CN114985753A - Method for preparing reduced spherical titanium powder through calcium-heat self-propagating reaction - Google Patents
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Abstract
A method for preparing reduced spherical titanium powder by calcium heat self-propagating reaction belongs to the technical field of powder preparation in powder metallurgy process. The preparation method is characterized by comprising the following steps: 1) mixing the dried nano titanium dioxide powder and micron-sized calcium powder, adding the mixture into a self-propagating reaction furnace, and reacting to obtain a mixture of titanium powder and calcium oxide serving as reduction products; the molar ratio of the nano titanium dioxide powder to the calcium powder is TiO 2 Ca is 1: 2.0-3.5; the particle size of the calcium powder is 0.1-30 μm; leaching the mixture of the titanium powder and the calcium oxide of the reduction product, washing the product after filtering, and drying in vacuum to obtain the reduced titanium powder of the product. The invention relates to a method for preparing reduced spherical titanium powder by calcium thermal self-propagating reaction, which is implemented by self-propagatingThe high-temperature reaction and the acid leaching reaction obtain the reduced titanium powder product with high purity, uniform particle size distribution, low oxygen content and high sphericity.
Description
Technical Field
A method for preparing reduced spherical titanium powder by calcium heat self-propagating reaction belongs to the technical field of powder preparation in powder metallurgy process.
Background
Titanium metal is a new type of structural functional material known as the third largest metal behind iron and aluminum. The metal titanium has special physical and chemical properties of high temperature resistance, corrosion resistance, high specific strength, low density and the like. The titanium powder is an important titanium material, has wide application, and is mainly used as a grain refinement agent of cast aluminum, a pyrotechnic agent and an explosion agent for fireworks. The titanium powder can also be used for preparing titanium and aluminum alloy additives, surface coating materials, raw materials for 3D printing and the like by powder metallurgy. The industrial production method of the titanium powder in China takes sponge titanium as a raw material and utilizes a physical mechanical crushing method or a hydrogenation dehydrogenation method to prepare the titanium powder, and the prepared titanium powder has the defects of low purity, uneven particle size distribution, poor activity and the like, thereby seriously influencing the application and development of the titanium powder.
In the process of preparing titanium powder described in Chinese patent CN202011550311.7, it is described that titanium dioxide precursor prepared from titanium tetrachloride is subjected to secondary reduction to obtain low-oxygen titanium powder; wherein the reducing agents each independently comprise one or a combination of at least two of Mg, Ca, Mg-Li alloy, or Mg-Ca alloy. The method comprises the following steps of reducing titanium dioxide by using Ca to prepare titanium powder: titanium dioxide is reduced by reducing agent in vacuum or protective atmosphere at 600-1200 deg.C, and is repeatedly carried out after acid leaching. Although titanium powder with higher purity is prepared in the reaction process, the prepared titanium powder has low sphericity due to the fact that the control of process conditions and the preparation process is not accurate enough.
Aiming at the technical problems in the existing preparation method of the metal titanium powder, the invention reduces the additive in the reaction, simplifies the reaction operation process and prepares the titanium powder with high purity, uniform particle size distribution and high sphericity.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, and provides a method for preparing reduced spherical titanium powder by a micron-sized calcium thermal self-propagating reaction with high purity, uniform particle size distribution and high sphericity.
The technical scheme adopted by the invention for solving the technical problems is as follows: the method for preparing the reduced spherical titanium powder by the calcium-heat self-propagating reaction is characterized by comprising the following preparation process steps:
1) uniformly mixing the dried nano titanium dioxide powder with calcium powder to obtain a mixed material; adding the mixed material into a self-propagating reaction furnace to initiate a self-propagating reaction, and cooling the reaction material to obtain a mixture of titanium powder and calcium oxide serving as a reduction product; wherein, the nanometer titanium dioxide powder and the calcium powder are TiO according to the mol ratio 2 Ca is 1: 2.0-3.5; the particle size of the calcium powder is 0.1-30 μm;
2) placing the mixture of the reduction product titanium powder and calcium oxide in a closed reactor, leaching the crude product by using dilute hydrochloric acid as a leaching solution, and filtering to obtain a filtrate and a leaching product; wherein the molar concentration of the hydrochloric acid is 0.5-5.5 mol/L;
3) and washing and vacuum drying the leached product to obtain the reduced titanium powder product.
The method for preparing the reduced spherical titanium powder through the calcium-heat self-propagating reaction obtains the reduced titanium powder product with high purity, uniform particle size distribution, low oxygen content and high sphericity through the self-propagating high-temperature reaction and the acid leaching reaction.
The invention takes titanium dioxide and calcium powder as raw materials, provides a new idea of preparing reduced spherical titanium powder by calcium thermal self-propagating, simultaneously completes material synthesis and sintering, has the advantages of short process flow, simple operation, low energy consumption and the like, solves the technical problems of complex process, long process flow, high energy consumption, large pollution and the like in the existing titanium powder preparation process, and effectively solves the problems of energy consumption, time consumption, environmental pollution and the like.
The invention adopts the first-stage reduction reaction operation, namely the dosage of the reducing agent is 120 to 150 percent of the theoretical amount in the self-propagating reaction stage, so that the oxygen in the titanium powder is completely removed.
The raw material titanium dioxide powder is nano-scale, the calcium powder is micron-scale (0.1-10 μm), namely the particle size of the calcium powder is close to thousand times of that of the titanium dioxide powder, and the titanium dioxide powder and the calcium powder have very large volume difference. In the micro world, the titanium dioxide powder is actually dispersed on the surface of calcium powder particles for replacement reaction. The inventors thought that the reduced titanium powder product of high sphericity was obtained because the particle size was originally extremely small but the particle size ratio was large enough to allow the reduced titanium obtained after completion of the reaction to be more easily aggregated into a spherical shape even under a self-propagating high-temperature reaction.
The reduced titanium powder is mainly applied to the aspects of plasma spraying, powder metallurgy, 3D printing and the like, and can also be used for a dehydrogenation and deoxidation process. The method has the advantages of low raw material cost, simple operation, short process flow and reaction time, low energy consumption and low requirements on instruments and equipment, and lays a foundation for industrial production.
According to the method for preparing the reduced spherical titanium powder through the calcium-heat self-propagating reaction, the obtained reduced titanium powder comprises the following chemical components in percentage by mass: 99-99.5% of Ti, O: 0.1 to 0.9 percent of the total weight of the composition, and the balance of impurities; the granularity of the obtained product reduced titanium powder is 5-100 mu m.
According to the method for preparing the reduced spherical titanium powder through the calcium-heat self-propagating reaction, the sphericity of the obtained reduced titanium powder is 0.76-0.93.
Preferably, in the method for preparing reduced spherical titanium powder by the calcium thermal self-propagating reaction, the mixed material in the step 1) is treated in the following manner before being added into a self-propagating reaction furnace: pressing under 5 MPa-50 MPa to obtain block material, and adding into a self-propagating reaction furnace. After the materials are pressed into block materials with certain density, the process of self-propagating reaction is more controllable, the yield of the obtained reduced titanium powder is higher, and the particle size distribution is more uniform.
Preferably, in the method for preparing reduced spherical titanium powder by calcium thermal self-propagating reaction, the drying process of the dried nano titanium dioxide powder in the step 1) is as follows: and (3) placing the nano titanium dioxide in an oven for drying, wherein the drying temperature is controlled to be 100-180 ℃, and the drying time is 24-30 h.
The invention adopts a self-propagating high-temperature synthesis technology, and is a new method for preparing inorganic compound high-temperature materials. The method successfully overcomes the defects of the traditional method for preparing the high-temperature refractory material, such as: high-temperature smelting, high-temperature sintering and the like cause large energy and time consumption due to high smelting temperature and long process time. The self-propagating high-temperature synthesis technology is that raw materials are ignited in high vacuum or medium atmosphere to generate chemical reaction, the temperature of adjacent materials is suddenly raised by the generated heat generated by the chemical reaction, so that new chemical reaction is caused and propagated to the whole reactant in the form of combustion wave, and the reactant is changed into a product when the combustion wave advances. Preferably, in the method for preparing the reduced spherical titanium powder by the calcium thermal self-propagating reaction, the initiation mode of the self-propagating reaction in the step 1) is a local ignition method: heating the local part of the mixed raw material by an electric heating wire in a self-propagating reaction furnace to initiate the self-propagating reaction. The equation for the self-propagating high temperature synthesis reaction is: TiO 2 2 +2Ca ═ Ti +2 CaO. The process of self-propagating reaction initiated by the local ignition method is more controllable, the yield of the obtained reduced titanium powder is higher, and the particle size distribution is more uniform.
Preferably, in the method for preparing reduced spherical titanium powder by the calcium thermal self-propagating reaction, the addition amount of the dilute hydrochloric acid in the step 2) is as follows: the molar weight of the calcium powder is 2.1-2.6 times of the molar weight of the calcium powder. When dilute hydrochloric acid is used as leachate to leach the reduction product, the addition of the dilute hydrochloric acid and the reduction product is proportioned according to 5-30% of hydrochloric acid excess required by a reaction theory, and the reaction chemical equation is CaO +2H + ＝Ca 2+ +H 2 And O. The measured dilute hydrochloric acid ensures that the leaching effect is more thorough, and the obtained reduced titanium powder has higher purity.
The preferable method for preparing the reduced spherical titanium powder through the calcium-heat self-propagating reaction is that the leaching temperature in the step 2) is 25-45 ℃, and the leaching time is 60-180 min.
The preferable method for preparing the reduced spherical titanium powder by the calcium thermal self-propagating reaction comprises the following steps of (1) washing and vacuum drying: washing the leached product with water to neutrality, and drying in a vacuum oven at 30-40 deg.c for 8-24 hr.
Compared with the prior art, the method for preparing the reduced spherical titanium powder by the calcium-heat self-propagating reaction has the beneficial effects that: (1) the invention takes titanium dioxide and calcium powder as raw materials, provides a new idea of preparing reduced spherical titanium powder by calcium thermal self-propagating, simultaneously completes material synthesis and sintering, has the advantages of short process flow, simple operation, low energy consumption and the like, solves the technical problems of complex process, long process flow, high energy consumption, large pollution and the like in the existing titanium powder preparation process, and effectively solves the problems of energy consumption, time consumption, environmental pollution and the like.
(2) The invention adopts the first-stage reduction reaction operation, namely the dosage of the reducing agent is 120 to 150 percent of the theoretical amount in the self-propagating reaction stage, so that the oxygen in the titanium powder is completely removed.
(3) The method carries out operations such as acid leaching and washing on the prepared titanium powder crude product, and thoroughly removes impurities such as calcium oxide and the like in the titanium powder. Therefore, the prepared titanium powder product has high sphericity, high purity and low oxygen content, and is suitable for titanium powder and alloy powder which are urgently needed in high-end fields and 3D printing.
(4) The method has the advantages of simple process, short process flow, short reaction time, low requirement on equipment and easy industrial popularization.
(5) The metal reduced titanium powder prepared by the method has the advantages of oxygen content of less than or equal to 0.15 percent, nitrogen content of less than or equal to 0.03 percent, hydrogen content of less than or equal to 0.01 percent, narrow particle size distribution and high sphericity, and overcomes the defects of low sphericity, high impurity content, particularly high oxygen content and the like of the existing domestic spherical titanium powder.
Drawings
FIG. 1 is a process flow diagram of the method for preparing reduced spherical titanium powder by calcium thermal self-propagating reaction of the invention.
Detailed Description
The invention is further illustrated by the following specific examples, of which example 1 is the best mode of practice. The following examples serve to illustrate the invention. Parameters characterizing the morphology of the particles. Particles that are morphologically closer to a sphere have a sphericity closer to 1. The ratio of the surface area of a sphere of the same volume as the object to the surface area of the object. The sphericity of the ball is equal to 1 and the sphericity of other objects is less than 1.
Sphericity formula for arbitrary particles:
vp is the particle volume and Sp is the particle surface area.
Example 1
Referring to the reaction flow of the attached figure 1, the method for preparing the reduced spherical titanium powder by the calcium thermal self-propagating reaction specifically comprises the following steps:
step 1: self-propagating reaction
Placing the nano titanium dioxide in an oven, and drying for 24h at 150 ℃; uniformly mixing the dried nano titanium dioxide powder with calcium powder, wherein the average particle size of the calcium powder is 4 mu m; pressing the mixed materials into blocks under 10MPa, adding the block materials into a self-propagating reaction furnace, heating part of the mixed materials in the self-propagating reaction furnace by using an electric heating wire to initiate self-propagating reaction, and cooling the reaction materials to obtain a mixture of titanium powder and calcium oxide serving as reduction products; wherein, according to the molar ratio of TiO 2 Adding materials in a ratio of 1:2.5 when Ca is added;
step 2: acid leaching reaction
Placing the mixture of the titanium powder and the calcium oxide which are reduction products in a closed reactor, and leaching the crude product by taking dilute hydrochloric acid as a leaching agent, wherein the molar concentration of the hydrochloric acid is 1.5mol/L, the leaching temperature is 30 ℃, and the leaching time is 100 min; the addition of the dilute hydrochloric acid and the reduction product is the ratio of 15% excess hydrochloric acid calculated theoretically, namely the addition of the dilute hydrochloric acid is as follows: the molar weight of the calcium powder is 2.3 times that of the calcium powder;
and step 3: washing and drying
Washing the leached product with water to be neutral, then drying the leached product in a vacuum drying oven under the vacuum condition, wherein the drying temperature is 30 ℃, the drying time is 12 hours, and drying to obtain the product reduced titanium powder;
the obtained reduced titanium powder comprises the following chemical components in percentage by mass: 99.7% of Ti, O: 0.06%, the average particle diameter was 40 μm, the square deviation of the particle diameter was 0.12 μm, the average sphericity value was 0.93, and the square deviation of the sphericity was 0.011.
Example 2
Referring to the reaction flow of the attached figure 1, the method for preparing the reduced spherical titanium powder by the calcium thermal self-propagating reaction specifically comprises the following steps:
step 1: self-propagating reaction
Placing the nano titanium dioxide in a drying oven, and drying for 28h at 120 ℃; uniformly mixing the dried nano titanium dioxide powder with calcium powder, wherein the average particle size of the calcium powder is 4.2 mu m; pressing the mixed materials into blocks under 8MPa, adding the block materials into a self-propagating reaction furnace, heating part of the mixed materials in the self-propagating reaction furnace by using an electric heating wire to initiate self-propagating reaction, and cooling the reaction materials to obtain a mixture of titanium powder and calcium oxide serving as reduction products; wherein, in molar ratio of TiO 2 Adding materials in a ratio of 1:2.3 when Ca is added;
step 2: acid leaching reaction
Placing the mixture of the reduction product titanium powder and calcium oxide in a closed reactor, and leaching the crude product by using dilute hydrochloric acid as a leaching solution, wherein the molar concentration of the hydrochloric acid is 1.0mol/L, the leaching temperature is 35 ℃, and the leaching time is 80 min; the addition of the dilute hydrochloric acid and the reduction product is the ratio of 13% excess hydrochloric acid calculated theoretically, namely the addition of the dilute hydrochloric acid is as follows: 2.26 times of the molar weight of the calcium powder;
and step 3: washing and drying
Washing the leached product with water to be neutral, then drying the leached product in a vacuum drying oven under the vacuum condition, wherein the drying temperature is 33 ℃, the drying time is 10 hours, and drying to obtain the product reduced titanium powder;
the obtained reduced titanium powder comprises the following chemical components in percentage by mass: 99.6% of Ti, O: 0.09%, the average particle diameter was 48 μm, the square deviation of particle diameter was 0.12, the average sphericity value was 0.91, and the square deviation of sphericity was 0.010.
Example 3
Referring to the reaction flow of the attached figure 1, the method for preparing the reduced spherical titanium powder by the calcium thermal self-propagating reaction specifically comprises the following steps:
step 1: self-propagating reaction
Placing the nano titanium dioxide in an oven 1Drying for 26h at 60 ℃; uniformly mixing the dried nano titanium dioxide powder with calcium powder, wherein the average particle size of the calcium powder is 2.7 mu m; pressing the mixed material into blocks under 20MPa, adding the block-shaped material into a self-propagating reaction furnace, heating the local part of the mixed material by using an electric heating wire in the self-propagating reaction furnace to initiate a self-propagating reaction, and cooling the reaction material to obtain a mixture of reduced products titanium powder and calcium oxide; wherein, according to the molar ratio of TiO 2 Adding materials with Ca being 1: 3.0;
step 2: acid leaching reaction
Placing the mixture of the reduction product titanium powder and calcium oxide in a closed reactor, and leaching the crude product by using dilute hydrochloric acid as a leaching solution, wherein the molar concentration of the hydrochloric acid is 2.8mol/L, the leaching temperature is 28 ℃, and the leaching time is 120 min; the addition of the dilute hydrochloric acid and the reduction product is the ratio of 20% excess hydrochloric acid calculated theoretically, namely the addition of the dilute hydrochloric acid is as follows: the molar weight of the calcium powder is 2.4 times that of the calcium powder;
and step 3: washing and drying
Washing the leached product with water to be neutral, then drying the leached product in a vacuum drying oven under the vacuum condition, wherein the drying temperature is 38 ℃ and the drying time is 8h, and drying to obtain the product reduced titanium powder;
the obtained reduced titanium powder comprises the following chemical components in percentage by mass: 99.5% of Ti, O: 0.10%, average particle diameter of 32 μm, mean square deviation of particle diameter of 0.07, mean value of sphericity of 0.90, and square deviation of sphericity of 0.012.
Example 4
Referring to the reaction flow of the attached figure 1, the method for preparing the reduced spherical titanium powder by the calcium thermal self-propagating reaction specifically comprises the following steps:
step 1: self-propagating reaction
Placing the nano titanium dioxide in an oven, and drying for 24h at 180 ℃; uniformly mixing the dried nano titanium dioxide powder with calcium powder, wherein the average particle size of the calcium powder is 0.1 mu m; pressing the mixed materials into blocks under 50MPa, adding the block materials into a self-propagating reaction furnace, heating the local part of the mixed materials by using an electric heating wire in the self-propagating reaction furnace to initiate self-propagating reaction, and cooling the reaction materials to obtain a mixture of reduced products titanium powder and calcium oxide; wherein, according to the molar ratioTiO 2 Adding materials with Ca being 1: 2.0;
step 2: acid leaching reaction
Placing the mixture of the reduction product titanium powder and calcium oxide in a closed reactor, and leaching the crude product by using dilute hydrochloric acid as a leaching solution, wherein the molar concentration of the hydrochloric acid is 5.5mol/L, the leaching temperature is 25 ℃, and the leaching time is 60 min; the addition of the dilute hydrochloric acid and the reduction product is the ratio of 30% excess hydrochloric acid calculated theoretically, namely the addition of the dilute hydrochloric acid is as follows: the molar weight of the calcium powder is 2.1-2.6 times that of the calcium powder;
and step 3: washing and drying
Washing the leached product with water to be neutral, then drying the leached product in a vacuum drying oven under the vacuum condition, wherein the drying temperature is 30 ℃ and the drying time is 24 hours, and drying to obtain the product reduced titanium powder;
the obtained reduced titanium powder comprises the following chemical components in percentage by mass: 99.3% of Ti, O: 0.34%, an average particle diameter of 5 μm, a particle size square deviation of 0.09, a sphericity average value of 0.89, and a sphericity square deviation of 0.007.
Example 5
Referring to the reaction flow of the attached figure 1, the method for preparing the reduced spherical titanium powder by the calcium thermal self-propagating reaction specifically comprises the following steps:
step 1: self-propagating reaction
Placing the nano titanium dioxide in an oven, and drying for 30h at 100 ℃; uniformly mixing the dried nano titanium dioxide powder with calcium powder, wherein the average particle size of the calcium powder is 30 mu m; pressing the mixed material into blocks under 5MPa, adding the block-shaped material into a self-propagating reaction furnace, heating the local part of the mixed material by using an electric heating wire in the self-propagating reaction furnace to initiate self-propagating reaction, and cooling the reaction material to obtain a mixture of reduced products titanium powder and calcium oxide; wherein, according to the molar ratio of TiO 2 Adding materials in a ratio of 1:3.5 when Ca is added;
step 2: acid leaching reaction
Placing the mixture of the reduction product titanium powder and calcium oxide in a closed reactor, and leaching the crude product by using dilute hydrochloric acid as a leaching solution, wherein the molar concentration of the hydrochloric acid is 0.5mol/L, the leaching temperature is 45 ℃, and the leaching time is 180 min; the addition of the dilute hydrochloric acid and the reduction product is the ratio of 5.0% of the excessive hydrochloric acid calculated theoretically, namely the addition of the dilute hydrochloric acid is as follows: 2.1 times of the molar weight of the calcium powder;
and step 3: washing and drying
Washing the leached product with water to be neutral, then drying the leached product in a vacuum drying oven under the vacuum condition, wherein the drying temperature is 40 ℃, and the drying time is 8 hours, and drying to obtain the product reduced titanium powder;
the obtained reduced titanium powder comprises the following chemical components in percentage by mass: 99.2% of Ti, O: 0.43%, average particle size 89 μm, particle size square deviation 0.15, sphericity average 0.86, and sphericity square deviation 0.009.
Example 6
Referring to the reaction flow of the attached figure 1, the method for preparing the reduced spherical titanium powder by the calcium thermal self-propagating reaction specifically comprises the following steps:
step 1: self-propagating reaction
Placing the nano titanium dioxide in an oven, and drying for 24h at 150 ℃; uniformly mixing the dried nano titanium dioxide powder with calcium powder, wherein the average particle size of the calcium powder is 4 mu m; pressing the mixed materials into blocks under 10MPa, adding the block materials into a self-propagating reaction furnace, integrally heating the mixed materials in the self-propagating reaction furnace to initiate self-propagating reaction, and cooling the reaction materials to obtain a mixture of reduced products titanium powder and calcium oxide; wherein, according to the molar ratio of TiO 2 Adding materials in a ratio of 1:2.5 when Ca is added;
and 2, step: acid leaching reaction
Placing the mixture of the reduction product titanium powder and calcium oxide in a closed reactor, and leaching the crude product by using dilute hydrochloric acid as a leaching solution, wherein the molar concentration of the hydrochloric acid is 1.5mol/L, the leaching temperature is 30 ℃, and the leaching time is 100 min; the addition of the dilute hydrochloric acid and the reduction product is the ratio of 15% excess hydrochloric acid calculated theoretically, namely the addition of the dilute hydrochloric acid is as follows: the molar weight of the calcium powder is 2.3 times that of the calcium powder;
and step 3: washing and drying
Washing the leached product with water to be neutral, then drying the leached product in a vacuum drying oven under the vacuum condition, wherein the drying temperature is 30 ℃, the drying time is 12 hours, and drying to obtain the product reduced titanium powder;
the obtained reduced titanium powder comprises the following chemical components in percentage by mass: 99.4% of Ti, O: 0.26%, an average particle diameter of 42 μm, a mean square deviation of particle diameter of 0.35, a mean value of sphericity of 0.81, and a mean square deviation of sphericity of 0.017.
Example 7
Referring to the reaction flow of the attached figure 1, the method for preparing the reduced spherical titanium powder by the calcium thermal self-propagating reaction specifically comprises the following steps:
step 1: self-propagating reaction
Placing the nano titanium dioxide in an oven, and drying for 24h at 150 ℃; uniformly mixing the dried nano titanium dioxide powder with calcium powder, wherein the average particle size of the calcium powder is 4 mu m; directly adding the mixed material into a self-propagating reaction furnace, heating part of the mixed material in the self-propagating reaction furnace by using an electric heating wire to initiate self-propagating reaction, and cooling the reaction material to obtain a mixture of reduced products titanium powder and calcium oxide; wherein, according to the molar ratio of TiO 2 Adding materials in a ratio of 1:2.5 when Ca is added;
step 2: acid leaching reaction
Placing the mixture of the reduction product titanium powder and calcium oxide in a closed reactor, and leaching the crude product by using dilute hydrochloric acid as a leaching solution, wherein the molar concentration of the hydrochloric acid is 1.5mol/L, the leaching temperature is 30 ℃, and the leaching time is 100 min; the addition of the dilute hydrochloric acid and the reduction product is the ratio of 15% excess hydrochloric acid calculated theoretically, namely the addition of the dilute hydrochloric acid is as follows: the molar weight of the calcium powder is 2.3 times that of the calcium powder;
and step 3: washing and drying
Washing the leached product with water to be neutral, then drying the leached product in a vacuum drying oven under the vacuum condition, wherein the drying temperature is 30 ℃, and the drying time is 12 hours, and drying to obtain the product reduced titanium powder;
the obtained reduced titanium powder comprises the following chemical components in percentage by mass: 99.0% of Ti, O: 0.9%, the average particle diameter of 38.7 μm, the square deviation of particle diameter of 0.32, the average sphericity of 0.76, and the square deviation of sphericity of 0.028.
Comparative example 1
The method specifically comprises the following steps:
step 1: self-propagating reaction
The dioxygen having an average particle diameter of 4 μmPutting the titanium into a drying oven, and drying for 24h at 150 ℃; uniformly mixing the dried titanium dioxide powder with calcium powder with the average particle size of 4 mu m; pressing the mixed material into blocks under 10MPa, adding the block-shaped material into a self-propagating reaction furnace, heating the local part of the mixed material by using an electric heating wire in the self-propagating reaction furnace to initiate a self-propagating reaction, and cooling the reaction material to obtain a mixture of reduced products titanium powder and calcium oxide; wherein, according to the molar ratio of TiO 2 Adding materials in a ratio of 1:2.5 when Ca is added;
step 2: acid leaching reaction
Placing the mixture of the reduction product titanium powder and calcium oxide in a closed reactor, and leaching the crude product by using dilute hydrochloric acid as a leaching solution, wherein the molar concentration of the hydrochloric acid is 1.5mol/L, the leaching temperature is 30 ℃, and the leaching time is 100 min; the addition of the dilute hydrochloric acid and the reduction product is the ratio of 15% excess hydrochloric acid calculated theoretically, namely the addition of the dilute hydrochloric acid is as follows: 2.3 times of the molar weight of the calcium powder;
and step 3: washing and drying
Washing the leached product with water to be neutral, then drying the leached product in a vacuum drying oven under the vacuum condition, wherein the drying temperature is 30 ℃, the drying time is 12 hours, and drying to obtain the product reduced titanium powder;
the obtained reduced titanium powder comprises the following chemical components in percentage by mass: 96.3% of Ti, O: 2.08%, the average particle diameter was 47 μm, the square deviation of particle diameter was 13.5 μm, the average sphericity value was 0.58, and the square deviation of sphericity was 0.26.
Comparative example 2
Referring to the reaction flow of the attached figure 1, the method for preparing the reduced spherical titanium powder by the calcium thermal self-propagating reaction specifically comprises the following steps:
step 1: self-propagating reaction
Placing the nano titanium dioxide in an oven, and drying for 24h at 150 ℃; uniformly mixing the dried nano titanium dioxide powder with calcium powder, wherein the average particle size of the calcium powder is 4 mu m; pressing the mixed material into blocks under 10MPa, adding the block-shaped material into a self-propagating reaction furnace, heating the local part of the mixed material by using an electric heating wire in the self-propagating reaction furnace to initiate a self-propagating reaction, and cooling the reaction material to obtain a mixture of reduced products titanium powder and calcium oxide; wherein, the massage is carried outMolar ratio of TiO 2 The Ca accounts for 1:1.25 of the materials;
step 2: acid leaching reaction
Placing the mixture of the titanium powder and the calcium oxide which are reduction products in a closed reactor, and leaching the crude product by taking dilute hydrochloric acid as a leaching agent, wherein the molar concentration of the hydrochloric acid is 1.5mol/L, the leaching temperature is 30 ℃, and the leaching time is 100 min; the addition of the dilute hydrochloric acid and the reduction product is the ratio of 15% excess hydrochloric acid calculated theoretically, namely the addition of the dilute hydrochloric acid is as follows: the molar weight of the calcium powder is 2.3 times that of the calcium powder;
and step 3: washing and drying
Washing the leached product with water to be neutral, then drying the leached product in a vacuum drying oven under the vacuum condition, wherein the drying temperature is 30 ℃, the drying time is 12 hours, and drying to obtain the product reduced titanium powder;
the obtained reduced titanium powder comprises the following chemical components in percentage by mass: 93.4% of Ti, O: 5.6%, the average particle diameter was 43 μm, the square deviation of the particle diameter was 1.32 μm, the average sphericity value was 0.81, and the square deviation of the sphericity was 0.067.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (9)
1. A method for preparing reduced spherical titanium powder by calcium-heat self-propagating reaction is characterized by comprising the following preparation process steps:
1) uniformly mixing the dried nano titanium dioxide powder with calcium powder to obtain a mixed material; adding the mixed material into a self-propagating reaction furnace to initiate a self-propagating reaction, and cooling the reaction material to obtain a mixture of reduced products titanium powder and calcium oxide; wherein, the nanometer titanium dioxide powder and the calcium powder are TiO according to the mol ratio 2 Ca is 1: 2.0-3.5; the particle size of the calcium powder is 0.1-30 μm;
2) placing the mixture of the reduction product titanium powder and calcium oxide in a closed reactor, leaching the crude product by using dilute hydrochloric acid as a leaching solution, and filtering to obtain a filtrate and a leaching product; wherein, the molar concentration of the hydrochloric acid is 0.5 mol/L-5.5 mol/L;
3) and washing and vacuum drying the leached product to obtain the reduced titanium powder product.
2. The method for preparing reduced spherical titanium powder by the calcium thermal self-propagating reaction according to claim 1, wherein the method comprises the following steps: the reduced titanium powder of the obtained product comprises the following chemical components in percentage by mass: 99-99.5% of Ti, O: 0.1 to 0.9 percent, and the balance of impurities; the granularity of the obtained product reduced titanium powder is 5-100 mu m.
3. The method for preparing reduced spherical titanium powder by the calcium thermal self-propagating reaction according to claim 1, wherein the method comprises the following steps: the sphericity of the obtained reduced titanium powder is 0.76-0.93.
4. The method for preparing reduced spherical titanium powder by the calcium thermal self-propagating reaction according to claim 1, wherein the method comprises the following steps: the mixed material in the step 1) is firstly treated in the following way before being added into a self-propagating reaction furnace: pressing under 5 MPa-50 MPa to obtain block material, and adding into a self-propagating reaction furnace.
5. The method for preparing reduced spherical titanium powder by the calcium-thermal self-propagating reaction according to claim 1, wherein: the drying process of the dried nano titanium dioxide powder in the step 1) comprises the following steps: and (3) placing the nano titanium dioxide in an oven for drying, wherein the drying temperature is controlled to be 100-180 ℃, and the drying time is 24-30 h.
6. The method for preparing reduced spherical titanium powder by the calcium thermal self-propagating reaction according to claim 1, wherein the method comprises the following steps: the initiation mode of the self-propagating reaction in the step 1) is a local ignition method: heating the local part of the mixed raw material by an electric heating wire in a self-propagating reaction furnace to initiate the self-propagating reaction.
7. The method for preparing reduced spherical titanium powder by the calcium thermal self-propagating reaction according to claim 1, wherein the method comprises the following steps: the addition amount of the dilute hydrochloric acid in the step 2) is as follows: the molar weight of the calcium powder is 2.1-2.6 times of the molar weight of the calcium powder.
8. The method for preparing reduced spherical titanium powder by the calcium thermal self-propagating reaction according to claim 1, wherein the method comprises the following steps: the leaching temperature of the leaching in the step 2) is 25-45 ℃, and the leaching time is 60-180 min.
9. The method for preparing reduced spherical titanium powder by the calcium thermal self-propagating reaction according to claim 1, wherein the method comprises the following steps: the washing and vacuum drying process in the step 2) comprises the following steps: washing the leached product with water to neutrality, and drying in a vacuum oven at 30-40 deg.c for 8-24 hr.
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