example F1 except that the first reduced powder and the second reduced powder were mixed in a mass ratio of 1:0.1 in step (2).

Example F6

[0402] The preparation method of this example is the same as the preparation method of Example F1 except that the first reduced powder and the second reduced powder were mixed in a mass ratio of 1:14 in step (2).

[0403] The measurement and calculation results as well as the effects of the preceding examples are shown in Tables 19 and 20.

TABLE-US-00019 TABLE 19 Oxygen content Oxygen of the Oxygen Aluminum Calcium Magnesium Reductant content of titanium- content of consumed consumed consumed cost of Value of x second oxygen titanium per ton of per ton of per ton of per ton of in TiO.sub.x reduced solid metal titanium titanium titanium titanium intermediate powder solution powder metal metal metal metal powder (wt %) (wt %) (wt %) powder powder powder powder Example 0.38 2.10 6.67 0.11 0.294 0 0.685 33,280 F1 CNY Example 0.50 1.98 3.10 0.08 0.045 0.0929 0.9196 41,865 F2 CNY Example 0.333 0.51 8.00 0.09 0.535 0.272 0.236 32,380 F3 CNY Example 0.36 1.22 3.60 0.16 0.150 0 0.9106 39,420 F4 CNY

TABLE-US-00020 TABLE 20 Oxygen content Product obtained after Oxygen content of the titanium- Oxygen content the first wet treatment of second oxygen solid of titanium is performed on the reduced powder solution metal powder first reduction product (wt %) (wt %) (wt %) Example Mixture of Ti.sub.2O and Ti.sub.3O, 2.10 8, which is / F5 with an average chemical beyond formula of TiO.sub.0.38 expectation Example Mixture of Ti.sub.2O and Ti.sub.3O, 2.10 2.71 0.10 F6 with an average chemical formula of TiO.sub.0.38

[0404] / in the preceding tables indicates that there is no related data.

[0405] The following conclusions can be drawn from Table 19 and Table 20.

[0406] (1) As can be seen from Examples F1 to F4, the method of preparing a titanium metal powder provided by the present disclosure can prepare a titanium metal powder having an oxygen content less than 0.200 while such a low oxygen content cannot be achieved through the simple reduction of titanium dioxide with magnesium, and the cost of the reductant is reduced by more than 20% compared with the cost of the reductant in the full-magnesium reduction process.

[0407] (2) As can be seen from Example F1, Example F5 and Example F6, in Example F5, the mass ratio of the first reduced powder and the second reduced powder is 1:0.1, the oxygen content of the titanium-oxygen solid solution thus exceeds the expected 8 wt %, the subsequent sintering effect is poor, and the expected low-oxygen titanium metal powder cannot be achieved after the reduction; in Example F6, the amount of the second reduced powder used is high, the amount of the reductant Mg used is thus significantly increased, and the effect of reducing the cost of the reductant cannot be achieved. Therefore, in the present disclosure, by controlling the mass ratio of the first reduced powder and the second reduced powder within a specific range, the oxygen content can be better controlled, and the cost of the reductant can be reduced.

[0408] Embodiment seven: The present disclosure provides a method of preparing a Ti6Al4V alloy powder. As shown in FIG. 7, the preparation method includes the following steps.

[0409] (1) First reduction is performed on a mixture of a vanadium oxide and a calcium oxide with a first reductant and a first adjuvant to obtain a first reduced material, and a first wet treatment is performed on the first reduced material to obtain a 6Al4V alloy powder, wherein the mass ratio of vanadium to aluminum in the 6Al4V alloy powder is (3.5 to 4.5):(5.5 to 6.75), and the first reductant includes aluminum.

[0410] Third reduction is performed on titanium dioxide with a third reductant to obtain a third reduced material, and a third wet treatment is performed on the third reduced material to obtain a third reduced powder, wherein a calcium oxide is added in the third reduction, the third reduced powder is TiO.sub.x, and x is less than or equal to 0.5.

[0411] (2) The 6Al4V alloy powder and the third reduced powder are mixed, fourth sintering is performed on resulting mixture to obtain an oxygen-containing Ti6Al4V alloy powder, second deoxidization is performed on the oxygen-containing Ti6Al4V alloy powder with a second deoxidizer and a second deoxidization adjuvant, and a fourth wet treatment is performed to obtain a Ti6Al4V alloy powder.

Example G1

[0412] This example provides a method of preparing a Ti6Al4V alloy powder. The preparation method includes the following steps.

[0413] (1) Third reduction was performed on titanium dioxide with a third reductant aluminum (fragmental), a third adjuvant CaCl.sub.2KCl eutectic salt and a calcium oxide at 1200 C. under an argon atmosphere for 10 h to obtain a third reduced material, wherein the molar ratio of aluminum to titanium dioxide was 1.02:1, the molar ratio of the calcium oxide to aluminum was 0.8:1, and the mass ratio of the CaCl.sub.2KCl eutectic salt to titanium dioxide was 2.5:1.

[0414] Slurrying was performed on the third reduced material with a hydrochloric acid liquid whose pH was 0.5 to obtain a slurry; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 2.2; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 45 C. and dried at 55 C. under vacuum to obtain a third reduced powder TiO.sub.x.

[0415] A vanadium oxide (where the molar ratio of vanadium trioxide to vanadium pentoxide was 2:3), a calcium oxide, an aluminum powder and a CaCl.sub.2KCl eutectic salt were mixed, wherein the molar ratio of the aluminum powder to the vanadium oxide was 42.33:5, the molar ratio of the calcium oxide to the aluminum powder was 1.5:1, and the mass ratio of the CaCl.sub.2KCl eutectic salt to the vanadium oxide was 2.5:1; and first reduction was performed on the resulting mixture at 800 C. under a helium atmosphere for 10 h to obtain a first reduced material.

[0416] Slurrying was performed on the first reduced material with water to obtain a slurry; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 2.5; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 25 C. and dried at 45 C. under vacuum to obtain a 6Al4V alloy powder.

[0417] (2) The third reduced powder TiO.sub.x and the 6Al4V alloy powder were mixed, crushed by ball milling, spray-pelletized, and sintered at 1200 C. under vacuum for 12 h to obtain an oxygen-containing Ti6Al4V alloy powder. Second deoxidization was performed on the oxygen-containing Ti6Al4V alloy powder with magnesium (granular) as a second deoxidizer at 740 C. under a hydrogen-argon mixed atmosphere (where the volume fraction of hydrogen was 65%) for 12 h to obtain a second deoxidization product, wherein the mass ratio of the oxygen-containing Ti6Al4V alloy powder to the second deoxidizer was 1:0.4, anhydrous MgCl.sub.2 was added in the second deoxidization, and the mass ratio of anhydrous MgCl.sub.2 to the oxygen-containing Ti6Al4V alloy powder was 2:1.

[0418] Slurrying was performed on the second deoxidization product with a hydrochloric acid liquid whose pH was 0.8 to obtain a slurry; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 1.5; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 40 C. and dried at 50 C. under vacuum to obtain a Ti6Al4V alloy powder.

[0419] The SEM diagram of the 6Al4V alloy powder obtained after the first reduction of this example is shown in FIG. 8. As can be seen from FIG. 8, the 6Al4V alloy powder is spherical. As can be seen from FIG. 9, the mass fraction of A1 is 59.48 wt %, and the mass fraction of V is 40.52 wt %, which accords with the compositions of the 6Al4V alloy powder.

Example G2

[0420] This example provides a method of preparing a Ti6Al4V alloy powder. The preparation method includes the following steps.

[0421] (1) Third reduction was performed on titanium dioxide with a third reductant magnesium (granular) and a third adjuvant MgCl.sub.2NaCl eutectic salt at 900 C. under an argon atmosphere for 2 h to obtain a third reduced material, wherein the molar ratio of magnesium to titanium dioxide was 4:1, and the mass ratio of the MgCl.sub.2NaCl eutectic salt to titanium dioxide was 2.5:1.

[0422] Slurrying was performed on the third reduced material with a hydrochloric acid liquid whose pH was 1.0 to obtain a slurry; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 1.0 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 1.5; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 40 C. and dried at 60 C. under vacuum to obtain a third reduced powder TiO.sub.x.

[0423] A vanadium oxide (where the molar ratio of vanadium trioxide to vanadium pentoxide was 1:3), a calcium oxide, an aluminum powder and anhydrous CaCl.sub.2 were mixed, wherein the molar ratio of the aluminum powder to the vanadium oxide was 34.68:4, the molar ratio of the calcium oxide to the aluminum powder was 2:1, and the mass ratio of anhydrous CaCl.sub.2 to the vanadium oxide was 0.05:1; and first reduction was performed on the resulting mixture at 1400 C. under an argon atmosphere for 0.25 h to obtain a first reduced material.

[0424] Slurrying was performed on the first reduced material with water to obtain a slurry; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 1.5; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 0 C. and dried at 40 C. under vacuum to obtain a 6Al4V alloy powder.

[0425] (2) The third reduced powder TiO.sub.x and the 6Al4V alloy powder were mixed, crushed by ball milling, spray-pelletized, and sintered at 900 C. under a helium atmosphere for 20 h to obtain an oxygen-containing Ti6Al4V alloy powder. Second deoxidization was performed on the oxygen-containing Ti6Al4V alloy powder with magnesium (fragmental) as a second deoxidizer at 650 C. under a pure hydrogen atmosphere for 48 h to obtain a second deoxidization product, wherein the mass ratio of the oxygen-containing Ti6Al4V alloy powder to the second deoxidizer was 1:0.1, a MgCl.sub.2KCl eutectic salt was added in the second deoxidization, and the mass ratio of the MgCl.sub.2KCl eutectic salt to the oxygen-containing Ti6Al4V alloy powder was 3:1.

[0426] Slurrying was performed on the second deoxidization product with a hydrochloric acid liquid whose pH was 1.8 to obtain a slurry; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 1.2 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 3.0; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 0 C. and dried at 40 C. under vacuum to obtain a Ti6Al4V alloy powder.

Example G3

[0427] This example provides a method of preparing a Ti6Al4V alloy powder. The preparation method includes the following steps.

[0428] (1) Third reduction was performed on titanium dioxide with a third reductant magnesium (granular) and a third adjuvant MgCl.sub.2CaCl.sub.2 eutectic salt at 700 C. under a hydrogen atmosphere for 10 h to obtain a third reduced material, wherein the molar ratio of magnesium to titanium dioxide was 2.5:1, and the mass ratio of the MgCl.sub.2CaCl.sub.2 eutectic salt to titanium dioxide was 0.1:1.

[0429] Slurrying was performed on the third reduced material with a hydrochloric acid liquid whose pH was 2.5 to obtain a slurry; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 1.5; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 30 C. and dried at 55 C. under vacuum to obtain a third reduced powder TiO.sub.x.

[0430] A vanadium oxide (vanadium pentoxide), a calcium oxide, an aluminum powder and a CaCl.sub.2NaCl eutectic salt were mixed, wherein the molar ratio of the aluminum powder to the vanadium oxide was 9.0:1, the molar ratio of the calcium oxide to the aluminum powder was 0.6:1, and the mass ratio of the CaCl.sub.2NaCl eutectic salt to the vanadium oxide was 3.0:1; and first reduction was performed on the resulting mixture at 1400 C. under an argon atmosphere for 0.25 h to obtain a first reduced material.

[0431] Slurrying was performed on the first reduced material with water to obtain a slurry; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 3.0; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 15 C. and dried at 40 C. under vacuum to obtain a 6Al4V alloy powder.

[0432] (2) The third reduced powder TiO.sub.x and the 6Al4V alloy powder were mixed, crushed by stirred milling, tumble-pelletized, and sintered at 900 C. under an argon atmosphere for 24 h to obtain an oxygen-containing Ti6Al4V alloy powder. Second deoxidization was performed on the oxygen-containing Ti6Al4V alloy powder with calcium (powdery) as a second deoxidizer at 900 C. under a helium atmosphere for 12 h to obtain a second deoxidization product, wherein the mass ratio of the oxygen-containing Ti6Al4V alloy powder to the second deoxidizer was 1:0.15, anhydrous CaCl.sub.2 was added in the second deoxidization, and the mass ratio of anhydrous CaCl.sub.2 to the oxygen-containing Ti6Al4V alloy powder was 3:1.

[0433] Slurrying was performed on the second deoxidization product with a hydrochloric acid liquid whose pH was 0.5 to obtain a slurry; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 2.0; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 25 C. and dried at 55 C. under vacuum to obtain a Ti6Al4V alloy powder.

Example G4

[0434] This example provides a method of preparing a Ti6Al4V alloy powder. The preparation method includes the following steps.

[0435] (1) Third reduction was performed on titanium dioxide with a third reductant aluminum (powdery), a third adjuvant CaCl.sub.2LiCl eutectic salt and a calcium oxide at 1400 C. under a helium atmosphere for 0.25 h to obtain a third reduced material, wherein the molar ratio of aluminum to titanium dioxide was 1.33:1, the molar ratio of the calcium oxide to aluminum was 0.6:1, and the mass ratio of the CaCl.sub.2LiCl eutectic salt to titanium dioxide was 3:1.

[0436] Slurrying was performed on the third reduced material with a hydrochloric acid liquid whose pH was 2.5 to obtain a slurry; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 2.0; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 25 C. and dried at 55 C. under vacuum to obtain a third reduced powder TiO.sub.x.

[0437] A vanadium oxide (vanadium trioxide), a calcium oxide, aluminum (granular) and a CaCl.sub.2LiCl eutectic salt were mixed, wherein the molar ratio of aluminum to the vanadium oxide was 7.666:1, the molar ratio of the calcium oxide to aluminum was 1.2:1, and the mass ratio of the CaCl.sub.2LiCl eutectic salt to the vanadium oxide was 2.2:1; and first reduction was performed on the resulting mixture at 1000 C. under a helium atmosphere for 15 h to obtain a first reduced material.

[0438] Slurrying was performed on the first reduced material with a hydrochloric acid whose pH was 1.0 to obtain a slurry; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.8 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 2.3; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 10 C. and dried at 45 C. under vacuum to obtain a 6Al4V alloy powder.

[0439] (2) The third reduced powder TiO.sub.x and the 6Al4V alloy powder were mixed, crushed by tumble milling, compact-pelletized, and sintered at 1000 C. under a hydrogen atmosphere for 20 h to obtain an oxygen-containing Ti6Al4V alloy powder. Second deoxidization was performed on the oxygen-containing Ti6Al4V alloy powder with calcium (granular) as a second deoxidizer at 700 C. under a hydrogen atmosphere for 24 h to obtain a second deoxidization product, wherein the mass ratio of the oxygen-containing Ti6Al4V alloy powder to the second deoxidizer was 1:0.8, a CaCl.sub.2KCl eutectic salt was added in the second deoxidization, and the mass ratio of the CaCl.sub.2KCl to the oxygen-containing Ti6Al4V alloy powder was 1.3:1.

[0440] Slurrying was performed on the second deoxidization product with a hydrochloric acid liquid whose pH was 0.8 to obtain a slurry; pH adjustment was performed on the pH of the slurry, wherein the pH of the slurry was controlled to be greater than or equal to 0.9 during the pH adjustment, and the pH of the slurry after the pH adjustment was stabilized to 2.2; the slurry was filtered to obtain a solid phase; and the solid phase was washed at 20 C. and dried at 50 C. under vacuum to obtain a Ti6Al4V alloy powder.

Example G5

[0441] The preparation method of this example is the same as the preparation method of Example G1 except that the temperature of sintering in step (2) was 1600 C.

Example G6

[0442] The preparation method of this example is the same as the preparation method of Example G1 except that the temperature of sintering in step (2) was 700 C.

Comparative Example G1

[0443] The preparation method of this example is the same as the preparation method of Example G1 except that sintering was not performed in step (2).

Comparative Example G2

[0444] The preparation method of this example is the same as the preparation method of Example G1 except that the second deoxidization and fourth wet treatment were not performed in step (2).

[0445] The measurement results are shown in Table 21.

TABLE-US-00021 TABLE 21 V/Al mass ratio in x in third 6Al4V 6Al4V alloy powder reduced alloy Oxygen Particle Ti:Al:V mass powder TiO.sub.x powder Purity content size range ratio Example G1 approximately 3.98:6.02 99.88% 0.09% 20 to 106 90:6.02:3.98 0.5 m Example G2 0.077 3.98:6.04 99.90% 0.07% 20 to 106 89.98:6.04:3.98 m Example G3 0.036 4.01:5.98 99.92% 0.05% 45 to 300 90.01:5.98:4.01 to m Example G4 0.167 4.01:5.99 99.89% 0.08% 100 to 500 90.00:5.99:4.01 m Example G5 approximately 3.98:6.02 99.88% 0.09% 20 to 106 90:6.02:3.98 0.5 m Example G6 approximately 3.98:6.02 98.00% 1.95% 20 to 106 90:6.02:3.98 0.5 m Comparative approximately 3.98:6.02 Fully alloyed Ti6Al4V cannot be obtained without Example G1 0.5 sintering before the second deoxidization Comparative approximately 3.98:6.02 84.5% 15.5% 20 to 106 90:6.02:3.98 Example G2 0.5 m

[0446] The following conclusions can be drawn from Table 20.

[0447] (1) As can be seen from Examples G1 to G4, the method of preparing a Ti6Al4V alloy powder provided by the present disclosure can prepare a Ti6Al4V alloy powder whose purity is 99.8 wt % and above, oxygen content is less than or equal to 0.1 wt % and particle size range can be effectively controlled, and the mass ratio of Ti:Al:V in the final product meets the requirements.

[0448] (2) As can be seen from Example G1, Example G5, Example G6 and Comparative Example G1, when the sintering temperature is too high, the oxygen content in the Ti6Al4V alloy powder is barely reduced, the energy consumption becomes too high, and the requirements for the equipment accordingly becomes stringent; in Example G6, since the sintering temperature is only 700 C., the purity of the product is only 98.00 wt %, and the oxygen content is as high as 1.95 wt %; in Comparative Example G1, since sintering is not performed, the fully alloyed Ti6Al4V cannot be obtained. Therefore, in the present disclosure, titanium, aluminum and vanadium can be fully alloyed by sintering, and the sintering temperature is preferably controlled within a specific range, thereby guaranteeing the purity of the Ti6Al4V alloy powder.

[0449] It is to be noted that the above are only the embodiments of the present disclosure and are not intended to limit the scope of the present disclosure. Those skilled in the art should understand that any modifications or substitutions easily conceivable by those skilled in the art within the scope of the present disclosure fall within the protection scope and the disclosed scope of the present disclosure.