CN106623962A - Method for preparing nanometer tungsten powder by organizing sodium tungstate - Google Patents
Method for preparing nanometer tungsten powder by organizing sodium tungstate Download PDFInfo
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- CN106623962A CN106623962A CN201611267559.6A CN201611267559A CN106623962A CN 106623962 A CN106623962 A CN 106623962A CN 201611267559 A CN201611267559 A CN 201611267559A CN 106623962 A CN106623962 A CN 106623962A
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- tungsten
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- sodium tungstate
- tungsten powder
- salicylic acid
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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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- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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Abstract
The invention relates to a preparation method of nanometer tungsten powder, which is mainly used for preparing the nanometer tungsten powder by organizing tungsten. The method comprises the following steps: organizing sodium tungstate into tungsten salicylate, wherein the molar ratio of the sodium tungstate to sulfuric acid to salicylic acid is 1:(0.8-1.2):(0.8-1.2), and the molar concentration of tungstate ions in the prepared aqueous solution is 1 to 2 mol/L; performing thermal decomposition on the tungsten salicylate to obtain nanometer tungsten oxide, wherein the temperature is 200 to 340 DEG C and is preserved for 0.5 to 8 hours; and performing hydrogen reduction on the nanometer tungsten oxide to obtain the nanometer tungsten powder. The tungsten salicylate with low boiling point is formed by organizing the tungsten and then is subjected to thermal decomposition at 200 to 300 DEG C to form the nanometer tungsten oxide, the nanometer tungsten oxide is subjected to hydrogen reduction to obtain the nanometer tungsten powder with uniform granularity, the granularity of the nanometer tungsten powder is 20 to 40 nm, the purity of the nanometer tungsten powder is 99.99 percent, and the yield of the nanometer tungsten powder exceeds 99 percent. The method has the prominent advantages of simplicity in operation, cleanness and environmental friendliness.
Description
Technical field
The present invention relates to a kind of preparation method of nano-tungsten powder.It is to obtain bigcatkin willow by sodium tungstate and salicylic acid thermal response
Sour molybdenum, by wash purifying, through thermal decomposition obtain nanometer tungsten oxide, then through hydrogen reduction obtain nano-tungsten powder, for military project,
Space flight, medicine and other fields.
Technical background
Tungsten there is high density, high-melting-point, high rigidity, high-wearing feature, low thermal coefficient of expansion, excellent electrical and thermal conductivity performance with
And good decay resistance, it is widely used in many fields.Nano hard alloy is due to nanocrystalline burl
Structure and show the superior functions such as the incomparable high intensity of conventional material, high tenacity, high rigidity.Produce nano hard alloy
The most important condition is to prepare nanoscale WC powder, and the prerequisite for preparing nanometer WC powder is to prepare nano-tungsten powder, therefore prepares high-quality
Nano-tungsten powder it is of far-reaching significance, be hard alloy research focus.
At present, preparing the main method of nano-tungsten powder has：Efficiently ball-milling method, plasma method, sol-gel process, spraying
Seasoning, APT pyrolysis reduction methods, tungsten hexachloride hydrogen reduction method and tungsten oxide hydrogen reduction method, commercial Application it is more be plasma
Body method and tungsten oxide reducing process.
Plasma method is to provide an energy using induction plasma torch to concentrate（Plasma Center area temperature reaches
More than 10000 DEG C）, the higher reaction environment of temperature, coarse tungsten powder under high-purity H2/Ar2 mixed gas atmosphere Quick-gasifying,
Cracking forms tiny nano-tungsten powder particle.The method can be evenly distributed, the high nano-tungsten powder of sphericity.But the method
Equipment needed thereby has high demands；Need to consume the substantial amounts of energy；Yield poorly, it is difficult to big industrial scale production.
Tungsten oxide hydrogen reduction method, is to be made the hydrogen reduction in tungsten oxide powder using the reproducibility of hydrogen under atmosphere of hydrogen
Nano-tungsten powder method, tungsten oxide hydrogen reduction method is because its Preparation equipment is simple, technical maturity and be relatively easy to control, course of reaction not
It is easily introduced impurity, easy mass production, it has also become most widely used to prepare one of method of ultrafine tungsten powder.But tungsten oxide is also
Former method is high to the granularity requirements of tungsten oxide, it is necessary to have nano level tungsten oxide to be possible to obtain nano level tungsten powder.
The content of the invention
A kind of method for preparing nano-tungsten powder it is an object of the invention to provide sodium tungstate organises.Concrete preparation process is such as
Under：
A sodium tungstates organise
Sodium tungstate, sulfuric acid and salicylic acid are weighed, is reaction dissolvent with distilled water, at 90～120 DEG C 4～8h is reacted, obtain bigcatkin willow
Sour tungsten.Wherein sodium tungstate, sulfuric acid and salicylic molar ratio are 1:0.8～1.2:0.8～1.2, tungsten in the aqueous solution of configuration
The molar concentration of acid ion is 1～2mol/L.
B salicylic acids tungsten is purified
Reaction is obtained into salicylic acid tungsten through ion, distillation eliminating water obtains pure salicylic acid tungsten.
C pyrolysis
Salicylic acid tungsten after purification is warming up to into 200～340 DEG C, 0.5～8 hour is incubated.Using dry circulation during thermal decomposition
Argon gas is protected.Continuously produced using tube furnace, batch-type furnace etc., salicylic acid tungsten is thermally decomposed at high temperature, the steam-energy of decomposition
Enough realize the even of tungsten oxide, tungsten dioxide powder diameter is 5～20nm, the organic matter reuse of acquisition.
D is reduced
By the nanometer tungsten oxide of above-mentioned acquisition at 550～650 DEG C, hydrogen reducing is nano-tungsten powder.Entered using tube furnace, batch-type furnace
The continuous production of row, the Tungsten Powder Size of acquisition is 10～40nm.
Sodium tungstate, sulfuric acid are 1 with salicylic molar ratio:0.8～1.0:0.8～1.0.
The temperature of the pyrolysis of step C is 200～300 DEG C.
Sodium tungstate and salicylic acid fully react generation salicylic acid tungsten；Salicylic acid tungsten decomposes rapidly in 200～340 DEG C of liquefaction,
Substantial amounts of gas and heat are released, finely dispersed nanoscale tungsten can be obtained.There occurs bigcatkin willow during this first
The decomposition reaction of sour tungsten oxide complex, obtains the gas such as tungsten oxide and salicylic acid.
When salicylic acid tungsten in the presence of oxygen, reaction equation is as follows：
(C7H6O3)2WO2+1/2O2→WO3+2C7H6O3
When salicylic acid tungsten under an inert atmosphere, reaction equation is as follows：
(C7H6O3)2WO2→WO2+2C7H6O3
The link that tungstic acid is reduced to tungsten dioxide has been lacked in tungsten dioxide reduction.The hydrogen reduction of tungsten dioxide, reduction temperature exists
550～650 DEG C, reducing agent is hydrogen, and reaction equation is：
WO2+H2→W+2H2O
The present invention for producing nano Mo powder, with reaction temperature is low and the features such as efficiency high, reduction process is directly with dioxy
Change molybdenum to be reduced.Compared with conventional evaporation molybdenum trioxide is reduced, the temperature in each stage is reduced, equipment is simple to operation,
The material of equipment is required simultaneously relatively low；Compared with conventional precipitation reducing process, even particle size distribution, high income, more than 90% all
It is the molybdenum powder of 20～30nm, overcomes the phenomenon that general precipitation reducing process prepares the reunion of molybdenum powder high temperature.
Present invention process process is simple, yield is high, molybdenum powder nanosizing thorough, and even particle size distribution, it is easy to industrial metaplasia
Produce, with the characteristics of cleaning, energy-conservation and environmental protection.Gained nano Mo powder particle diameter is in 10～40nm, and purity is spherical 99.99%
Degree is high, and uniformity coefficient is high.
Specific embodiment
Below the present invention is described in further detail.
Embodiment 1
A sodium tungstates organise
Sodium tungstate, sulfuric acid and salicylic acid are weighed, is reaction dissolvent with distilled water, at 90 DEG C 4h is reacted, obtain salicylic acid tungsten, wolframic acid
Sodium, sulfuric acid are 1 with salicylic molar ratio:0.8:0.9, the molar concentration of tungstate ion is in the aqueous solution of configuration
1mol/L；
B salicylic acids tungsten is purified
Reaction is obtained into salicylic acid tungsten through ion, distillation eliminating water obtains pure salicylic acid tungsten；
C pyrolysis
Salicylic acid tungsten after purification is warming up to into 200 DEG C, 0.5 hour is incubated, is protected using dry circulation argon gas during thermal decomposition,
Continuously produced using tube furnace or batch-type furnace, salicylic acid tungsten is thermally decomposed at high temperature, the steam of decomposition realizes tungsten oxide
Even, tungsten dioxide powder diameter be 5～20nm, the organic matter reuse of acquisition；
D is reduced
By the nanometer tungsten oxide of above-mentioned acquisition at 550 DEG C, hydrogen reducing is nano-tungsten powder, is connected using tube furnace or batch-type furnace
Continuous production, the Tungsten Powder Size of acquisition is 10～40nm.
Embodiment 2
A sodium tungstates organise
Sodium tungstate, sulfuric acid and salicylic acid are weighed, is reaction dissolvent with distilled water, at 110 DEG C 6h is reacted, obtain salicylic acid tungsten, tungsten
Sour sodium, sulfuric acid are 1 with salicylic molar ratio: 1:0.8, the molar concentration of tungstate ion is in the aqueous solution of configuration
1.2mol/L；
B salicylic acids tungsten is purified
Reaction is obtained into salicylic acid tungsten through ion, distillation eliminating water obtains pure salicylic acid tungsten；
C pyrolysis
Salicylic acid tungsten after purification is warming up to into 240 DEG C, 3 hours are incubated, is protected using dry circulation argon gas during thermal decomposition, adopted
Continuously produced with tube furnace or batch-type furnace, salicylic acid tungsten is thermally decomposed at high temperature, the steam of decomposition realizes the equal of tungsten oxide
Even nanosizing, tungsten dioxide powder diameter be 5～20nm, the organic matter reuse of acquisition；
D is reduced
By the nanometer tungsten oxide of above-mentioned acquisition at 650 DEG C, hydrogen reducing is nano-tungsten powder, is connected using tube furnace or batch-type furnace
Continuous production, the Tungsten Powder Size of acquisition is 10～40nm.
Embodiment 3
A sodium tungstates organise
Sodium tungstate, sulfuric acid and salicylic acid are weighed, is reaction dissolvent with distilled water, at 120 DEG C 8h is reacted, obtain salicylic acid tungsten, tungsten
Sour sodium, sulfuric acid are 1 with salicylic molar ratio: 1.1:1.2, the molar concentration of tungstate ion is in the aqueous solution of configuration
2mol/L；
B salicylic acids tungsten is purified
Reaction is obtained into salicylic acid tungsten through ion, distillation eliminating water obtains pure salicylic acid tungsten；
C pyrolysis
Salicylic acid tungsten after purification is warming up to into 330 DEG C, 8 hours are incubated, is protected using dry circulation argon gas during thermal decomposition, adopted
Continuously produced with tube furnace or batch-type furnace, salicylic acid tungsten is thermally decomposed at high temperature, the steam of decomposition realizes the equal of tungsten oxide
Even nanosizing, tungsten dioxide powder diameter be 5～20nm, the organic matter reuse of acquisition；
D is reduced
By the nanometer tungsten oxide of above-mentioned acquisition at 630 DEG C, hydrogen reducing is nano-tungsten powder, is connected using tube furnace or batch-type furnace
Continuous production, the Tungsten Powder Size of acquisition is 10～40nm.
Claims (3)
1. a kind of sodium tungstate organises the method for preparing nano-tungsten powder, it is characterised in that preparation process is as follows：
A sodium tungstates organise
Sodium tungstate, sulfuric acid and salicylic acid are weighed, is reaction dissolvent with distilled water, at 90～120 DEG C 4～8h is reacted, obtain bigcatkin willow
Sour tungsten, sodium tungstate, sulfuric acid are 1 with salicylic molar ratio:0.8～1.2:0.8～1.2, tungstate radicle in the aqueous solution of configuration
The molar concentration of ion is 1～2mol/L；
B salicylic acids tungsten is purified
Reaction is obtained into salicylic acid tungsten through ion, distillation eliminating water obtains pure salicylic acid tungsten；
C pyrolysis
Salicylic acid tungsten after purification is warming up to into 200～340 DEG C, 0.5～8 hour is incubated, using dry circulation during thermal decomposition
Argon gas is protected, and is continuously produced using tube furnace or batch-type furnace, and salicylic acid tungsten is thermally decomposed at high temperature, and the steam of decomposition is realized
The even of tungsten oxide, tungsten dioxide powder diameter be 5～20nm, the organic matter reuse of acquisition；
D is reduced
By the nanometer tungsten oxide of above-mentioned acquisition at 550～650 DEG C, hydrogen reducing is nano-tungsten powder, using tube furnace or batch-type furnace
Continuously produced, the Tungsten Powder Size of acquisition is 10～40nm.
2. sodium tungstate as claimed in claim 1 organises the method for preparing nano-tungsten powder, it is characterised in that：Sodium tungstate, sulfuric acid
It is 1 with salicylic molar ratio:0.8～1.0:0.8～1.0.
3. sodium tungstate as claimed in claim 1 organises the method for preparing nano-tungsten powder, it is characterised in that：The heat of step C point
The temperature of solution reaction is 200～300 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107470646A (en) * | 2017-08-28 | 2017-12-15 | 湖南科技大学 | A kind of preparation method of ultrafine tungsten powder composite granule |
| CN107686729A (en) * | 2017-09-30 | 2018-02-13 | 五邑大学 | Preparation method of metal tungsten quantum dots |
| CN108500283A (en) * | 2018-04-23 | 2018-09-07 | 北京科技大学 | A kind of method that inexpensive two sections of reduction prepare nano-tungsten powder |
| CN115383128A (en) * | 2022-09-01 | 2022-11-25 | 江西理工大学 | Method for preparing coarse-particle tungsten powder by tungsten trioxide reduction |
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| CN103302300A (en) * | 2013-06-24 | 2013-09-18 | 刘亚静 | Preparation method of tungsten nano powder |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107470646A (en) * | 2017-08-28 | 2017-12-15 | 湖南科技大学 | A kind of preparation method of ultrafine tungsten powder composite granule |
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| CN107686729B (en) * | 2017-09-30 | 2020-09-29 | 五邑大学 | Preparation method of metal tungsten quantum dots |
| CN108500283A (en) * | 2018-04-23 | 2018-09-07 | 北京科技大学 | A kind of method that inexpensive two sections of reduction prepare nano-tungsten powder |
| CN115383128A (en) * | 2022-09-01 | 2022-11-25 | 江西理工大学 | Method for preparing coarse-particle tungsten powder by tungsten trioxide reduction |
| CN115383128B (en) * | 2022-09-01 | 2024-05-14 | 江西理工大学 | Method for preparing coarse-particle tungsten powder by reduction of tungsten trioxide |
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