CN109290586A - A kind of preparation method of high-purity vanadium powder - Google Patents
A kind of preparation method of high-purity vanadium powder Download PDFInfo
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- CN109290586A CN109290586A CN201811222443.XA CN201811222443A CN109290586A CN 109290586 A CN109290586 A CN 109290586A CN 201811222443 A CN201811222443 A CN 201811222443A CN 109290586 A CN109290586 A CN 109290586A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- 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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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Abstract
The invention discloses a kind of preparation methods of high-purity vanadium powder, first mix vanadium-containing material with alkali or alkaline earth metal chloride salt, then mix with calcium hydride, then carry out vacuum-thermal reduction, obtain reduzate；It is successively washed again with ammonium chloride solution, lye and acid solution, finally carries out Dehydroepiandrosterone derivative, high-purity vanadium powder can be obtained.The present invention has many advantages, such as that at low cost, energy consumption is small, reaction condition is mild, safe operation.
Description
Technical field
The invention belongs to rare metal refinement technique fields, and in particular to a kind of preparation method of high-purity vanadium powder.
Background technique
With the development and progress of PM technique, the application field of its main raw material(s) metal powder is constantly expanded
Exhibition, the market demand also sharply increases, and shows and develop to high-purity, ultra-fine direction, at present the metal powder preparation of comparative maturity
Method mainly has solid phase method and vapor phase method, and both of which has the shortcomings that certain and deficiency.
Solid phase method (Mechanical Method) is although the treating capacity for preparing powder is big, and capacity usage ratio is low, during the preparation process easily
Introducing impurity, the diameter of particle prepared is big and distribution width, form are difficult to control, and synchronous work surface treatment is difficult.Vapor phase method preparation
Nano-powder purity is high, granularity is small, good dispersion, however the disadvantage that its Preparation equipment is expensive, miscellaneous, energy consumption is high, at high cost from
The application and development of vapor phase method are seriously constrained again.
Vanadium powder activity is high, easily adsorbs the elements such as N, O in environment and is formed on its surface oxide, and the thinner ratio of powder
Surface area is bigger, the content of more uncontrollable impurity.Therefore, high-purity high thin vanadium powder is prepared more difficult.
Summary of the invention
In view of the above shortcomings of the prior art, the present invention provides a kind of preparation method of high-purity vanadium powder, it is intended to solve
The technical problems such as the prior art is at high cost, energy consumption is high, equipment valuableness, severe reaction conditions.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of preparation method of high-purity vanadium powder, including the following steps:
1) vanadium-containing material is mixed with alkali or alkaline earth metal chloride salt, obtains mixed raw material.It will be by vanadium-containing material
With alkali or alkaline earth metal chloride salt mixing be in order to be uniformly mixed vanadium-containing material with alkaline earth metal chloride fused salt, can
The effective wellability increased when hydrogenating calcium reduction vanadium-containing material, enhancing vanadium-containing material restore interface kinetics process, reduce also
The former time.
2) mixed raw material obtained in step 1) is mixed with calcium hydride, forms mix products；Mix products are carried out again
Vacuum-thermal reduction obtains reduzate.For vacuum tube furnace can be used convenient for operation.Obtained reduzate is Vanadium hydride
And calcium oxide.Be shown below, which can generate hydrogen, using vacuum tube furnace can make the reaction to positive direction carry out from
And improve reaction efficiency.
V2O5+5CaH2=2VH2+5CaO+3H2(g)
3) with ammonium chloride solution washing step 2) reduzate is obtained, to remove the calcium oxide on its surface, washed for the first time
Wash product.It is washed using stirred tank.
4) by initial wash product, then alkali cleaning and pickling are successively carried out, further to remove impurity, obtains finally washing production
Object, i.e. hydrogenation vanadium powder.Pickling mainly goes iron ions, chromium ion, and alkali cleaning is primarily to removal silicon ion.
5) final washed product is placed under certain temperature and carries out dehydrogenation, obtain high-purity vanadium powder.
Wherein: the vanadium-containing material described in step 1) is at least one of vanadic anhydride or metavanadic acid；Described
Vanadic anhydride mass content is not less than 99.5%；The mass content of the metavanadic acid is not less than 98%.Five oxidation two of selection
Vanadium or metavanadic acid as reaction raw materials mainly because in contrast the raw material is easy to get, and advantage of lower cost.
The molar ratio of the vanadium-containing material and alkali or alkaline earth metal chloride salt is 1:5~6, wherein vanadium-containing material
In terms of vanadic anhydride.Select the propriation primarily to alkaline earth metal chloride fused salt is made to be dissolved in vanadium-containing material surface
The calcium oxide of generation can be such that the reaction goes on smoothly.Alkaline earth metal chloride fused salt amount is not enough to dissolve vanadium-containing material very little
The calcium oxide of Surface Creation, amount is too many to be caused to waste again.
Step 1) uses ball milling mixing, Ball-milling Time 2h.It is preferred that high-energy ball milling is used, to reach required for the present invention
Fineness, and it is sufficiently mixed raw material uniformly.Ball milling can make material mixing more evenly, improve the infiltration at vanadium-containing material reduction interface
Property.
In step 2).The molar ratio of vanadium-containing material in calcium hydride and mixed raw material is 5~6:1, wherein vanadium-containing material
In terms of vanadic anhydride.
The temperature of vacuum-thermal reduction is 600~800 DEG C.The alkali metal chloride fused salt that the temperature can make sufficiently melts,
The calcium oxide that effective dissolving and reducing interface generates.Improve dynamic conditions.
The vacuum degree of vacuum-thermal reduction is not higher than 5Pa；The vacuum-thermal reduction time is 24~36h, to guarantee fully reacting.
In step 3), the molar concentration of the ammonium chloride solution is 1~2mol/L；The temperature of ammonium chloride solution is 70
DEG C, wash time is 6~8h.By by the way of stirring trough washery, stirred tank be can be improved between powder material and cleaning solution
Transmission efficiency and rate.And the dosage of cleaning solution can be effectively reduced, setting temperature is 70 DEG C, can be effectively improved washing process
Dynamic conditions, the dissolution of accelerating impurity.
In step 4), acid used in the pickling is the hydrochloric acid of 1mol/L；Alkali used in alkali cleaning is 1mol/L's
Sodium hydroxide solution；The time of alkali cleaning and pickling washing is 2~3h.It is equally washed by the way of stirred tank, and detects washing
PH and foreign ion concentration, with this determine a need for replacement cleaning solution.
In step 5), the temperature of dehydrogenation is 400~500 DEG C, and the reaction time is 5~7h.
Low cost of the invention is using vanadium-containing material as raw material, using the high reproducibility of calcium hydride, to restore in vanadium-containing material
Vanadium, and and using the calcium oxide for dissolving vanadium-containing material Surface Creation using alkaline earth metal chloride fused salt as medium, can be with
Greatling improve reaction rate carries out reaction forward.Using vacuum-thermal reduction, energy consumption is reduced, significantly reduces vanadium powder preparation
Cost, the recovery rate of resulting vanadium powder purity is high, vanadium powder is high, provides a highly effective path for the production of vanadium powder.
Compared with prior art, the invention has the following beneficial effects:
1, by hydrogenation calcium reduction vanadium-containing material, the presence of hydrogen can be effectively protected vanadium powder surface and can purified gas the present invention
Atmosphere avoids oxide from being formed, to obtain high-purity vanadium powder.
2, method used in the present invention only needs the conventional equipments such as airtight tube type furnace and vacuum pump without complicated large size
Equipment, it is easy to operate, it is low in cost.
3, the processing route of this method prepares high-purity vanadium powder from vanadium-containing material oxide, and comprehensive energy consumption is far low
In the method for preparing vanadium powder from vanadium metal.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
In figure: 101-alkaline earth metal chloride salt；102-vanadium-containing materials；103-calcium hydrides；104-other metals are miscellaneous
Matter；105-Vanadium hydrides；106-calcium oxide；107-high-purity vanadium powders.
Specific embodiment
Invention is further described in detail combined with specific embodiments below.
Embodiment one
100g vanadic anhydride (99.5%) powder and 350g calcium chloride and sodium chloride (99%) eutectics fused salt are taken, is added high
170g calcium hydride powder (99%) is added later and mixes 0.5h, it is hot also to be put into progress in vacuum tube furnace by energy ball mill ball milling 2h
Original, control in-furnace temperature is 600 DEG C, after restoring 12h under an argon atmosphere, carries out vacuum-thermal reduction control vacuum degree and is less than 5Pa,
Recovery time 16h, the product after reduction are washed in sink in 1mol/L ammonium chloride solution, and cleaning solution temperature 70 C is washed
Wash time 7h.Product after washing continues sodium hydroxide solution and 1mol/L hydrochloric acid solution that 1mol/L is successively used in sink
Middle washing, wash time 3h finally carry out Dehydroepiandrosterone derivative to product, 400 DEG C of desorption temperature, high-purity vanadium powder can be obtained later,
Purity is 99.95%.Process flow chart is as shown in Figure 1.
Embodiment two
110g metavanadic acid (98%) powder and 350g calcium chloride and sodium chloride (99%) eutectics fused salt are taken, high-energy ball milling is added
170g calcium hydride powder (99%) is added later and mixes 0.5h, is put into vacuum tube furnace and is heat-treated, controlled by machine ball milling 2h
In-furnace temperature is 600 DEG C, after restoring 12h under an argon atmosphere, carries out vacuum-thermal reduction control vacuum degree and is less than 5Pa, when reduction
Between 16h, the product after reduction washs in sink in 1mol/L ammonium chloride solution, cleaning solution temperature 70 C, wash time
7h.Product continuation after washing is successively washed in the sodium hydroxide solution of 1mol/L and 1mol/L hydrochloric acid solution in sink
It washs, wash time 3h, Dehydroepiandrosterone derivative finally is carried out to product, 400 DEG C of desorption temperature, high-purity vanadium powder, purity can be obtained later
It is 99.9%.Process flow chart is as shown in Figure 1.
Embodiment three
100g vanadic anhydride (99.5%) powder and 350g calcium chloride and sodium chloride (99%) eutectics fused salt are taken, is added high
170g calcium hydride powder (99%) is added later and mixes 0.5h, it is hot also to be put into progress in vacuum tube furnace by energy ball mill ball milling 2h
Original, control in-furnace temperature is 750 DEG C, after restoring 12h under an argon atmosphere, carries out vacuum-thermal reduction control vacuum degree and is less than 5Pa,
Recovery time 16h, the product after reduction are washed in sink in 1mol/L ammonium chloride solution, and cleaning solution temperature 70 C is washed
Wash time 7h.Product after washing continues sodium hydroxide solution and 1mol/L hydrochloric acid solution that 1mol/L is successively used in sink
Middle washing, wash time 3h finally carry out Dehydroepiandrosterone derivative to product, 400 DEG C of desorption temperature, high-purity vanadium powder can be obtained later,
Purity is 99.99%.Process flow chart is as shown in Figure 1.
Example IV
110g metavanadic acid (98%) powder and 350g calcium chloride and sodium chloride (99%) eutectics fused salt are taken, high-energy ball milling is added
170g calcium hydride powder (99%) is added later and mixes 0.5h, is put into vacuum tube furnace and is heat-treated, controlled by machine ball milling 2h
In-furnace temperature is 750 DEG C, after restoring 12h under an argon atmosphere, carries out vacuum-thermal reduction control vacuum degree and is less than 5Pa, when reduction
Between 16h, the product after reduction washs in sink in 1mol/L ammonium chloride solution, cleaning solution temperature 70 C, wash time
7h.Product continuation after washing is successively washed in the sodium hydroxide solution of 1mol/L and 1mol/L hydrochloric acid solution in sink
It washs, wash time 3h, Dehydroepiandrosterone derivative finally is carried out to product, 400 DEG C of desorption temperature, high-purity vanadium powder, purity can be obtained later
It is 99.95%.Process flow chart is as shown in Figure 1.
The above embodiment of the present invention is only example to illustrate the invention, and is not to implementation of the invention
The restriction of mode.For those of ordinary skill in the art, other can also be made not on the basis of the above description
With the variation and variation of form.Here all embodiments can not be exhaustive.It is all to belong to technical solution of the present invention
Changes and variations that derived from are still in the scope of protection of the present invention.
Claims (10)
1. a kind of preparation method of high-purity vanadium powder, which is characterized in that including the following steps:
1) vanadium-containing material is mixed with alkali or alkaline earth metal chloride salt, obtains mixed raw material；
2) mixed raw material obtained in step 1) is mixed with calcium hydride, forms mix products；Mix products are subjected to vacuum again
Thermal reduction, obtains reduzate；
3) with ammonium chloride solution washing step 2) reduzate is obtained, obtain initial wash product；
4) by initial wash product, then alkali cleaning and pickling is successively carried out and obtains final washed product further to remove impurity；
5) final washed product is placed under certain temperature and carries out dehydrogenation, obtain high-purity vanadium powder.
2. the preparation method of high-purity vanadium powder according to claim 1, which is characterized in that vanadium-containing material described in step 1)
For at least one of vanadic anhydride or metavanadic acid；The vanadic anhydride mass content is not less than 99.5%；Described
The mass content of metavanadic acid is not less than 98%.
3. the preparation method of high-purity vanadium powder according to claim 1, which is characterized in that vanadium-containing material described in step 1) with
The molar ratio of alkali or alkaline earth metal chloride salt is 1:5~6, and wherein vanadium-containing material is in terms of vanadic anhydride.
4. the preparation method of high-purity vanadium powder according to claim 1, which is characterized in that step 1) uses ball milling mixing, ball
Time consuming is 2h.
5. the preparation method of high-purity vanadium powder according to claim 1, which is characterized in that in step 2) calcium hydride with mix original
The molar ratio of vanadium-containing material in material is 5~6:1, and wherein vanadium-containing material is in terms of vanadic anhydride.
6. the preparation method of high-purity vanadium powder according to claim 1, which is characterized in that the temperature of vacuum-thermal reduction in step 2)
Degree is 600~800 DEG C.
7. the preparation method of high-purity vanadium powder according to claim 1, which is characterized in that vacuum-thermal reduction is true in step 2)
Reciprocal of duty cycle is not higher than 5Pa；The vacuum-thermal reduction time is 24~36h.
8. the preparation method of high-purity vanadium powder according to claim 1, which is characterized in that in step 3), the ammonium chloride is molten
The molar concentration of liquid is 1~2mol/L；The temperature of ammonium chloride solution is 70 DEG C, and wash time is 6~8h.
9. the preparation method of high-purity vanadium powder according to claim 1, which is characterized in that in step 4), the pickling institute
The acid used is the hydrochloric acid of 1mol/L；Alkali used in alkali cleaning is the sodium hydroxide solution of 1mol/L；What alkali cleaning and pickling were washed
Time is 2~3h.
10. the preparation method of high-purity vanadium powder according to claim 1, which is characterized in that in step 5), the temperature of dehydrogenation
It is 400~500 DEG C, the reaction time is 5h~7h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110340369A (en) * | 2019-08-08 | 2019-10-18 | 南昌大学 | A kind of Ultra Low Cost spherical shape vanadium powder preparation method |
| CN111283210A (en) * | 2020-02-27 | 2020-06-16 | 有研工程技术研究院有限公司 | High-purity metal vanadium powder and preparation method thereof |
| CN111957984A (en) * | 2020-08-25 | 2020-11-20 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of metal vanadium powder |
| CN113732297A (en) * | 2021-09-04 | 2021-12-03 | 湖南众鑫新材料科技股份有限公司 | High-purity vanadium purification process |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110340369A (en) * | 2019-08-08 | 2019-10-18 | 南昌大学 | A kind of Ultra Low Cost spherical shape vanadium powder preparation method |
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