CN114101695A - Production process of polyhedral tungsten powder - Google Patents
Production process of polyhedral tungsten powder Download PDFInfo
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- CN114101695A CN114101695A CN202111385244.2A CN202111385244A CN114101695A CN 114101695 A CN114101695 A CN 114101695A CN 202111385244 A CN202111385244 A CN 202111385244A CN 114101695 A CN114101695 A CN 114101695A
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 166
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims abstract description 80
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 76
- 239000002245 particle Substances 0.000 claims abstract description 43
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 22
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 239000002270 dispersing agent Substances 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 18
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 18
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 abstract description 48
- 238000000034 method Methods 0.000 abstract description 24
- 230000006911 nucleation Effects 0.000 abstract description 8
- 238000010899 nucleation Methods 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 8
- 238000001694 spray drying Methods 0.000 description 8
- 229910052721 tungsten Inorganic materials 0.000 description 8
- 239000010937 tungsten Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910001080 W alloy Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 238000011197 physicochemical method Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000875 high-speed ball milling Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011800 void material Substances 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)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a production process of polyhedral tungsten powder, which relates to the technical field of tungsten powder production and comprises the following steps: dispersing tungsten powder in water with the aid of a dispersing agent, adding ammonium metatungstate powder and ammonium paratungstate powder, and uniformly stirring to obtain a mixed solution; drying the mixed solution to obtain dry powder; uniformly mixing the dry powder with ammonium carbonate to obtain composite powder; and adding the composite powder into a reduction furnace, and introducing hydrogen for reduction to prepare the polyhedral tungsten powder. The method has the beneficial effects that the prepared tungsten powder is in a polyhedral structure by regulating and controlling the nucleation and growth process of decomposing ammonium metatungstate and ammonium paratungstate into tungsten trioxide, the particle size of the tungsten powder is uniform, the particle size distribution is narrow, and the average size of the tungsten powder is 0.3-0.9 mu m.
Description
Technical Field
The invention relates to the technical field of tungsten powder production, in particular to a production process of polyhedral tungsten powder.
Background
Tungsten is a precious rare metal and is widely used as cemented carbide, special steel and various tungsten products. The metal tungsten powder is a raw material for preparing the metal tungsten and the tungsten alloy, the production of the metal tungsten powder is a key step for producing the metal tungsten and the tungsten alloy, and the performance of the tungsten powder influences the performance of tungsten and alloy products thereof in the aspects of pressing, sintering, processing and the like to a great extent.
At present, methods for preparing tungsten powder at home and abroad mainly comprise methods such as a mechanical ball milling method, a spray drying method, a sol-gel method, a physicochemical method and a plasma physicochemical method, and the tungsten powder prepared by different methods has respective characteristics. Taking a mechanical ball milling method as an example, the tungsten powder prepared by the method has thick particles and uneven micro-morphology, other elements are easily doped in the ball milling process, and meanwhile, uncontrollable side reactions can be brought by high temperature caused by high-speed ball milling. The spray drying method is a method for preparing hollow tungsten powder by mixing tungsten trioxide, a surfactant and a pore-forming agent into slurry, and performing spray drying and hydrogen reduction, and the obtained product has large particles and strong dependence on equipment. The sol-gel method is to hydrolyze inorganic salt or metal alkoxide, add organic acid as ligand, obtain fine and uniform tungsten trioxide powder through drying and calcining, and then prepare tungsten powder through hydrogen reduction.
Ammonium paratungstate is commonly used in the prior art as a raw material, and Ammonium Paratungstate (APT) is firstly heated and decomposed into WO3/WO2.9And then gradually reducing the W into W by hydrogen to obtain the tungsten powder. In decomposition of ammonium paratungstate to WO3/WO2.9In the process, the tungsten trioxide is easy to agglomerate, so that the particle size of the tungsten trioxide is too large; the tungsten powder prepared by reducing tungsten trioxide by hydrogen has the disadvantage that the original microscopic morphology of the tungsten trioxide can be changed due to the volatilization-deposition effect while the tungsten trioxide is reduced at high temperature, so that the purpose of controlling the morphology of the tungsten powder can not be achieved by controlling the morphology of the oxide.
Disclosure of Invention
The invention aims to at least solve one of the technical problems in the prior art and provides a production process of polyhedral tungsten powder.
The technical solution of the invention is as follows:
a production process of polyhedral tungsten powder comprises the following steps:
s1, dispersing tungsten powder in water with the aid of a dispersing agent, adding ammonium metatungstate powder and ammonium paratungstate powder, and uniformly stirring to obtain a mixed solution;
s2, drying the mixed solution obtained in the step S1 to obtain dry powder;
s3, uniformly mixing the dried powder obtained in the step S2 with ammonium carbonate to obtain composite powder;
s4, adding the composite powder obtained in the step S3 into a reduction furnace, and introducing hydrogen for reduction to obtain the polyhedral tungsten powder.
In a specific embodiment of the present invention, in step S3, ammonium polyphosphate is further added and uniformly mixed to obtain a composite powder.
In a specific embodiment of the present invention, in step S3, the amount of ammonium polyphosphate added is 0.1 to 1% of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder.
In a specific embodiment of the present invention, in step S1, the amount of tungsten powder added is 1 to 2% of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder.
In a specific embodiment of the invention, in step S1, the mass ratio of the ammonium metatungstate powder to the ammonium paratungstate powder is 4-6: 4-6; the purity of the ammonium metatungstate powder and the purity of the ammonium paratungstate powder are both more than 99.5%, and the particle size of the ammonium metatungstate powder and the particle size of the ammonium paratungstate powder are both 20-30 mu m.
In a specific embodiment of the present invention, in step S1, the dispersant is polyethylene glycol, and the addition amount of the dispersant is 0.2 to 0.3% of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder.
In a specific embodiment of the present invention, the drying temperature in step S2 is 60 to 80 ℃.
In a specific embodiment of the present invention, in step S3, the amount of ammonium carbonate added is 1 to 2% of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder.
In a specific embodiment of the present invention, the reduction temperature in step S4 is 700 to 850 ℃.
In a specific embodiment of the invention, in the step S4, the temperature is first raised to 700-750 ℃ at a rate of 3-5 ℃/min and is kept for 2-5 h, and then the temperature is continuously raised to 800-850 ℃ at a rate of 6-8 ℃/min and is kept for 2-3 h.
The invention has at least one of the following beneficial effects:
firstly, the method takes ammonium metatungstate and ammonium paratungstate as raw materials, and because the reduction paths and the reduction speeds of the ammonium metatungstate and the ammonium paratungstate are different, the method takes multiple phases consisting of the ammonium metatungstate and the ammonium paratungstate as the raw materials, can reduce the agglomeration of tungsten trioxide obtained by decomposition, and finally enables the granularity of the prepared tungsten powder to be smaller; and the volatilization-deposition function of the tungsten trioxide can be reduced, and the local reduction reaction is facilitated, so that the prepared tungsten powder is uniform in size. Secondly, because the gradual decomposition of ammonium metatungstate and ammonium paratungstate into tungsten trioxide goes through the process that the tungsten trioxide goes from crystals to amorphous clusters and then goes to nucleation to generate crystals, the tungsten trioxide is easy to agglomerate in the decomposition process, in order to solve the technical problem, the invention disperses tungsten powder in water and uniformly mixes with the ammonium metatungstate and the ammonium paratungstate through a dispersing agent, and adds ammonium carbonate and polyphosphoric acid, the tungsten powder and ammonium carbonate which are uniformly distributed in the ammonium metatungstate and the ammonium paratungstate and the polyphosphoric acid provide a large amount of heterogeneous nucleation points for amorphous cluster nucleation, thereby improving the nucleation rate of the tungsten trioxide, forming steric hindrance, hindering the coalescence growth of tungsten trioxide crystal nuclei and being beneficial to reducing the particle size of the tungsten trioxide; meanwhile, in the decomposition process of ammonium metatungstate and ammonium paratungstate, ammonium carbonate and ammonium polyphosphate are heated and oxidized, the ammonium carbonate is decomposed to generate ammonia gas and carbon dioxide, the ammonium polyphosphate is decomposed to generate ammonia gas and phosphoric acid, the gas generated by decomposition improves the void ratio of the nano tungsten trioxide, the function of a pore-forming agent is played, the coalescence of tungsten trioxide is further avoided, the appearance and the granularity of the nano tungsten trioxide are effectively ensured, the nano tungsten trioxide with a loose structure is obtained, the nucleation and growth control in the process of forming the tungsten trioxide by decomposing the ammonium metatungstate are realized, and the problem of regulation and control of the nucleation, the granularity and the dispersity in the production process of tungsten powder is solved. Finally, the applicant finds that the suitable reduction temperature of the ammonium metatungstate is 700-750 ℃, and the suitable reduction temperature of the ammonium paratungstate is 800-850 ℃, so that the ammonium metatungstate is firstly heated to 700-750 ℃ at a low speed in a sectional heating mode, and the decomposition and the reduction of the ammonium metatungstate are facilitated; and then rapidly heating to 800-850 ℃, which is beneficial to the decomposition and reduction of ammonium paratungstate and can also reduce the volatilization of tungsten trioxide, so that the prepared tungsten powder is in a polyhedral structure.
In conclusion, the tungsten powder prepared by the method is in a polyhedral structure through regulating and controlling nucleation and growth processes of decomposing ammonium metatungstate and ammonium paratungstate into tungsten trioxide, the particle size of the tungsten powder is uniform, the particle size distribution is narrow, and the average size of the tungsten powder is 0.3-0.9 mu m.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
A production process of polyhedral tungsten powder comprises the following steps:
s1, dispersing tungsten powder in water with the aid of polyethylene glycol serving as a dispersing agent, adding ammonium metatungstate powder and ammonium paratungstate powder, and uniformly stirring to obtain a mixed solution; wherein the adding amount of the tungsten powder is 1 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder, the adding amount of the dispersing agent is 0.2 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder, and the adding amount of the water is 2 times of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder; the mass ratio of the ammonium metatungstate powder to the ammonium paratungstate powder is 4: 6; the purity of the ammonium metatungstate powder and the purity of the ammonium paratungstate powder are both more than 99.5%, and the particle size of the ammonium metatungstate powder and the particle size of the ammonium paratungstate powder are both 20 micrometers.
S2, spray drying the mixed solution obtained in the step S1 at the drying temperature of 60 ℃ to obtain dry powder;
s3, uniformly mixing the dry powder obtained in the step S2 with ammonium carbonate and ammonium polyphosphate to obtain composite powder; wherein the adding amount of ammonium carbonate is 1 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder, and the adding amount of ammonium polyphosphate is 1 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder.
S4, adding the composite powder obtained in the step S3 into a reduction furnace, introducing hydrogen for reduction, heating to 700 ℃ at the speed of 3 ℃/min, keeping the temperature for 5 hours, then continuously heating to 800 ℃ at the speed of 6 ℃/min, and keeping the temperature for 2 hours to obtain the polyhedral tungsten powder.
Example 2
A production process of polyhedral tungsten powder comprises the following steps:
s1, dispersing tungsten powder in water with the aid of polyethylene glycol serving as a dispersing agent, adding ammonium metatungstate powder and ammonium paratungstate powder, and uniformly stirring to obtain a mixed solution; wherein the adding amount of the tungsten powder is 1.2 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder, the adding amount of the dispersing agent is 0.22 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder, and the adding amount of the water is 3 times of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder; the mass ratio of the ammonium metatungstate powder to the ammonium paratungstate powder is 4.5: 5.5; the purity of the ammonium metatungstate powder and the purity of the ammonium paratungstate powder are both more than 99.5%, and the particle size of the ammonium metatungstate powder and the particle size of the ammonium paratungstate powder are both 20-30 mu m.
S2, spray drying the mixed solution obtained in the step S1 at 65 ℃ to obtain dry powder;
s3, uniformly mixing the dry powder obtained in the step S2 with ammonium carbonate and ammonium polyphosphate to obtain composite powder; wherein the adding amount of ammonium carbonate is 1.2 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder, and the adding amount of ammonium polyphosphate is 0.9 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder.
S4, adding the composite powder obtained in the step S3 into a reduction furnace, introducing hydrogen for reduction, heating to 710 ℃ at the speed of 3 ℃/min, preserving heat for 4 hours, then continuously heating to 810 ℃ at the speed of 6 ℃/min, preserving heat for 2 hours, and obtaining the polyhedral tungsten powder.
Example 3
A production process of polyhedral tungsten powder comprises the following steps:
s1, dispersing tungsten powder in water with the aid of polyethylene glycol serving as a dispersing agent, adding ammonium metatungstate powder and ammonium paratungstate powder, and uniformly stirring to obtain a mixed solution; wherein the adding amount of the tungsten powder is 1.5 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder, the adding amount of the dispersing agent is 0.25 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder, and the adding amount of the water is 4 times of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder; the mass ratio of the ammonium metatungstate powder to the ammonium paratungstate powder is 5: 5; the purity of the ammonium metatungstate powder and the purity of the ammonium paratungstate powder are both more than 99.5%, and the particle size of the ammonium metatungstate powder and the particle size of the ammonium paratungstate powder are both 20-30 mu m.
S2, spray drying the mixed solution obtained in the step S1 at the drying temperature of 70 ℃ to obtain dry powder;
s3, uniformly mixing the dry powder obtained in the step S2 with ammonium carbonate and ammonium polyphosphate to obtain composite powder; wherein the adding amount of ammonium carbonate is 1.5 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder, and the adding amount of ammonium polyphosphate is 0.5 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder.
S4, adding the composite powder obtained in the step S3 into a reduction furnace, introducing hydrogen for reduction, heating to 730 ℃ at the speed of 4 ℃/min, preserving heat for 3 hours, then continuously heating to 820 ℃ at the speed of 7 ℃/min, preserving heat for 2.5 hours, and obtaining the polyhedral tungsten powder.
Example 4
A production process of polyhedral tungsten powder comprises the following steps:
s1, dispersing tungsten powder in water with the aid of polyethylene glycol serving as a dispersing agent, adding ammonium metatungstate powder and ammonium paratungstate powder, and uniformly stirring to obtain a mixed solution; wherein the adding amount of the tungsten powder is 1.8 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder, the adding amount of the dispersing agent is 0.22 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder, and the adding amount of the water is 3 times of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder; the mass ratio of the ammonium metatungstate powder to the ammonium paratungstate powder is 5.5: 4.5; the purity of the ammonium metatungstate powder and the purity of the ammonium paratungstate powder are both more than 99.5%, and the particle size of the ammonium metatungstate powder and the particle size of the ammonium paratungstate powder are both 20-30 mu m.
S2, spray drying the mixed solution obtained in the step S1 at 65 ℃ to obtain dry powder;
s3, uniformly mixing the dry powder obtained in the step S2 with ammonium carbonate and ammonium polyphosphate to obtain composite powder; wherein the adding amount of ammonium carbonate is 1.8 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder, and the adding amount of ammonium polyphosphate is 0.3 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder.
S4, adding the composite powder obtained in the step S3 into a reduction furnace, introducing hydrogen for reduction, heating to 740 ℃ at the speed of 4 ℃/min, keeping the temperature for 3 hours, then continuously heating to 840 ℃ at the speed of 7 ℃/min, and keeping the temperature for 2.5 hours to obtain the polyhedral tungsten powder.
Example 5
A production process of polyhedral tungsten powder comprises the following steps:
s1, dispersing tungsten powder in water with the aid of polyethylene glycol serving as a dispersing agent, adding ammonium metatungstate powder and ammonium paratungstate powder, and uniformly stirring to obtain a mixed solution; wherein the adding amount of the tungsten powder is 2 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder, the adding amount of the dispersing agent is 0.3 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder, and the adding amount of the water is 6 times of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder; the mass ratio of the ammonium metatungstate powder to the ammonium paratungstate powder is 6: 4; the purity of the ammonium metatungstate powder and the purity of the ammonium paratungstate powder are both more than 99.5%, and the particle size of the ammonium metatungstate powder and the particle size of the ammonium paratungstate powder are both 20-30 mu m.
S2, spray drying the mixed solution obtained in the step S1 at the drying temperature of 80 ℃ to obtain dry powder;
s3, uniformly mixing the dry powder obtained in the step S2 with ammonium carbonate and ammonium polyphosphate to obtain composite powder; wherein the adding amount of ammonium carbonate is 2 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder, and the adding amount of ammonium polyphosphate is 0.1 percent of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder.
S4, adding the composite powder obtained in the step S3 into a reduction furnace, introducing hydrogen for reduction, heating to 750 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, then continuously heating to 850 ℃ at the speed of 8 ℃/min, and keeping the temperature for 2 hours to obtain the polyhedral tungsten powder.
Comparative example 1
The difference from example 1 is that: the same procedure as in example 1 was repeated except that no tungsten powder was added in step S1 and no ammonium carbonate or ammonium polyphosphate was added in step S3.
Comparative example 2
The difference from example 1 is that: the procedure of example 1 was otherwise the same as the procedure of example 1 except that the ammonium metatungstate powder in step S1 was changed to ammonium paratungstate powder, i.e., only ammonium paratungstate powder was used as a raw material.
Comparative example 3
The difference from example 1 is that:
step S4 is changed to: and (4) adding the composite powder obtained in the step (S3) into a reduction furnace, introducing hydrogen for reduction, heating to 700 ℃ at the speed of 3 ℃/min, and preserving heat for 7 hours to obtain the polyhedral tungsten powder. I.e. no staged heating.
The average size and the particle size distribution of the tungsten powders prepared in examples 1 to 5 and comparative examples 1 to 3 were measured by a laser particle sizer, and the results are shown in table 1:
TABLE 1
| Shape of tungsten powder | Average size D50 | D100/D50 | |
| Example 1 | About 82% is polyhedral and about 18% is spherical | 0.85μm | 1.8 |
| Example 2 | About 89% is polyhedral and about 11% is spherical | 0.78μm | 1.6 |
| Example 3 | About 91% is polyhedral and about 9% is spherical | 0.62μm | 1.4 |
| Example 4 | About 93% is polyhedral and about 7% is spherical | 0.59μm | 1.3 |
| Example 5 | About 94% is polyhedral and about 6% is spherical | 0.41μm | 1.5 |
| Comparative example 1 | About 8% is polyhedral and about 92% is spherical | 3.48μm | 4.1 |
| Comparative example 2 | About 46% is polyhedral shape, and about 54% is spherical shape | 2.12μm | 2.9 |
| Comparative example 3 | About 57% is polyhedral and about 43% is spherical | 1.49μm | 2.3 |
As can be seen from Table 1, the tungsten powders obtained in examples 1 to 5Most of which are polyhedral in shape and a few of which are spherical in shape, and an average particle diameter D500.4 to 0.9 μm, maximum particle diameter D100With an average particle diameter D50The ratio of the particle diameter to the particle diameter is 1.3 to 1.8, i.e., the maximum particle diameter D100Less than the average particle diameter D50Twice as much as that of the tungsten powder obtained in examples 1 to 5, it can be seen that the tungsten powder obtained in examples 1 to 5 is polyhedral in average particle diameter D50The particle size is between 0.4 and 0.9 mu m, and the particle size distribution is narrow. As can be seen from comparison of examples 1 to 5 with comparative examples 1 to 3, the tungsten powders obtained in comparative example 1 (without addition of tungsten powder, ammonium carbonate or ammonium polyphosphate), comparative example 2 (using only ammonium paratungstate as a raw material) and comparative example 3 (without sectional heating) were mostly spherical and rarely polyhedral in shape, and had an average particle diameter D50Greater than practical examples 1 to 5, maximum particle diameter D100With an average particle diameter D50The ratio of the particle diameter to the particle diameter is 2.1 to 3.9, i.e., the maximum particle diameter D100Greater than the average particle diameter D50The two times of the total weight of the tungsten powder are shown in the specification, and whether the tungsten powder, the ammonium carbonate and the polyphosphoric acid are added or not and whether the sectional heating is carried out or not are all influenced by the structure, the particle size and the particle size distribution of the prepared tungsten powder.
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.
Claims (10)
1. The production process of the polyhedral tungsten powder is characterized by comprising the following steps of:
s1, dispersing tungsten powder in water with the aid of a dispersing agent, adding ammonium metatungstate powder and ammonium paratungstate powder, and uniformly stirring to obtain a mixed solution;
s2, drying the mixed solution obtained in the step S1 to obtain dry powder;
s3, uniformly mixing the dried powder obtained in the step S2 with ammonium carbonate to obtain composite powder;
s4, adding the composite powder obtained in the step S3 into a reduction furnace, and introducing hydrogen for reduction to obtain the polyhedral tungsten powder.
2. The production process of polyhedral tungsten powder according to claim 1, wherein in step S3, ammonium polyphosphate is further added and mixed uniformly to obtain composite powder.
3. A polyhedral tungsten powder production process according to claim 2, wherein in step S3, the addition amount of ammonium polyphosphate is 0.1-1% of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder.
4. A polyhedral tungsten powder production process according to claim 1, wherein in step S1, the addition amount of tungsten powder is 1-2% of the total mass of ammonium metatungstate powder and ammonium paratungstate powder.
5. A polyhedral tungsten powder production process according to claim 1, wherein in step S1, the mass ratio of ammonium metatungstate powder to ammonium paratungstate powder is 4-6: 4-6; the purity of the ammonium metatungstate powder and the purity of the ammonium paratungstate powder are both more than 99.5%, and the particle size of the ammonium metatungstate powder and the particle size of the ammonium paratungstate powder are both 20-30 mu m.
6. A polyhedral tungsten powder production process according to claim 1, wherein in step S1, the dispersant is polyethylene glycol, and the addition amount of the dispersant is 0.2-0.3% of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder.
7. The production process of polyhedral tungsten powder according to claim 1, wherein the drying temperature in the step S2 is 60-80 ℃.
8. A polyhedral tungsten powder production process according to claim 1, wherein in step S3, the addition amount of ammonium carbonate is 1-2% of the total mass of the ammonium metatungstate powder and the ammonium paratungstate powder.
9. The production process of polyhedral tungsten powder according to claim 1, wherein the reduction temperature in the step S4 is 700 to 850 ℃.
10. The production process of polyhedral tungsten powder according to claim 9, wherein in step S4, the temperature is raised to 700-750 ℃ at a rate of 3-5 ℃/min and kept for 2-5 h, and then the temperature is raised to 800-850 ℃ at a rate of 6-8 ℃/min and kept for 2-3 h.
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