CN105780059B - A kind of electrolytic preparation method of vananum - Google Patents
A kind of electrolytic preparation method of vananum Download PDFInfo
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- CN105780059B CN105780059B CN201610140170.9A CN201610140170A CN105780059B CN 105780059 B CN105780059 B CN 105780059B CN 201610140170 A CN201610140170 A CN 201610140170A CN 105780059 B CN105780059 B CN 105780059B
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- vananum
- molten
- fused salt
- alundum
- al2o3
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/36—Alloys obtained by cathodic reduction of all their ions
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- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a kind of electrolytic preparation method of vananum, step are as follows：A, vanadic anhydride, alundum (Al2O3) are uniformly mixed with binding agent, additive, compressing using forcing press, simultaneously solid state cathode block is made by high temperature sintering in drying；B, using graphite block as anode, the fused salt mixt of sodium chloride and calcium chloride is electrolyte, carries out molten-salt electrolysis；C, after the completion of molten-salt electrolysis, by cathode block lift-off fused salt, it is cleaned, is dry, and remelting under an inert atmosphere, finally come out of the stove to obtain vananum.The deficiencies of this method overcomes complex procedures existing in the prior art various at present, impurity content is high, has the advantages that material process is simple, energy consumption is low.
Description
Technical field
The invention belongs to vananum preparation field, more particularly to a kind of fused salt electrolysis preparation method thereof of vananum.
Background technology
Vananum is one of titanium alloy material primary raw materials such as production Ti-6Al-4V and Ti-8Al-1Mo-1V.Titanium alloy
Material is chiefly used in aerospace field, and the requirement to impurity is very harsh, therefore ensures that the purity of vananum is extremely important.
Vananum mainly has tri- kinds of products of AlV50, AlV60 and AlV80, and current production method is based on aluminothermic reduction
Method, raw materials used is vanadic anhydride, aluminium, lime and fluorite etc., and each raw material is put into reacting furnace after drying, dispensing, batch mixing
It is interior, magnesium chips is added on surface and is lighted a fire, starts the smelting process from exothermic reaction, after reaction, through cooling down after a while,
Alloy oxidation skin is removed, obtains vananum.This method reaction speed is fast, but thermal discharge is excessive, be easy to cause splash, and high temperature
In fusion process, the slag former and reducing agent of addition be easy to cause alloy contamination, increase impurity content.In addition, fusion process is also
Certain waste residue containing vanadium can be produced, not only causes the waste of vanadium resource, environment is returned and brings pressure.
The content of the invention
To overcome vananum of the prior art to prepare the problem of extensive, impurity content is high, it is an object of the present invention to
A kind of fused salt electrolysis preparation method thereof of vananum is provided, to lift vananum quality.
In order to realize above-mentioned task, the present invention takes following technical solution：
A kind of electrolytic preparation method of vananum, it is characterised in that carry out according to the following steps：
A, vanadic anhydride, alundum (Al2O3) are uniformly mixed with binding agent, additive, it is compressing using forcing press,
After drying, solid state cathode block is made by high temperature sintering；
B, using graphite block as anode, the fused salt mixt of sodium chloride and calcium chloride is electrolyte, carries out molten-salt electrolysis；
C, after the completion of being electrolysed, by cathode block lift-off fused salt surface, it is cleaned, is dry, and is weighed under an inert atmosphere
It is molten, finally come out of the stove to obtain vananum.
The vanadic anhydride and alundum (Al2O3) dosage of wherein described step A is produced with reference to AlV50, AlV60 and AlV80 aluminium vanadium
The stoichiometric ratio of product is prepared, and specific mass ratio is 1:1~5:Between 1.
Additive described in step A is NaCl or CaCl2Therein a kind of or their mixture, additive amount five
The 0~6% of V 2 O and alundum (Al2O3) gross mass.The addition of additive predominantly increases reaction speed, its dosage is unsuitable
Excessively, cathode is otherwise easy to cause to crush in electrolytic process.
The binding agent of the step A is poly-vinyl alcohol solution or distilled water.
High temperature sintering temperature control described in step A vanadic anhydride fusing point (690 DEG C) below, to avoid five oxidations
Two vanadium melt in sintering process, and high temperature sintering time control is between 5~15h.
The temperature control of molten-salt electrolysis described in step B melts below 660 DEG C to avoid aluminium.In addition, to avoid chlorination
Thing electrochemical dissolution, the voltage of molten-salt electrolysis is unsuitable excessive, controls in 2.5~3.3V, the time is 10~20h.
Compared with the prior art the electrolytic preparation method of the vananum of the present invention, has the advantages that as is evident below：
1st, vananum is prepared using the present invention, temperature is low, technique is simple, and alloying component is easy to control；
2nd, process prepared by vananum is not required to addition reducing agent and slag former, avoids the pollution to vananum, drops
The low impurity content of vananum；
3rd, waste residue containing vanadium and flue dust are not produced, energy consumption is low, and production environment is friendly.
Embodiment
The present invention is described in further detail by the following examples, it is necessary to which explanation is that following embodiment only supplies
Those skilled in the art is clearer to understand the present invention, and the present invention is not limited to these Examples.
Below in an example, the polyvinyl alcohol (0.03g/ml) binding agent, be with the polyvinyl alcohol of solid and
Water is formulated, and preparation method is, according to the polyvinyl alcohol that 0.03g solids are added in every milliliter of pure water (or distilled water), to protect
Temperature stirring is completely dissolved until polyvinyl alcohol to obtain the final product.
Embodiment 1：
By the vanadic anhydride below 200 mesh and alundum (Al2O3) in mass ratio 1:1 mixing, obtains mixed material, in addition
NaCl and certain polyvinyl alcohol (0.03g/ml) binding agent into mixed material with addition of mixed material gross mass 3%, bond
The specific dosage of agent is with addition of 1ml per 20g mixed materials.
By with addition of the mixed material of NaCl and binding agent under 50MPa it is compressing, fire 8h at 680 DEG C, obtain anti-
Answer cathode.
Using molar ratio as 1：1 NaCl-CaCl2Fused salt is electrolyte, graphite block is anode, and fused salt is carried out to cathode (also
It is former) electrolysis, 650 DEG C, voltage 3.3V, time 15h of temperature.After fused salt (reduction) is electrolysed, by cathode block lift-off fused salt surface,
It is once purged to obtain cellular vananum, then by the cellular vananum remelting under an argon atmosphere, obtain vananum
Ingot casting.Measured through chemical analysis, gained vananum 51.3wt% containing vanadium, oxygen-containing 0.17wt%.
Embodiment 2：
By the vanadic anhydride below 200 mesh and alundum (Al2O3) in mass ratio 1.5:1 mixing, obtains mixed material, separately
With addition of the CaCl of mixed material gross mass 1% in export-oriented mixed material2With certain polyvinyl alcohol (0.03g/ml) binding agent, glue
It is with addition of 1ml per 20g mixed materials to tie agent dosage.
Will be with addition of CaCl2With the mixed material of binding agent under 40MPa it is compressing, fire 6h at 680 DEG C, obtain anti-
Answer cathode.
Using molar ratio as 1：1 NaCl-CaCl2Fused salt is electrolyte, graphite block is anode, and fused salt is carried out to cathode (also
It is former) electrolysis, 650 DEG C, voltage 3.2V, time 18h of temperature.After fused salt (reduction) is electrolysed, by cathode block lift-off fused salt surface,
It is once purged to obtain cellular vananum, then by the cellular vananum remelting under an argon atmosphere, obtain vananum
Ingot casting.Measured through chemical analysis, gained vananum 59.1wt% containing vanadium, oxygen-containing 0.19wt%.
Embodiment 3：
By the vanadic anhydride below 200 mesh and alundum (Al2O3) in mass ratio 2:1 mixing, obtains mixed material, in addition
Into mixed material with addition of the CaCl of mixed material gross mass 2%2With polyvinyl alcohol (0.03g/ml) binding agent, consumption of binder
It is every 30g mixed materials with addition of 1ml.
Will be with addition of CaCl2With the mixed material of binding agent under 40MPa it is compressing, fire 6h at 680 DEG C, obtain anti-
Answer cathode.
Using molar ratio as 1：1 NaCl-CaCl2Fused salt is electrolyte, graphite block is anode, and fused salt is carried out to cathode (also
It is former) electrolysis, 650 DEG C, voltage 3.2V, time 18h of temperature.After fused salt (reduction) is electrolysed, by cathode block lift-off fused salt surface,
It is once purged to obtain cellular vananum, then by the cellular vananum remelting under an argon atmosphere, obtain vananum
Ingot casting.Measured through chemical analysis, gained vananum 63.8wt% containing vanadium, oxygen-containing 0.19wt%.
Embodiment 4：
By the vanadic anhydride below 200 mesh and alundum (Al2O3) in mass ratio 3.5:1 mixing, obtains mixed material, separately
Used in export-oriented mixed material with addition of NaCl and polyvinyl alcohol (0.03g/ml) binding agent of mixed material gross mass 1%, binding agent
Measure is every 35g mixed materials with addition of 1ml.
By with addition of the mixed material of NaCl and binding agent under 40MPa it is compressing, fire 5h at 680 DEG C, obtain anti-
Answer cathode.
Using molar ratio as 1：1 NaCl-CaCl2Fused salt is electrolyte, graphite block is anode, and fused salt is carried out to cathode (also
It is former) electrolysis, 650 DEG C, voltage 3.2V, time 20h of temperature.After fused salt (reduction) is electrolysed, by cathode block lift-off fused salt surface,
It is once purged to obtain cellular vananum, then by the remelting under an argon atmosphere of the cellular vananum, obtain vananum
Ingot casting.Measured through chemical analysis, gained vananum 75.1wt% containing vanadium, oxygen-containing 0.20wt%.
Embodiment 5：
By the vanadic anhydride below 200 mesh and alundum (Al2O3) in mass ratio 4:1 mixing, obtains mixed material, in addition
Into mixed material with addition of certain distilled water, distillation water consumption is every 20g mixed materials with addition of 1ml.
By with addition of the mixture of distilled water under 40MPa it is compressing, fire 5h at 680 DEG C, obtain reaction cathode.With
Molar ratio is 1：1 NaCl-CaCl2Fused salt is electrolyte, graphite block is anode, and fused salt (reduction) electrolysis, temperature are carried out to cathode
650 DEG C, voltage 3.2V, time 20h of degree.It is once purged to obtain by cathode block lift-off fused salt surface after fused salt (reduction) is electrolysed
To cellular vananum, then by the cellular vananum remelting under an argon atmosphere, vananum ingot casting is obtained.Through chemistry
Analysis measure, gained vananum 78.2wt% containing vanadium, oxygen-containing 0.20wt%.
Claims (2)
1. a kind of electrolytic preparation method of vananum, it is characterised in that follow these steps to carry out：
A, vanadic anhydride, alundum (Al2O3), binding agent, additive are uniformly mixed, it is compressing using forcing press, it is dry
Afterwards, solid state cathode block is made by high temperature sintering；
B, using graphite block as anode, the fused salt mixt of sodium chloride and calcium chloride is electrolyte, carries out molten-salt electrolysis；
C, after the completion of molten-salt electrolysis, by cathode block lift-off fused salt, it is cleaned, is dry, and remelting under an inert atmosphere, most
After come out of the stove to obtain vananum；
The molar ratio of sodium chloride and calcium chloride described in step B is 1:1, the temperature of molten-salt electrolysis is 650 DEG C, the electricity of molten-salt electrolysis
It is 10~20h to press as 2.5~3.3V, time；
The binding agent of the step A is poly-vinyl alcohol solution or distilled water；
Additive in the step A is NaCl or CaCl2One of which or their mixture, additive amount are five oxidations
The 1~3% of two vanadium and alundum (Al2O3) gross mass；
The temperature control of the high temperature sintering of the step A is at 680 DEG C, 5~15h of sintering time.
2. the method as described in claim 1, it is characterised in that the vanadic anhydride of the step A and the tool of alundum (Al2O3)
Body mass ratio is 1:1~5:Between 1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004522851A (en) * | 2000-11-15 | 2004-07-29 | ケンブリッジ ユニヴァーシティ テクニカル サービスイズ リミティッド | Metal and alloy powders and powder manufacturing |
| CN101280438A (en) * | 2008-05-09 | 2008-10-08 | 北京大学 | Method for directly preparing ferrochromium alloy with chromite powder |
| CN104060300A (en) * | 2014-07-15 | 2014-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method for titanium-aluminum-vanadium alloy powder |
| CN104404573A (en) * | 2014-12-18 | 2015-03-11 | 河北联合大学 | Preparation method of vanadium metal |
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2016
- 2016-03-11 CN CN201610140170.9A patent/CN105780059B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004522851A (en) * | 2000-11-15 | 2004-07-29 | ケンブリッジ ユニヴァーシティ テクニカル サービスイズ リミティッド | Metal and alloy powders and powder manufacturing |
| CN101280438A (en) * | 2008-05-09 | 2008-10-08 | 北京大学 | Method for directly preparing ferrochromium alloy with chromite powder |
| CN104060300A (en) * | 2014-07-15 | 2014-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method for titanium-aluminum-vanadium alloy powder |
| CN104404573A (en) * | 2014-12-18 | 2015-03-11 | 河北联合大学 | Preparation method of vanadium metal |
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Granted publication date: 20180504 Termination date: 20210311 |