CN115383128A - Method for preparing coarse-particle tungsten powder by tungsten trioxide reduction - Google Patents
Method for preparing coarse-particle tungsten powder by tungsten trioxide reduction Download PDFInfo
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- CN115383128A CN115383128A CN202211064009.XA CN202211064009A CN115383128A CN 115383128 A CN115383128 A CN 115383128A CN 202211064009 A CN202211064009 A CN 202211064009A CN 115383128 A CN115383128 A CN 115383128A
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title claims abstract description 108
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 38
- 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 53
- 239000001257 hydrogen Substances 0.000 claims abstract description 53
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 53
- 239000002245 particle Substances 0.000 claims abstract description 49
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 12
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 12
- 239000010937 tungsten Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 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
- 239000000843 powder Substances 0.000 claims description 23
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000001340 alkali metals Chemical group 0.000 abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 4
- 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 13
- 229910001930 tungsten oxide Inorganic materials 0.000 description 13
- 238000001816 cooling Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 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
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution 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
- 238000002360 preparation method 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
- 238000001035 drying 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
- 238000005065 mining Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000004663 powder metallurgy 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
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- 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 tungsten trioxide reduction, which comprises the steps of putting tungsten trioxide and tungsten hexachloride into a ball mill according to a certain mass ratio, uniformly mixing, putting the mixture of the tungsten trioxide and the tungsten hexachloride into a reduction furnace, introducing hydrogen at a relatively low temperature for first-stage reduction, volatilizing the tungsten hexachloride, reducing the tungsten hexachloride into metal tungsten deposited on the surface of the tungsten trioxide, and introducing a mixed gas of hydrogen and water vapor at a high temperature for second-stage enhanced reduction to promote the growth of tungsten powder particles, thereby preparing the coarse-particle tungsten powder. The method has the advantages that the defect that the product purity is reduced due to alkali metal residues in the traditional method for preparing the coarse-grained tungsten powder by doping the alkali metal Na/Li can be avoided, and the coarse-grained tungsten powder with high purity and complete crystallization can be prepared under mild 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 reducing tungsten trioxide powder.
Background
The macrocrystalline tungsten carbide hard alloy has the advantages of good toughness, high hardness, high thermal conductivity, good red hardness and the like, and is widely applied to various fields of petroleum drilling, mining tools, hard surface materials, stamping dies and the like. The tungsten powder is a raw material for preparing the tungsten carbide hard alloy, and the preparation of the coarse-particle tungsten powder is the key for preparing the ultra-coarse tungsten carbide hard alloy because the granularity of the tungsten powder and the tungsten carbide has obvious heredity.
Tungsten powder is generally prepared from tungsten oxide powder by a reduction process. At present, the process for preparing the coarse-particle tungsten powder is more, and the following methods are mainly classified according to the process principle: (1) Tungsten oxide is reduced by high-temperature hydrogen to prepare coarse-particle tungsten powder. Using yellow tungsten (WO) 3 ) Or blue tungsten (WO) 2.92 ) The raw material is prepared by adopting hydrogen to reduce for a long time at the temperature of more than 1300 ℃ to prepare coarse-grain tungsten powder. The process has the advantages of uniform tungsten powder particles and few false particles, but has the defects of high energy consumption and high cost due to high reduction temperature and high requirement on furnace body 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 ultra-coarse tungsten powder with an average particle size of 58-70um is prepared by using tungsten oxide and tungsten powder as raw materials and reducing with hydrogen at 1420-1600 ℃ for 0.5-2 hours. (2) The coarse-grained tungsten powder is prepared by adopting a method of doping tungsten oxide powder with alkali metal (Na or Li) through hydrogen reduction. The process utilizes the property that tungsten oxide and alkali metal oxide are easy to form low-melting-point compounds, and performs hydrogen reduction at higher temperature to prepare coarse-particle tungsten powder. Because of the limited volatility of alkali metals, particularly the Li doping, tungsten powder prepared by reduction often has a certain amount of alkali metal residues, which has adverse effects 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 mixing tungsten oxide, sodium tungstate and water, drying to obtain sodium-doped tungsten oxide powder, and performing hydrogen reduction in a tube furnace at 1000 ℃ to prepare ultra-coarse tungsten powder with average particle size of 40 um. (3) Tungsten oxide or a mixture of tungsten oxide powder and tungsten powder is used as a raw material, and water vapor and hydrogen are introduced into a reduction furnace for long-time reduction to prepare the ultra-coarse tungsten powder. The process has the defects of long reduction time and low production efficiency. For example patent 200910044492.3 discloses that the tungsten oxide powder is introduced into a reducing furnace and reduced at 1350 deg.c for 50 hr to obtain extra-coarse tungsten powder of 30um average particle size.
Disclosure of Invention
The invention mainly aims to solve the technical problem of preparing the ultra-coarse tungsten powder to a certain extent by the existing process, provides a novel method for preparing the ultra-coarse tungsten powder with uniform granularity under a mild condition, and provides a high-quality raw material for preparing the ultra-coarse grain tungsten carbide hard alloy.
In order to achieve the purpose, the invention provides a method for preparing coarse-particle tungsten powder by tungsten trioxide reduction, which 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 the tungsten trioxide and the tungsten hexachloride;
(2) Putting the mixture of tungsten trioxide and tungsten hexachloride into a boat, putting the boat in a reduction furnace, raising the temperature to a certain temperature, introducing hydrogen to carry out reduction for a period of time, and keeping the time for the tungsten hexachloride to volatilize and reduce the tungsten hexachloride into metal tungsten which is deposited on the surface of the tungsten trioxide;
(3) And then further raising the temperature in the reduction furnace, introducing a mixed gas of hydrogen and steam into the reduction furnace for secondary reinforced reduction, and keeping the temperature for a certain time to prepare the coarse-particle tungsten powder.
Preferably, the particle size of the tungsten trioxide in the step (1) is 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 particle size in step (1) is 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 technical principle adopted by the invention is as follows:
the method takes tungsten trioxide as a raw material, mixes a certain proportion of tungsten hexachloride powder and tungsten oxide powder, uniformly mixes the tungsten hexachloride powder and the tungsten oxide powder, performs first-stage reduction by using hydrogen at a lower temperature by utilizing the characteristics of high activity and high volatility of tungsten chloride, so that the tungsten chloride is reduced into metal tungsten and deposited on the surface of the tungsten trioxide, simultaneously pre-reduces part of the tungsten trioxide, and then performs second-stage enhanced reduction by using mixed gas of hydrogen and water vapor at a higher temperature, thereby preparing the coarse-particle tungsten powder. Because the boiling point of the 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 the tungsten trioxide, so that the tungsten trioxide particles are increased, and meanwhile, the tungsten deposited on the surface of the tungsten trioxide can play a role of a seed crystal, so that the particle size of the tungsten powder is increased in the two-stage reinforced reduction process, and the tungsten powder with coarse particles is prepared. Because tungsten hexachloride has the natural advantages of easy volatility and easy reduction, the tungsten powder is promoted to grow by means of volatilization-deposition compared with means of doping alkali metal, introducing wet hydrogen and the like, and the tungsten powder has a better effect. In addition, the process adopts a two-stage reduction process, and the tungsten trioxide powder with tungsten deposited on the surface can be further reduced and grown in the two-stage enhanced reduction process, so that the preparation of coarse-grained tungsten powder is facilitated.
Compared with the prior art, the invention has the following beneficial effects:
by adjusting corresponding process parameters, the novel method can be used for preparing coarse tungsten powder with uniform particle size, complete morphology and average particle size of 22-36 um. The process has the advantages of uniform tungsten powder granularity, mild reaction conditions, high product purity, complete tungsten powder crystal form and easy realization of industrialization.
Drawings
FIG. 1 is an SEM photograph of a tungsten powder prepared in example 3;
FIG. 2 is an XRD pattern of the tungsten powder prepared in example 3;
FIG. 3 is an SEM photograph of the tungsten powder prepared in example 4;
FIG. 4 is an XRD pattern of the tungsten powder prepared in example 4;
FIG. 5 is an SEM photograph of the 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 intended to illustrate the invention without further limiting its scope.
Example 1
The method comprises the following steps: 30 g of tungsten trioxide powder with the average particle size of 18um and 3.0 g of tungsten hexachloride powder are put into a ball mill to be mixed for 1 hour, so as to obtain a mixture of tungsten trioxide and tungsten hexachloride.
Step two: and (4) placing the mixture obtained in the first step into a reduction furnace, heating to 400 ℃, then introducing hydrogen into the reduction furnace for reduction, wherein the hydrogen flow is 400ml/min, and reacting for 2 hours.
Step three: and raising the temperature in the reduction furnace to 1000 ℃, introducing mixed gas of hydrogen and water vapor, reacting for 5 hours, wherein the hydrogen flow is 600ml/min, and the water vapor flow is 300ml/min, and then cooling along with the furnace to prepare the coarse-particle tungsten powder with the average particle size of 30 um. The tungsten powder has uniform granularity, regular appearance and less adhesion among particles.
Example 2
The method comprises the following steps: 30 g of tungsten trioxide powder with the average particle size of 18um and 6.0 g of tungsten hexachloride powder are put into a ball mill to be mixed for 1 hour, so as to obtain a mixture of tungsten trioxide and tungsten hexachloride.
Step two: and (3) putting the mixture obtained in the step one into a reduction furnace, heating to 400 ℃, introducing hydrogen into the reduction furnace for reduction, wherein the hydrogen flow is 400ml/min, and reacting for 2 hours.
Step three: and raising the temperature in the reduction furnace to 1000 ℃, introducing a mixed gas of hydrogen and steam, reacting for 5 hours, wherein the hydrogen flow is 600ml/min, and the steam flow is 300ml/min, and then cooling along with the furnace to prepare the coarse-particle tungsten powder with the average particle size of 36 um. The tungsten powder has uniform granularity, regular appearance and good dispersibility.
Example 3
The method comprises the following steps: 30 g of tungsten trioxide powder with the average particle size of 18um and 9 g of tungsten hexachloride powder are put into a ball mill to be mixed for 1 hour, so as to obtain a mixture of tungsten trioxide and tungsten hexachloride.
Step two: and (3) putting the mixture obtained in the step one into a reduction furnace, heating to 400 ℃, introducing hydrogen into the reduction furnace for reduction, wherein the hydrogen flow is 400ml/min, and reacting for 2 hours.
Step three: and raising the temperature in the reduction furnace to 1000 ℃, introducing mixed gas of hydrogen and water vapor, reacting for 5 hours, wherein the hydrogen flow is 600ml/min, the water vapor flow is 300ml/min, and cooling along with the furnace to obtain the coarse-particle tungsten powder with complete appearance, part of particles adhered and average particle size of 32 um. The results of scanning electron microscope SEM and XRD analysis of the tungsten powder are shown in fig. 1 and 2.
Comparative example 1
The method comprises the following steps: 30 g of tungsten trioxide powder with the average particle size of 18um and 2.4 g of tungsten hexachloride powder are put into a ball mill to be mixed for 1 hour, so as to obtain a mixture of tungsten trioxide and tungsten hexachloride.
Step two: and (3) putting the mixture obtained in the step one into a reduction furnace, heating to 400 ℃, introducing hydrogen into the reduction furnace for reduction, wherein the hydrogen flow is 400ml/min, and reacting for 2 hours.
Step three: and raising the temperature in the reduction furnace to 1000 ℃, introducing mixed gas of hydrogen and water vapor, reacting for 5 hours, wherein the hydrogen flow is 600ml/min, and the water vapor flow is 300ml/min, and then cooling along with the furnace to prepare the coarse-particle tungsten powder with the average particle size of 27 microns. The tungsten powder has uniform granularity, regular appearance and less adhesion among particles.
Comparative example 2
The method comprises the following steps: 30 g of tungsten trioxide powder with the average particle size of 18um and 10.5 g of tungsten hexachloride powder are put into a ball mill to be mixed for 1 hour, so as to obtain a mixture of tungsten trioxide and tungsten hexachloride.
Step two: and (4) placing the mixture obtained in the first step into a reduction furnace, heating to 400 ℃, then introducing hydrogen into the reduction furnace for reduction, wherein the hydrogen flow is 400ml/min, and reacting for 2 hours.
Step three: and raising the temperature in the reduction furnace to 1000 ℃, introducing mixed gas of hydrogen and water vapor, reacting for 5 hours, wherein the hydrogen flow is 600ml/min, and the water vapor flow is 300ml/min, and then cooling along with the furnace to prepare the coarse-particle tungsten powder with the average particle size of 28 um. The tungsten powder has regular appearance, the uniformity of the tungsten powder granularity is deviated, and partial particles are adhered.
As can be seen from the particle diameter data of the tungsten powders in examples 1 to 3 and comparative examples 1 to 2 described above, 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 particle size of the prepared tungsten powder is 27 mu m, and the tungsten powder is uniform in particle size, regular in shape and good in dispersibility. When the mass ratio of the tungsten hexachloride to the tungsten trioxide is 20%, the average particle size of the prepared tungsten powder is 36 mu m, and the tungsten powder is uniform in particle size and good in dispersibility. When the mass ratio of tungsten hexachloride to tungsten trioxide was increased to 30%, the average particle size of tungsten powder produced by reduction was 32um, but the uniformity of particle size distribution was deviated. When the mass ratio of the tungsten hexachloride to the tungsten trioxide is further increased to 35%, the average particle size of the tungsten powder prepared by reduction is 28 μm, the uniformity of the particle size distribution of the tungsten powder is deteriorated, and part of the tungsten powder is seriously adhered. This is probably because the mass ratio of tungsten hexachloride is increased, and a part of tungsten is not precipitated on the surface of the tungsten trioxide powder in the first-stage reduction process, but the tungsten powder in fine particles is formed and crystallized separately, so that the uniformity of the particle size of the tungsten powder is deteriorated in the second-stage enhanced reduction. Therefore, in the operation process, the technological parameters need to be adjusted, and the coarse-particle tungsten powder with uniform particle size and complete crystallization is prepared.
Example 4
The method comprises the following steps: 30 g of tungsten trioxide powder with the average particle size of 12um and 6 g of tungsten hexachloride powder are put into a ball mill to be mixed for 1.0 hour, so as to obtain a mixture of tungsten trioxide and tungsten hexachloride.
Step two: and (3) putting the mixture obtained in the step one into a reduction furnace, heating to 350 ℃, introducing hydrogen into the reduction furnace for reduction, wherein the hydrogen flow is 200ml/min, and reacting for 0.5 hour.
Step three: and raising the temperature in the reduction furnace to 800 ℃, introducing a mixed gas of hydrogen and steam, reacting for 2 hours, wherein the hydrogen flow is 300ml/min, the steam flow is 100ml/min, and cooling along with the furnace to obtain the granular tungsten powder with relative deviation of grain size uniformity and average grain size of 22 um. The results of scanning electron microscope SEM and XRD analysis of the tungsten powder are shown in fig. 3 and 4.
Example 5
The method comprises the following steps: 30 g of tungsten trioxide powder with the average particle size of 15um and 3 g of tungsten hexachloride powder are put into a ball mill to be mixed for 0.5 hour, so as to obtain a mixture of tungsten trioxide and tungsten hexachloride.
Step two: and (3) putting the mixture obtained in the step one into a reduction furnace, heating to 350 ℃, introducing hydrogen into the reduction furnace for reduction, wherein the hydrogen flow is 200ml/min, and reacting for 0.5 hour.
Step three: and raising the temperature in the reduction furnace to 800 ℃, introducing mixed gas of hydrogen and water vapor, reacting for 2 hours, wherein the hydrogen flow is 300ml/min, and the water vapor flow is 100ml/min, and then cooling along with the furnace to prepare the coarse-particle tungsten powder with uniform particle size, complete shape and 24um average particle size. The results of scanning electron microscopy SEM and XRD analysis of the tungsten powder are shown in fig. 5 and 6.
Example 6
The method comprises the following steps: 30 g of tungsten trioxide powder with the average particle size of 18um and 6 g of tungsten hexachloride powder are put into a ball mill to be mixed for 0.6 hour, so as to obtain a mixture of tungsten trioxide and tungsten hexachloride.
Step two: and (4) putting the mixture obtained in the step one into a reduction furnace, heating to 370 ℃, then introducing hydrogen into the reduction furnace for reduction, wherein the hydrogen flow is 300ml/min, and reacting for 1.5 hours.
Step three: and raising the temperature in the reduction furnace to 900 ℃, introducing mixed gas of hydrogen and water vapor, reacting for 4 hours, wherein the hydrogen flow is 400ml/min, and the water vapor flow is 200ml/min, and then cooling along with the furnace to prepare the coarse-particle tungsten powder with the average particle size of 29 um. Compared with the tungsten powder in the embodiment 5, the tungsten powder in the embodiment 6 has uniform particle size and complete and regular appearance, and the result of XRD analysis and detection is the tungsten powder.
Claims (6)
1. A method for preparing coarse-particle tungsten powder by tungsten trioxide reduction is characterized by comprising 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 the tungsten trioxide and the tungsten hexachloride;
(2) Putting the mixture of tungsten trioxide and tungsten hexachloride into a boat, putting the boat in a reduction furnace, raising the temperature to a certain temperature, introducing hydrogen to carry out reduction for a period of time, and keeping the time for the tungsten hexachloride to volatilize and reduce the tungsten hexachloride into metal tungsten which is deposited on the surface of the tungsten trioxide;
(3) And then further raising the temperature in the reduction furnace, introducing a mixed gas of hydrogen and steam into the reduction furnace for secondary reinforced reduction, and keeping the temperature for a certain time to prepare the coarse-particle tungsten powder.
2. The method according to claim 1, wherein the particle size of the tungsten trioxide in the step (1) is 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.
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 the tungsten hexachloride to the tungsten trioxide powder in the step (1) is 20%.
5. The method according to claim 1, wherein the reaction temperature in the step (2) is 350-400 ℃, the hydrogen flow rate is 200-400ml/min, and the reaction time is 0.5-2 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 holding time is 2-5 hours.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101664809A (en) * | 2009-10-09 | 2010-03-10 | 株洲硬质合金集团有限公司 | Uniform macromeritic tungsten powder and method for preparing tungsten carbide powder |
| CN106623962A (en) * | 2016-12-31 | 2017-05-10 | 湖南省华京粉体材料有限公司 | Method for preparing nanometer tungsten powder by organizing sodium tungstate |
| CN109079151A (en) * | 2018-08-16 | 2018-12-25 | 南昌大学 | A kind of method of high temperature solution phase reduction method tungsten oxide preparation extra-coarse tungsten powder |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101664809A (en) * | 2009-10-09 | 2010-03-10 | 株洲硬质合金集团有限公司 | Uniform macromeritic tungsten powder and method for preparing tungsten carbide powder |
| CN106623962A (en) * | 2016-12-31 | 2017-05-10 | 湖南省华京粉体材料有限公司 | Method for preparing nanometer tungsten powder by organizing sodium tungstate |
| CN109079151A (en) * | 2018-08-16 | 2018-12-25 | 南昌大学 | A kind of method of high temperature solution phase reduction method tungsten oxide preparation extra-coarse tungsten powder |
Non-Patent Citations (3)
| Title |
|---|
| 万林生;曾学品;赖星任;杨亮;刘鹏;: "仲钨酸铵结晶掺Cr制备的WC粉和超细硬质合金的性能研究", 稀有金属与硬质合金, no. 06, 20 December 2016 (2016-12-20) * |
| 谢俊杰;张龙辉;常卿卿;黄一春;: "掺杂与湿氢工艺制备超粗钨粉及其对合金性能的影响", 硬质合金, no. 01, 15 February 2018 (2018-02-15) * |
| 黄劲松, 周继承, 刘文胜, 黄伯云: "高密度合金粉末的制备与处理", 稀有金属与硬质合金, no. 04, 30 December 2003 (2003-12-30) * |
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