CN101774024A - Preparation method of tungsten-cobalt composite oxide powder - Google Patents
Preparation method of tungsten-cobalt composite oxide powder Download PDFInfo
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- CN101774024A CN101774024A CN201010101162A CN201010101162A CN101774024A CN 101774024 A CN101774024 A CN 101774024A CN 201010101162 A CN201010101162 A CN 201010101162A CN 201010101162 A CN201010101162 A CN 201010101162A CN 101774024 A CN101774024 A CN 101774024A
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- tungsten
- cobalt
- composite oxide
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- oxide powder
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Abstract
The invention discloses a preparation method of tungsten-cobalt composite oxide powder. The method comprises the following steps: preparing metatungstic acid solution with a certain concentration; adding cobalt salt powder, crystal or solution in the metatungstic acid solution, heating, stirring, obtaining tungsten-cobalt composite solution after full reaction; drying the tungsten-cobalt composite solution to pelletize; and further drying the obtained powder particles after drying and pelletizing to obtain tungsten-cobalt composite oxide powder. The components of the oxide powder are uniform, the damage of the powder particles are little, the strength of the oxide powder is high, the cobalt content is accurately controlled; and the process is simple and the efficiency is high.
Description
Technical field
The present invention relates to a kind of preparation method's of metal dust, particularly a kind of tungsten-cobalt composite oxide powder industrialized process for preparing.
Background technology
Carbide alloy is a primary raw material with rare metals such as tungsten, cobalt, titaniums, wherein accounts for the principal status of public economy with tungsten carbide-cobalt hard alloy again.Carbide alloy has high rigidity, high density, property such as wear-resisting, is widely used in a plurality of fields such as machine-building, oil exploitation, military project, Aero-Space, is the novel force structure material with high-tech content, has very big market potential.The preparation method of tradition carbide alloy adopts methods such as fixed bed, rotary furnace, hydrogen plasma to make tungsten oxide be become tungsten powder by hydrogen reducing, tungsten (W) powder is mixed with carbon (C) sphere of powder mill, change into tungsten carbide (WC) through pyrocarbon, carrying out ball milling with prefabricated cobalt powder again mixes, obtain WC-Co (WC-Co) carbide alloy mixed-powder, and then prepare carbide alloy by compacting sintering.The method preparation technology's long flow path, efficient are low, tungsten carbide (WC) is difficult to even distribution at cobalt (Co) in mutually in the mixed-powder, influences follow-up carbide alloy performance.In cemented carbide industry to production high-performance, today of nanoscale hard alloy development cheaply, conventional method is difficult to effectively prepare the nanoscale hard alloy powder that is fit to production, and the production of carbide alloy is now developing to the direction that adopts WC-Co composite powder to prepare carbide alloy gradually.And, how to prepare the tungsten-cobalt composite oxide powder that composition is even, cobalt content is easy to control as the important source material of producing the Nanometre grade tungsten carbide Co composite powder, become the key of preparation high-performance nano level tungsten Co composite powder.
The method that the preparation of tungsten-cobalt composite oxide powder is usually adopted is as described in the patent application " production technology of nanoscale tungsten cobalt mixed-powder " (application number 03150684.4): prepare certain density ammonium metatungstate solution, add a certain amount of cobaltous carbonate powder, heating, stirring, fully reaction is with the cooling of gained complex salt solution, filtration; The dry composite salting liquid obtains the complex salt powder, and heating tungsten cobalt complex salt powder obtains tungsten-cobalt composite oxide powder in fluid bed.Adopt these class methods to prepare tungsten-cobalt composite oxide powder, the sluggish of ammonium metatungstate and cobalt carbonate, production efficiency is low; Reaction is difficult to fully carry out, and the reaction residue of generation not only must increase the solution filtration step to be handled, and is difficult to the cobalt content in the composite solution is accurately controlled; Spray-drying gained powder is that the form of mixtures with salt exists substantially, but not oxide completely, directly enter fluid bed and carry out thermal decomposition, can badly influence the intensity and the pattern of powder particle, and then to fluidized state generation harmful effect, thereby cause follow-up reduction and carbonization process normally not carry out, can not adapt to suitability for industrialized production simultaneously.
Summary of the invention
The present invention is directed to above-mentioned deficiency, a kind of preparation method of tungsten-cobalt composite oxide powder is provided, not only composition is even, powder particle is damaged less for the tungsten-cobalt composite oxide powder of preparation, the control of intensity height, cobalt content accurately, and efficient height, technical process is simple.
The preparation method of tungsten-cobalt composite oxide powder of the present invention may further comprise the steps successively:
(1) prepares certain density meta-tungsten acid solution;
(2) in above-mentioned meta-tungsten acid solution, add cobalt salt powder, crystal or solution, heating, stirring fully obtain tungsten cobalt composite solution after the reaction;
(3) above-mentioned tungsten cobalt composite solution is carried out drying and granulating;
(4) powder particle that drying and granulating is obtained further drying and dehydrating again obtains that composition is even, powder particle is damaged less, intensity height, cobalt content control accurate tungsten-cobalt composite oxide powder.
In the described tungsten-cobalt composite oxide powder, the W content scope is 68～78wt%, and the cobalt content scope is 1～15wt%; The cobalt content error is limited to ± and 0.1%.
The concentration range of described meta-tungsten acid solution in W content, is 10～30wt%; Described cobalt salt can be nitric hydrate cobalt Co (NO
3)
2.6H
2O, hydration cobalt acetate Co (CH
3COO)
2.4H
2O, hydration cobaltous formate Co (HCOO)
2.2H
2O, cobalt carbonate CoCO
3, cobalt oxalate CoC
2O
4In one or more.
The reaction temperature of described meta-tungsten acid solution and cobalt salt is 50～100 ℃.
W content is 30～50wt% in the described tungsten cobalt composite solution, and cobalt content is 1～5wt%.
As preferably, described drying and granulating mode is a spray-drying process, and device therefor is centrifugal spray drying tower, press spray drying tower, or flat flow spray drying tower.
The heating-up temperature of described drying and dehydrating is 300～600 ℃, is generally 1～3 hour heat time heating time; Drying and dehydrating device is heated-air circulation oven, Muffle furnace, rotary furnace, infrared drier or microwave dryer.
Meta-tungsten acid solution and cobalt salt reaction are very fast and abundant, and the efficient height can accurately be controlled the cobalt content in the tungsten cobalt composite solution.Spray-drying process not only equipment is simple, and is easy to operate, and the production temperature is low; energy consumption is little, and powder particle cracky not, and powder morphology is controlled well; but the powder particle of this moment is the form of mixtures with salt substantially to be existed, but not oxide completely, also with a certain amount of crystallization water.Follow-up drying and dehydrating is removed the crystallization water in the powder particle, can select a kind of in the following equipment for use: heated-air circulation oven, Muffle furnace, rotary furnace, infrared drier, microwave dryer, 300～600 ℃ of control heating-up temperatures, 1～3 hour heat time heating time, guarantee that powder particle removes the crystallization water fully, the acquisition composition is even, and powder particle is damaged few, the tungsten-cobalt composite oxide that intensity is high.
Therefore, the present invention has that technology is simple, flow process is short, be easy to control, easy to operate, characteristics such as cost of investment is low, be suitable for industrial-scale production, the composite oxide power composition of output evenly, breakage less, the intensity height, the production that can be widely used in preparing Nanometre grade tungsten carbide cobalt (WC-Co) composite powder.
Description of drawings
Fig. 1 is a flow chart of the present invention;
Fig. 2 is the electromicroscopic photograph (X100 doubly) of tungsten-cobalt composite oxide powder of the present invention.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further described.
Embodiment 1:
According to flow process shown in Figure 1 (following examples are identical), preparation proportion is the metatungstic acid (H of 1.10g/ml earlier
6H
2W
12O
40) solution (W content is 10.2wt%), add cobalt carbonate CoCO
3, metatungstic acid and cobalt carbonate react in glassed steel reaction vessels according to the proportioning of 95wt%WC+5wt%Co, and 90 ℃ of heating-up temperatures after stirring, fully reacting, obtain tungsten cobalt composite solution.Adopt the press spray tower to carry out spraying granulation gained tungsten cobalt composite solution, the spray tower inlet temperature is set to 280 ℃, and outlet temperature is set to 130 ℃.Powder particle behind the spraying granulation carries out drying and dehydrating in rotary furnace, heating-up temperature is 450 ℃, and be 2 hours heat time heating time.The tungsten-cobalt composite oxide powder that makes thus, wherein W content is 74.72%, cobalt content is 4.21%.The powder loose specific weight is 2.665g/cm
3, mobile 25.47s/50g, surface area average grain diameter 55.907 μ m, volume average particle size 81.616 μ m.According to the Co content in the WC-Co carbide alloy is 5% requirement, and cobalt content should be 4.19% in the tungsten-cobalt composite oxide, and the cobalt content error is 0.02%.The electromicroscopic photograph of the tungsten-cobalt composite oxide powder of the present invention preparation is seen Fig. 2, clearly among the figure shows that the tungsten-cobalt composite oxide powder composition of the present invention's preparation is even, and the powder particle breakage less, pattern is good.
Embodiment 2:
Preparation proportion is the metatungstic acid (H of 1.25g/ml
6H
2W
12O
40) solution (W content is 21.8wt%), add nitric hydrate cobalt Co (NO
3)
2.6H
2O, metatungstic acid and nitric hydrate cobalt Co (NO
3)
2.6H
2O reacts in glassed steel reaction vessels according to the proportioning of 92wt%WC+8wt%Co, and 80 ℃ of heating-up temperatures after stirring, fully reacting, obtain tungsten cobalt composite solution.Adopt the press spray tower to carry out spraying granulation gained tungsten cobalt composite solution, the spray tower inlet temperature is set to 300 ℃, and outlet temperature is set to 120 ℃.Powder particle behind the spraying granulation carries out drying and dehydrating in Muffle furnace, heating-up temperature is 550 ℃, and be 1 hour heat time heating time.The tungsten-cobalt composite oxide powder that makes thus, wherein W content is 72.67%, and cobalt content is 6.71%, and electromicroscopic photograph is referring to Fig. 2.The powder loose specific weight is 2.376g/cm
3, mobile 28.66s/50g.Surface area average grain diameter 60.333 μ m, volume average particle size 89.974 μ m.According to the Co content in the WC-Co carbide alloy is 8% requirement, and cobalt content should be 6.73% in the tungsten-cobalt composite oxide, and the cobalt content error is 0.02%.The electromicroscopic photograph of the tungsten-cobalt composite oxide powder of preparation is seen Fig. 2.
Embodiment 3:
Preparation proportion is the metatungstic acid (H of 1.15g/ml
6H
2W
12O
40) solution (W content is 14.2wt%), add cobalt oxalate CoC
2O
4, metatungstic acid and cobalt carbonate react in glassed steel reaction vessels according to the proportioning of 97wt%WC+3wt%Co, and 80 ℃ of heating-up temperatures after stirring, fully reacting, obtain tungsten cobalt composite solution.Adopt centrifugal spray tower to carry out spraying granulation gained tungsten cobalt composite solution, the spray tower inlet temperature is set to 240 ℃, and outlet temperature is set to 100 ℃.Powder particle behind the spraying granulation carries out drying and dehydrating in rotary furnace, heating-up temperature is 400 ℃, and be 2 hours heat time heating time.The tungsten-cobalt composite oxide powder that makes thus, its W content are 76.23%, and cobalt content is 2.51%, and electromicroscopic photograph is referring to Fig. 2.The powder loose specific weight is 2.415g/cm
3, mobile 28.87s/50g.Surface area average grain diameter 36.409 μ m, volume average particle size 57.418 μ m.According to the Co content in the WC-Co carbide alloy is 3% requirement, and cobalt content should be 2.55% in the tungsten-cobalt composite oxide, and the cobalt content error is 0.04%.The electromicroscopic photograph of the tungsten-cobalt composite oxide powder of preparation is seen Fig. 2.
Embodiment 4:
Preparation proportion is the metatungstic acid (H of 1.30g/ml
6H
2W
12O
40) solution (W content is 25.1wt%), add hydration cobalt acetate Co (CH
3COO)
2.4H
2O, metatungstic acid and hydration cobalt acetate Co (CH
3COO)
2.4H
2O reacts in glassed steel reaction vessels according to the proportioning of 88wt%WC+12wt%Co, and 70 ℃ of heating-up temperatures after stirring, fully reacting, obtain tungsten cobalt composite solution.Adopt centrifugal spray tower to carry out spraying granulation gained tungsten cobalt composite solution, the spray tower inlet temperature is set to 300 ℃, and outlet temperature is set to 130 ℃.Powder particle carries out drying and dehydrating behind the spraying granulation in Muffle furnace, and setting heating-up temperature is 600 ℃, and be 1 hour heat time heating time.The tungsten-cobalt composite oxide powder that makes thus, its W content are 69.23%, and cobalt content is 10.09%, and electromicroscopic photograph is referring to Fig. 2.The powder loose specific weight is 2.289g/cm
3, mobile 29.74s/50g.Surface area average grain diameter 38.397 μ m, volume average particle size 59.128 μ m.According to the Co content in the WC-Co carbide alloy is 12% requirement, and cobalt content should be 10.06% in the tungsten-cobalt composite oxide, and the cobalt content error is 0.03%.The electromicroscopic photograph of the tungsten-cobalt composite oxide powder of preparation is seen Fig. 2.
Claims (10)
1. the preparation method of a tungsten-cobalt composite oxide powder may further comprise the steps successively:
(1) prepares certain density meta-tungsten acid solution;
(2) in above-mentioned meta-tungsten acid solution, add cobalt salt powder, crystal or solution, heating, stirring fully obtain tungsten cobalt composite solution after the reaction;
(3) above-mentioned tungsten cobalt composite solution is carried out drying and granulating;
(4) powder particle that drying and granulating is obtained further drying and dehydrating again obtains that composition is even, powder particle is damaged less, intensity height, cobalt content control accurate tungsten-cobalt composite oxide powder.
2. the preparation method of a kind of tungsten-cobalt composite oxide powder according to claim 1, it is characterized in that: in the described tungsten-cobalt composite oxide powder, the W content scope is 68～78wt%, and the cobalt content scope is 1～15wt%.
3. the preparation method of a kind of tungsten-cobalt composite oxide powder according to claim 1 and 2 is characterized in that: in the described tungsten-cobalt composite oxide powder cobalt content error be limited to ± 0.1%.
4. the preparation method of a kind of tungsten-cobalt composite oxide powder according to claim 1, it is characterized in that: the concentration range of described meta-tungsten acid solution in W content, is 10～30wt%; Described cobalt salt can be nitric hydrate cobalt Co (NO
3)
2.6H
2O, hydration cobalt acetate Co (CH
3COO)
2.4H
2O, hydration cobaltous formate Co (HCOO)
2.2H
2O, cobalt carbonate CoCO
3, cobalt oxalate CoC
2O
4In one or more.
5. according to the preparation method of claim 1 or 4 described a kind of tungsten-cobalt composite oxide powders, it is characterized in that: the reaction temperature of described meta-tungsten acid solution and cobalt salt is 50～100 ℃.
6. the preparation method of a kind of tungsten-cobalt composite oxide powder according to claim 1, it is characterized in that: W content is 30～50wt% in the described tungsten cobalt composite solution, and cobalt content is 1～5wt%.
7. the preparation method of a kind of tungsten-cobalt composite oxide powder according to claim 1, it is characterized in that: the drying and granulating mode is a spray-drying process.
8. the preparation method of a kind of tungsten-cobalt composite oxide powder according to claim 7, it is characterized in that: described spray-drying process device therefor is centrifugal spray drying tower, press spray drying tower or flat flow spray drying tower.
9. the preparation method of a kind of tungsten-cobalt composite oxide powder according to claim 1, it is characterized in that: the heating-up temperature of described drying and dehydrating is 300～600 ℃, be 1～3 hour heat time heating time.
10. according to the preparation method of claim 1 or 9 described a kind of tungsten-cobalt composite oxide powders, it is characterized in that: described drying and dehydrating device is heated-air circulation oven, Muffle furnace, rotary furnace, infrared drier or microwave dryer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105458291A (en) * | 2015-12-09 | 2016-04-06 | 株洲硬质合金集团有限公司 | Preparing method of composite tungsten cobalt oxide powder |
| CN107570722A (en) * | 2017-09-04 | 2018-01-12 | 深圳职业技术学院 | A kind of preparation method of 3D printing material |
| CN110980810A (en) * | 2019-05-15 | 2020-04-10 | 江西理工大学 | Purple tungsten composite powder with different length-diameter ratios and controllable preparation method and application thereof |
-
2010
- 2010-01-26 CN CN201010101162A patent/CN101774024A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105458291A (en) * | 2015-12-09 | 2016-04-06 | 株洲硬质合金集团有限公司 | Preparing method of composite tungsten cobalt oxide powder |
| CN107570722A (en) * | 2017-09-04 | 2018-01-12 | 深圳职业技术学院 | A kind of preparation method of 3D printing material |
| CN107570722B (en) * | 2017-09-04 | 2019-03-29 | 深圳职业技术学院 | A kind of preparation method of 3D printing material |
| CN110980810A (en) * | 2019-05-15 | 2020-04-10 | 江西理工大学 | Purple tungsten composite powder with different length-diameter ratios and controllable preparation method and application thereof |
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Open date: 20100714 |