CN115383128B - Method for preparing coarse-particle tungsten powder by reduction of tungsten trioxide - Google Patents
Method for preparing coarse-particle tungsten powder by reduction of tungsten trioxide Download PDFInfo
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- CN115383128B CN115383128B CN202211064009.XA CN202211064009A CN115383128B CN 115383128 B CN115383128 B CN 115383128B CN 202211064009 A CN202211064009 A CN 202211064009A CN 115383128 B CN115383128 B CN 115383128B
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title claims abstract description 109
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000011362 coarse particle Substances 0.000 title claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000001257 hydrogen Substances 0.000 claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 54
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 13
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 239000010937 tungsten Substances 0.000 claims abstract description 11
- 230000002787 reinforcement Effects 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000011534 incubation Methods 0.000 claims 1
- 150000001340 alkali metals Chemical group 0.000 abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 12
- 229910001930 tungsten oxide Inorganic materials 0.000 description 12
- 238000001816 cooling Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000011946 reduction process Methods 0.000 description 5
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a method for preparing coarse-particle tungsten powder by reduction of tungsten trioxide, which comprises the steps of putting tungsten trioxide and tungsten hexachloride into a ball mill according to a certain mass ratio, uniformly mixing, putting a mixture of tungsten trioxide and tungsten hexachloride into a reduction furnace, introducing hydrogen at a relatively low temperature for one-stage reduction, volatilizing the tungsten hexachloride and reducing the tungsten hexachloride into metal tungsten to be deposited on the surface of the tungsten trioxide, and introducing mixed gas of hydrogen and steam at a high temperature for two-stage reinforcement reduction to promote tungsten powder particle growth, thereby preparing the coarse-particle tungsten powder. The invention has the advantages that the defect that the purity of the product is reduced due to alkali metal residues in the traditional alkali metal Na/Li doped method for preparing the coarse-particle tungsten powder can be avoided, and the coarse-particle tungsten powder with high purity and complete crystallization can be prepared under milder reaction conditions.
Description
Technical Field
The invention relates to the field of tungsten powder metallurgy, in particular to a method for preparing coarse-particle tungsten powder by reduction of tungsten trioxide powder.
Background
The coarse-grain tungsten carbide hard alloy has the advantages of good toughness, high hardness, high heat conductivity, good red hardness and the like, and is widely applied to various fields of petroleum drilling and mining, mining tools, hard surface materials, stamping dies and the like. Tungsten powder is a raw material for preparing tungsten carbide hard alloy, and because the granularity of tungsten powder and tungsten carbide has obvious inheritance, the preparation of coarse-particle tungsten powder is a key for preparing ultra-coarse tungsten carbide hard alloy.
Tungsten powder is usually prepared from tungsten oxide powder raw material by adopting a reduction process. At present, the process for preparing coarse tungsten powder is more, and the following methods are mainly classified according to the process principle: (1) Adopting tungsten oxide high-temperature hydrogen reduction to prepare coarse-particle tungsten powder. Adopting tungsten yellow (WO 3) or tungsten blue (WO 2.92) as raw materials, and adopting hydrogen to reduce for a long time at the temperature of more than 1300 ℃ to prepare coarse-particle tungsten powder. The process has the advantages of uniform tungsten powder particles and few pseudo particles, but has the defects of high energy consumption and high cost due to high reduction temperature and high requirements on furnace equipment. For example, patent 201810931907.8 'a method for preparing ultra-coarse tungsten powder by high-temperature liquid phase reduction of tungsten oxide' discloses that tungsten oxide and tungsten powder are used as raw materials, and the ultra-coarse tungsten powder with the average particle size of 58-70um is prepared by hydrogen reduction at 1420-1600 ℃ for 0.5-2 hours. (2) The method adopts tungsten oxide powder doped with alkali metal (Na or Li) to prepare coarse tungsten powder through hydrogen reduction. The process utilizes the property that tungsten oxide and alkali metal oxide are easy to form low-melting-point compounds, and hydrogen reduction is carried out at a higher temperature to prepare coarse-particle tungsten powder. Because of limited alkali metal volatility, especially Li-doped tungsten powder, a certain amount of alkali metal tends to remain in the tungsten powder produced by reduction, which has an adverse effect on the performance of tungsten products. In addition, the ultra-coarse tungsten powder prepared by the process has more pseudo particles. For example, patent 202010684540.1 "method for preparing ultra-coarse tungsten powder with narrow particle size distribution and tungsten powder" discloses that tungsten oxide, sodium tungstate and water are mixed, dried to obtain sodium-doped tungsten oxide powder, and hydrogen reduction is carried out in a tube furnace at 1000 ℃ to prepare ultra-coarse tungsten powder with average particle size of 40 um. (3) Tungsten oxide or tungsten oxide powder and tungsten powder mixture are used as raw materials, steam and hydrogen are introduced into a reduction furnace for long-time reduction, and ultra-coarse tungsten powder is prepared. The process has the defects of long reduction time and low production efficiency. For example, patent 200910044492.3 discloses that tungsten oxide powder is used as a raw material, mixed gas of steam and hydrogen is introduced into a reduction furnace, and the mixture is reduced for 50 hours at 1350 ℃ to prepare ultra-coarse tungsten powder with the average particle size of 30 um.
Disclosure of Invention
The invention mainly aims to solve the technical problem of preparing ultra-coarse tungsten powder by the existing process to a certain extent, and provides a novel method for preparing ultra-coarse tungsten powder with uniform granularity under milder conditions, which provides a high-quality raw material for preparing ultra-coarse grain tungsten carbide hard alloy.
In order to achieve the above object, the method for preparing coarse tungsten powder by reduction of tungsten trioxide provided by the invention comprises the following steps:
(1) Putting tungsten trioxide and tungsten hexachloride into a ball mill according to a certain mass ratio, and mixing for a certain time to obtain a mixture of tungsten trioxide and tungsten hexachloride;
(2) Placing the mixture of tungsten trioxide and tungsten hexachloride into a boat, placing the boat in a reduction furnace, raising the temperature to a certain level, and then introducing hydrogen to perform one-stage reduction for a certain period of time, so that the tungsten hexachloride volatilizes and reduces to metal tungsten to precipitate on the surface of the tungsten trioxide;
(3) Then further raising the temperature in the reduction furnace, introducing mixed gas of hydrogen and steam into the reduction furnace for two-stage reinforcement reduction, and preserving heat for a certain time to obtain coarse tungsten powder.
Preferably, the tungsten trioxide in the step (1) has a particle size of 12-18um, the mass ratio of the tungsten hexachloride to the tungsten trioxide powder is 10% -30%, and the mixing time is 0.5-1 hour.
Preferably, the tungsten trioxide in step (1) has a particle size of 18um.
Preferably, the mass ratio of the tungsten hexachloride to the tungsten trioxide powder in the step (1) is 20%.
Preferably, the reaction temperature in the step (2) is 350-400 ℃, the hydrogen flow is 200-400ml/min, and the reaction time is 0.5-2 hours.
Preferably, the reduction temperature in the step (3) is 800-1000 ℃, the hydrogen flow is 300-600ml/min, the water vapor flow is 100-300ml/min, and the heat preservation time is 2-5 hours.
The invention adopts the following technical principle:
According to the invention, tungsten trioxide is used as a raw material, mixed with a certain proportion of tungsten hexachloride powder and tungsten oxide powder uniformly, and the characteristics of high activity and high volatility of tungsten chloride are utilized, hydrogen is adopted to perform primary reduction at a lower temperature, so that the tungsten chloride is reduced into metal tungsten and deposited on the surface of the tungsten trioxide, meanwhile, part of tungsten trioxide is pre-reduced, and then secondary reinforcement reduction is performed by adopting a mixed gas of hydrogen and steam at a higher temperature, so that coarse-particle tungsten powder is prepared. Because the boiling point of tungsten hexachloride is 348 ℃, when the reduction temperature is above 350 ℃, the high-activity tungsten chloride volatilizes, and is reduced into metal tungsten through hydrogen to be deposited on the surface of tungsten trioxide, so that tungsten trioxide particles are enlarged, and meanwhile, tungsten deposited on the surface of tungsten trioxide can play a role of a seed crystal, so that the particle size of tungsten powder is enlarged in the two-stage strengthening reduction process, and coarse-particle tungsten powder is prepared. Because tungsten hexachloride has the natural advantages of easy volatilization and easy reduction, compared with the means of doping alkali metal, introducing wet hydrogen and the like, the tungsten powder is promoted to grow up by virtue of volatilization-deposition, and the tungsten powder has better effect. In addition, the process adopts a two-stage reduction process, and tungsten trioxide powder deposited on the surface of the tungsten can be further reduced and grown in the two-stage reinforcement reduction process, so that coarse-grained tungsten powder can be prepared.
Compared with the prior art, the invention has the following beneficial effects:
By adjusting corresponding technological parameters, the novel method can be adopted to prepare coarse-particle tungsten powder with uniform granularity, complete morphology and average granularity of 22-36 um. The process has the advantages of uniform tungsten powder granularity, mild reaction condition, high product purity, complete tungsten powder crystal form and easy realization of industrialization.
Drawings
FIG. 1 is an SEM image of tungsten powder prepared in example 3;
FIG. 2 is an XRD pattern of tungsten powder prepared in example 3;
FIG. 3 is an SEM image of tungsten powder prepared in example 4;
FIG. 4 is an XRD pattern of tungsten powder prepared in example 4;
FIG. 5 is an SEM image of tungsten powder prepared in example 5;
fig. 6 is an XRD pattern of the tungsten powder prepared in example 5.
Detailed Description
The following examples are given to illustrate embodiments of the present invention and are not intended to limit the scope of the invention.
Example 1
Step one: 30g of tungsten trioxide powder with the average granularity of 18um and 3.0 g of tungsten hexachloride powder are taken and put into a ball mill to be mixed for 1 hour, so as to obtain the mixture of tungsten trioxide and tungsten hexachloride.
Step two: and (3) placing the mixture in the step (I) into a reduction furnace, heating to 400 ℃, and then introducing hydrogen for reduction, wherein the flow rate of the hydrogen is 400ml/min, and reacting for 2 hours.
Step three: then the temperature in the reduction furnace is increased to 1000 ℃, and mixed gas of hydrogen and water vapor is introduced, the flow rate of the hydrogen is 600ml/min, the flow rate of the water vapor is 300ml/min, the reaction is carried out for 5 hours, and then the reaction is carried out along with furnace cooling, thus preparing the coarse-particle tungsten powder with the average particle size of 30 um. The tungsten powder has uniform granularity, regular morphology and less adhesion among particles.
Example 2
Step one: 30g of tungsten trioxide powder with the average granularity of 18um and 6.0 g of tungsten hexachloride powder are taken and put into a ball mill to be mixed for 1 hour, so as to obtain the mixture of tungsten trioxide and tungsten hexachloride.
Step two: and (3) placing the mixture in the step (I) into a reduction furnace, heating to 400 ℃, and then introducing hydrogen for reduction, wherein the flow rate of the hydrogen is 400ml/min, and reacting for 2 hours.
Step three: then the temperature in the reduction furnace is increased to 1000 ℃, and mixed gas of hydrogen and water vapor is introduced, the flow rate of the hydrogen is 600ml/min, the flow rate of the water vapor is 300ml/min, the reaction is carried out for 5 hours, and then the reaction is carried out along with furnace cooling, thus preparing the coarse-particle tungsten powder with the average particle size of 36 um. The tungsten powder has uniform granularity, regular morphology and good dispersibility.
Example 3
Step one: 30g of tungsten trioxide powder with the average granularity of 18um and 9 g of tungsten hexachloride powder are taken and put into a ball mill to be mixed for 1 hour, so as to obtain the mixture of tungsten trioxide and tungsten hexachloride.
Step two: and (3) placing the mixture in the step (I) into a reduction furnace, heating to 400 ℃, and then introducing hydrogen for reduction, wherein the flow rate of the hydrogen is 400ml/min, and reacting for 2 hours.
Step three: and then the temperature in the reduction furnace is increased to 1000 ℃, mixed gas of hydrogen and water vapor is introduced, the flow rate of the hydrogen is 600ml/min, the flow rate of the water vapor is 300ml/min, the reaction is carried out for 5 hours, and then the reaction is carried out along with the cooling of the furnace, so that the coarse-particle tungsten powder with complete morphology, partial particle adhesion and average particle diameter of 32um is prepared. The SEM and XRD analysis results of the tungsten powder are shown in fig. 1 and 2.
Comparative example 1
Step one: 30g of tungsten trioxide powder with the average granularity of 18um and 2.4 g of tungsten hexachloride powder are taken and put into a ball mill to be mixed for 1 hour, so as to obtain the mixture of tungsten trioxide and tungsten hexachloride.
Step two: and (3) placing the mixture in the step (I) into a reduction furnace, heating to 400 ℃, and then introducing hydrogen for reduction, wherein the flow rate of the hydrogen is 400ml/min, and reacting for 2 hours.
Step three: then the temperature in the reduction furnace is increased to 1000 ℃, and mixed gas of hydrogen and water vapor is introduced, the flow rate of the hydrogen is 600ml/min, the flow rate of the water vapor is 300ml/min, the reaction is carried out for 5 hours, and then the reaction is carried out along with furnace cooling, so as to prepare the coarse-particle tungsten powder with the average particle size of 27 mu m. The tungsten powder has uniform granularity, regular morphology and less adhesion among particles.
Comparative example 2
Step one: 30 g of tungsten trioxide powder with the average granularity of 18um and 10.5 g of tungsten hexachloride powder are taken and put into a ball mill to be mixed for 1 hour, so as to obtain the mixture of tungsten trioxide and tungsten hexachloride.
Step two: and (3) placing the mixture in the step (I) into a reduction furnace, heating to 400 ℃, and then introducing hydrogen for reduction, wherein the flow rate of the hydrogen is 400ml/min, and reacting for 2 hours.
Step three: then the temperature in the reduction furnace is increased to 1000 ℃, and mixed gas of hydrogen and water vapor is introduced, the flow rate of the hydrogen is 600ml/min, the flow rate of the water vapor is 300ml/min, the reaction is carried out for 5 hours, and then the reaction is carried out along with furnace cooling, thus preparing the coarse-particle tungsten powder with the average particle size of 28 um. The shape of the tungsten powder is more regular, the granularity uniformity of the tungsten powder is deviated, and part of particles are adhered.
As can be seen from the data of the particle diameters of the tungsten powders in examples 1-3 and comparative examples 1-2, the mass ratio of tungsten trioxide to tungsten hexachloride has a large influence on the particle diameter of the tungsten powder. When the mass ratio of the tungsten hexachloride to the tungsten trioxide is 8%, the average granularity of the prepared tungsten powder is 27um, and the tungsten powder has uniform granularity, regular morphology and good dispersibility. When the mass ratio of the tungsten hexachloride to the tungsten trioxide is 20%, the average granularity of the prepared tungsten powder is 36um, and the tungsten powder has uniform granularity and good dispersibility. When the mass ratio of tungsten hexachloride to tungsten trioxide is increased to 30%, the average particle size of the tungsten powder prepared by reduction is 32um, but the uniformity of the particle size distribution is deviated. When the mass ratio of tungsten hexachloride to tungsten trioxide is further increased to 35%, the average particle size of the tungsten powder prepared by reduction is 28um, the uniformity of the particle size distribution of the tungsten powder is poor, and part of tungsten powder is seriously adhered. This is probably because the mass ratio of tungsten hexachloride increases, and part of tungsten is not precipitated on the surface of tungsten trioxide powder in the first stage reduction process, but tungsten powder forming fine particles is crystallized and separated alone, so that the uniformity of the particle size of tungsten powder is deteriorated in the second stage reinforcement reduction. Therefore, in the operation process, the technological parameters are required to be adjusted, and the coarse-particle tungsten powder with uniform granularity and complete crystallization is prepared.
Example 4
Step one: 30g of tungsten trioxide powder with the average granularity of 12um and 6 g of tungsten hexachloride powder are taken and put into a ball mill to be mixed for 1.0 hour, so as to obtain the mixture of tungsten trioxide and tungsten hexachloride.
Step two: and (3) placing the mixture in the step (I) into a reduction furnace, heating to 350 ℃, then introducing hydrogen for reduction, wherein the flow rate of the hydrogen is 200ml/min, and reacting for 0.5 hour.
Step three: and then the temperature in the reduction furnace is increased to 800 ℃, mixed gas of hydrogen and water vapor is introduced, the flow rate of the hydrogen is 300ml/min, the flow rate of the water vapor is 100ml/min, the reaction is carried out for 2 hours, and then the reaction is carried out along with furnace cooling, so that the particle tungsten powder with the relative deviation of the uniformity of the particle size and the average particle size of 22um is prepared. The SEM and XRD analysis results of the tungsten powder are shown in fig. 3 and 4.
Example 5
Step one: 30g of tungsten trioxide powder with the average particle size of 15um and 3g of tungsten hexachloride powder are taken and put into a ball mill to be mixed for 0.5 hour, so as to obtain the mixture of tungsten trioxide and tungsten hexachloride.
Step two: and (3) placing the mixture in the step (I) into a reduction furnace, heating to 350 ℃, then introducing hydrogen for reduction, wherein the flow rate of the hydrogen is 200ml/min, and reacting for 0.5 hour.
Step three: and then the temperature in the reduction furnace is increased to 800 ℃, mixed gas of hydrogen and water vapor is introduced, the flow rate of the hydrogen is 300ml/min, the flow rate of the water vapor is 100ml/min, the reaction is carried out for 2 hours, and then the reaction is carried out along with furnace cooling, so that the coarse-particle tungsten powder with uniform granularity, complete morphology and 24 mu m average particle size is prepared. The SEM and XRD analysis results of the tungsten powder are shown in fig. 5 and 6.
Example 6
Step one: 30g of tungsten trioxide powder with the average granularity of 18um and 6 g of tungsten hexachloride powder are taken and put into a ball mill to be mixed for 0.6 hour, thus obtaining the mixture of tungsten trioxide and tungsten hexachloride.
Step two: and (3) placing the mixture in the step (I) into a reduction furnace, heating to 370 ℃, then introducing hydrogen for reduction, wherein the flow rate of the hydrogen is 300ml/min, and reacting for 1.5 hours.
Step three: then the temperature in the reduction furnace is increased to 900 ℃, and mixed gas of hydrogen and water vapor is introduced, the flow rate of the hydrogen is 400ml/min, the flow rate of the water vapor is 200ml/min, the reaction is carried out for 4 hours, and then the reaction is carried out along with furnace cooling, thus obtaining the coarse-particle tungsten powder with the average particle size of 29 um. Compared with the tungsten powder in the example 5, the tungsten powder in the example 6 has uniform granularity and complete and regular morphology, and the XRD analysis and detection result is tungsten powder.
Claims (6)
1. The method for preparing coarse-particle tungsten powder by reduction of tungsten trioxide is characterized by comprising the following steps of:
(1) Putting tungsten trioxide and tungsten hexachloride into a ball mill according to a certain mass ratio, and mixing for a certain time to obtain a mixture of tungsten trioxide and tungsten hexachloride;
(2) Placing the mixture of tungsten trioxide and tungsten hexachloride into a boat, placing the boat in a reduction furnace, raising the temperature to a certain level, and then introducing hydrogen to perform one-stage reduction for a certain period of time, so that the tungsten hexachloride volatilizes and reduces to metal tungsten to precipitate on the surface of the tungsten trioxide;
(3) Then further raising the temperature in the reduction furnace, introducing mixed gas of hydrogen and steam into the reduction furnace for two-stage reinforcement reduction, and preserving heat for a certain time to obtain coarse tungsten powder.
2. The method according to claim 1, wherein the tungsten trioxide in the step (1) has a particle size of 12-18um, the mass ratio of the hexachloride to the tungsten trioxide powder is 10% -30%, and the mixing time is 0.5-1 hour.
3. The method of claim 2, wherein the tungsten trioxide in step (1) has a particle size of 18um.
4. The method according to claim 2, wherein the mass ratio of tungsten hexachloride to tungsten trioxide powder in the step (1) is 20%.
5. The process according to claim 1, wherein the reaction temperature in step (2) is 350 to 400 ℃, the hydrogen flow rate is 200 to 400ml/min, and the reaction time is 0.5 to 2 hours.
6. The method according to claim 1, wherein the reduction temperature in the step (3) is 800-1000 ℃, the hydrogen flow rate is 300-600ml/min, the water vapor flow rate is 100-300ml/min, and the incubation time is 2-5 hours.
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