CN105780059A - Electrolytic preparation method of vanadium-aluminum alloy - Google Patents
Electrolytic preparation method of vanadium-aluminum alloy Download PDFInfo
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- CN105780059A CN105780059A CN201610140170.9A CN201610140170A CN105780059A CN 105780059 A CN105780059 A CN 105780059A CN 201610140170 A CN201610140170 A CN 201610140170A CN 105780059 A CN105780059 A CN 105780059A
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- fused salt
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- 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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Abstract
The invention discloses an electrolytic preparation method of vanadium-aluminum alloy. The method comprises the following steps that A, vanadium pentoxide, aluminum oxide, binding agents and addition agents are mixed evenly, pressed and formed by a press, dried, and sintered at a high temperature to obtain a solid cathode block; B, a graphite block serves as an anode, mixed fused salt of sodium chloride and calcium chloride serves as an electrolyte, and fused salt electrolysis is conducted; and C, after fused salt electrolysis is completed, the cathode block is lifted out of the fused salt, washed, dried, refused in the inert atmosphere, and finally taken out of a furnace to obtain the vanadium-aluminum alloy. The defects that procedures are complex and the impurity content is high in the prior art are overcome, and the electrolytic preparation method of the vanadium-aluminum alloy has the advantages of being simple in raw material procedure and low in energy consumption.
Description
Technical field
The invention belongs to vananum preparation field, particularly to the fused salt electrolysis preparation method thereof of a kind of vananum.
Background technology
Vananum is to produce one of titanium alloy material primary raw materials such as Ti-6Al-4V and Ti-8Al-1Mo-1V.Titanium alloy material is used for aerospace field, and the requirement of impurity is very harsh, thereby ensure that the purity of vananum is extremely important.
Vananum mainly has three kinds of products of AlV50, AlV60 and AlV80, current production method is based on thermit reduction, raw materials used for vanadic anhydride, aluminum, Calx and fluorite etc., after each raw material drying, dispensing, batch mixing, put into reacting furnace, add magnesium chips on surface and light a fire, starting from the smelting process of exothermic reaction, reaction cools down through after a while after terminating, remove alloy oxidation skin, obtain vananum.The method response speed is fast, but thermal discharge is excessive, it is easy to cause splash, and in high melt process, the slag former of addition and reducing agent easily cause alloy contamination, increase impurity content.It addition, fusion process also can produce certain for vanadium waste residue, not only cause the waste of vanadium resource, return environment and bring pressure.
Summary of the invention
For overcoming vananum of the prior art to prepare problem extensive, that impurity content is high, it is an object of the invention to, it is provided that the fused salt electrolysis preparation method thereof of a kind of vananum, to promote vananum quality.
In order to realize above-mentioned task, the present invention takes following technical solution:
The electrolytic preparation method of a kind of vananum, it is characterised in that sequentially include the following steps:
A, vanadic anhydride, aluminium sesquioxide are mixed homogeneously with binding agent, additive, utilize forcing press compressing, after drying, make solid state cathode block by high temperature sintering；
B, with graphite block for anode, the fused salt mixt of sodium chloride and calcium chloride is electrolyte, carries out molten-salt electrolysis；
After C, electrolysis complete, by cathode block lift-off fused salt surface, it is carried out, dries, and remelting under an inert atmosphere, finally come out of the stove and obtain vananum.
The vanadic anhydride of wherein said step A and aluminium sesquioxide consumption are prepared with reference to the stoichiometric proportion of AlV50, AlV60 and AlV80 aluminum vanadium product, and concrete mass ratio is between 1:1～5:1.
Additive described in step A is NaCl or CaCl2Therein a kind of or their mixture, additive amount is the 0～6% of vanadic anhydride and aluminium sesquioxide gross mass.The addition of additive is mainly increase response speed, and its consumption is unsuitable too much, is otherwise easily caused negative electrode broken in electrolytic process.
The binding agent of described step A is poly-vinyl alcohol solution or distilled water.
High temperature sintering temperature described in step A control vanadic anhydride fusing point (690 DEG C) below, to avoid vanadic anhydride to melt in sintering process, the high temperature sintering time controls between 5～15h.
The temperature of the molten-salt electrolysis described in step B controls below 660 DEG C, to avoid aluminum to melt.It addition, for avoiding chloride electrolyte to decompose, the voltage of molten-salt electrolysis is unsuitable too high, controls at 2.5～3.3V, and the time is 10～20h.
Compared with the prior art the electrolytic preparation method of the vananum of the present invention, has advantage will be apparent below:
1, adopting the present invention to prepare vananum, temperature is low, technique is simple, and alloying component is easily controlled；
2, process prepared by vananum does not need to add reducing agent and slag former, it is to avoid the pollution to vananum, reduces the impurity content of vananum；
3, not producing containing vanadium waste residue and flue dust, energy consumption is low, and production environment is friendly.
Detailed description of the invention
The present invention is described in further detail by the following examples, it is necessary to explanation is that below example is intended for that those skilled in the art is clearer understands the present invention, the invention is not restricted to these embodiments.
Below in an example, described polyvinyl alcohol (0.03g/ml) binding agent, it is formulated with the polyethylene alcohol and water of solid, compound method is, according to the polyvinyl alcohol adding 0.03g solid in every milliliter of pure water (or distilled water), insulated and stirred is until polyvinyl alcohol is completely dissolved and get final product.
Embodiment 1:
Vanadic anhydride below 200 orders and aluminium sesquioxide 1:1 in mass ratio are mixed, obtain mixed material, additionally with addition of the NaCl of mixed material gross mass 3% and certain polyvinyl alcohol (0.03g/ml) binding agent in mixed material, the concrete consumption of binding agent is that every 20g mixed material is with addition of 1ml.
By the mixed material with addition of NaCl and binding agent under 50MPa compressing, at 680 DEG C, fire 8h, obtain reaction negative electrode.
The NaCl-CaCl being 1:1 with mol ratio2Fused salt is electrolyte, graphite block is anode, and negative electrode carries out fused salt (reduction) electrolysis, temperature 650 DEG C, voltage 3.3V, time 15h.After fused salt (reduction) electrolysis terminates, by cathode block lift-off fused salt surface, the once purged cellular vananum that obtains, then by this cellular vananum remelting under an argon atmosphere, obtain vananum ingot casting.Measuring through chemical analysis, gained vananum is containing vanadium 51.3wt%, oxygen-containing 0.17wt%.
Embodiment 2:
Vanadic anhydride below 200 orders and aluminium sesquioxide 1.5:1 in mass ratio are mixed, obtains mixed material, additionally with addition of the CaCl of mixed material gross mass 1% in mixed material2With certain polyvinyl alcohol (0.03g/ml) binding agent, consumption of binder is that every 20g mixed material is with addition of 1ml.
Will with addition of CaCl2With the mixed material of binding agent under 40MPa compressing, at 680 DEG C, fire 6h, obtain reaction negative electrode.
The NaCl-CaCl being 1:1 with mol ratio2Fused salt is electrolyte, graphite block is anode, and negative electrode carries out fused salt (reduction) electrolysis, temperature 650 DEG C, voltage 3.2V, time 18h.After fused salt (reduction) electrolysis terminates, by cathode block lift-off fused salt surface, the once purged cellular vananum that obtains, then by this cellular vananum remelting under an argon atmosphere, obtain vananum ingot casting.Measuring through chemical analysis, gained vananum is containing vanadium 59.1wt%, oxygen-containing 0.19wt%.
Embodiment 3:
Vanadic anhydride below 200 orders and aluminium sesquioxide 2:1 in mass ratio are mixed, obtains mixed material, additionally with addition of the CaCl of mixed material gross mass 2% in mixed material2With polyvinyl alcohol (0.03g/ml) binding agent, consumption of binder is that every 30g mixed material is with addition of 1ml.
Will with addition of CaCl2With the mixed material of binding agent under 40MPa compressing, at 680 DEG C, fire 6h, obtain reaction negative electrode.
The NaCl-CaCl being 1:1 with mol ratio2Fused salt is electrolyte, graphite block is anode, and negative electrode carries out fused salt (reduction) electrolysis, temperature 650 DEG C, voltage 3.2V, time 18h.After fused salt (reduction) electrolysis terminates, by cathode block lift-off fused salt surface, the once purged cellular vananum that obtains, then by this cellular vananum remelting under an argon atmosphere, obtain vananum ingot casting.Measuring through chemical analysis, gained vananum is containing vanadium 63.8wt%, oxygen-containing 0.19wt%.
Embodiment 4:
Vanadic anhydride below 200 orders and aluminium sesquioxide 3.5:1 in mass ratio are mixed, obtain mixed material, additionally with addition of the NaCl of mixed material gross mass 1% and polyvinyl alcohol (0.03g/ml) binding agent in mixed material, consumption of binder is that every 35g mixed material is with addition of 1ml.
By the mixed material with addition of NaCl and binding agent under 40MPa compressing, at 680 DEG C, fire 5h, obtain reaction negative electrode.
The NaCl-CaCl being 1:1 with mol ratio2Fused salt is electrolyte, graphite block is anode, and negative electrode carries out fused salt (reduction) electrolysis, temperature 650 DEG C, voltage 3.2V, time 20h.After fused salt (reduction) electrolysis terminates, by cathode block lift-off fused salt surface, the once purged cellular vananum that obtains, then by cellular this vananum remelting under an argon atmosphere, obtain vananum ingot casting.Measuring through chemical analysis, gained vananum is containing vanadium 75.1wt%, oxygen-containing 0.20wt%.
Embodiment 5:
Vanadic anhydride below 200 orders and aluminium sesquioxide 4:1 in mass ratio being mixed, obtain mixed material, additionally with addition of certain distilled water in mixed material, distilled water consumption is that every 20g mixed material is with addition of 1ml.
By the compound with addition of distilled water under 40MPa compressing, at 680 DEG C, fire 5h, obtain reaction negative electrode.The NaCl-CaCl being 1:1 with mol ratio2Fused salt is electrolyte, graphite block is anode, and negative electrode carries out fused salt (reduction) electrolysis, temperature 650 DEG C, voltage 3.2V, time 20h.After fused salt (reduction) electrolysis terminates, by cathode block lift-off fused salt surface, the once purged cellular vananum that obtains, then by this cellular vananum remelting under an argon atmosphere, obtain vananum ingot casting.Measuring through chemical analysis, gained vananum is containing vanadium 78.2wt%, oxygen-containing 0.20wt%.
Claims (6)
1. the electrolytic preparation method of a vananum, it is characterised in that follow these steps to carry out:
A, by vanadic anhydride, aluminium sesquioxide, binding agent, additive mix homogeneously, utilize forcing press compressing, after drying, make solid state cathode block by high temperature sintering；
B, with graphite block for anode, the fused salt mixt of sodium chloride and calcium chloride is electrolyte, carries out molten-salt electrolysis；
After C, molten-salt electrolysis complete, by cathode block lift-off fused salt, it is carried out, dries, and remelting under an inert atmosphere, finally come out of the stove and obtain vananum.
2. the method for claim 1, it is characterised in that the vanadic anhydride of described step A and the consumption of aluminium sesquioxide are prepared with reference to the stoichiometric proportion of AlV50, AlV60 and AlV80 aluminum vanadium product, and concrete mass ratio is between 1:1～5:1.
3. the method for claim 1, it is characterised in that the binding agent of described step A is poly-vinyl alcohol solution or distilled water.
4. the method for claim 1, it is characterised in that: the additive in described step A is NaCl or CaCl2One of which or their mixture, additive amount is the 0～6% of vanadic anhydride and aluminium sesquioxide gross mass.
5. the method for claim 1, it is characterised in that the temperature of the high temperature sintering of described step A controls below the fusing point of vanadic anhydride, sintering time 5～15h.
6. the method for claim 1, it is characterised in that the temperature of the molten-salt electrolysis described in step B is less than 660 DEG C, the voltage of molten-salt electrolysis is 2.5～3.3V, and the time is 10～20h.
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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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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 |
Non-Patent Citations (1)
| Title |
|---|
| 《化工百科全书》编辑委员会: "《化工百科全书 第四卷》", 30 September 1993, 北京：化学工业出版社 * |
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Granted publication date: 20180504 Termination date: 20210311 |