CN101343755A - Method for preparing metal vanadium - Google Patents
Method for preparing metal vanadium Download PDFInfo
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- CN101343755A CN101343755A CNA2008102130254A CN200810213025A CN101343755A CN 101343755 A CN101343755 A CN 101343755A CN A2008102130254 A CNA2008102130254 A CN A2008102130254A CN 200810213025 A CN200810213025 A CN 200810213025A CN 101343755 A CN101343755 A CN 101343755A
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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
- C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
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Abstract
The invention discloses a metal vanadium production method. The metal vanadium production method comprises the following steps: vanadium oxide and a carbon reducing agent in the simple substance form are adopted as raw materials, which are mixed to form a mixture according to the chemical reaction stoichiometric proportion of VCmOn and CO generated from the vanadium oxide and the carbon reducing agent in the simple substance, the mixture is molded by pressing, wherein, m is larger than 0 and less than or equal to 1, n is larger than 0 and less than or equal to 1, and m is less than or equal to n; within the temperature range of 800 to 1600 DEG C, the mixture molded by pressing reacts to generate VCmOn with an electric conduction performance; the VCmOn is adopted as a consumption anode, a conducting material is adopted as a cathode, halide molten salt systems of the alkali metal, halide molten salt systems of the alkaline earth metal or the combination are adopted as the electrolytic solution, thereby combining the electrolytic cell, the electrolysis is performed within the temperature range of 400 to 1000 DEG C, during the electrolysis process, the carbon and oxygen contained at the consumption anode form gas of CO, CO2 or O2 which is discharged, and simultaneously vanadium enters the electrolytic solution in the ion form and is deposited at the cathode to obtain metal vanadium.
Description
Technical field
The present invention relates to a kind of method of producing vanadium metal, specifically, relate to a kind of method of utilizing vanadium oxide/vanadium carbide by the electrolysis production vanadium metal.
Background technology
Vanadium metal is much accounted of day by day as a kind of brand-new material, its have in light weight, intensity is big, heat absorption capacity is strong, the characteristics of stable mechanical performance.Vanadium metal is good aerospace material, in aerospace and aircraft industry, can be used for making the switching housing and the covering of rocket, guided missile, spaceship, the structured material that can be used as air dreadnought, shuttle, can be used for making the navigation parts of aircraft arrestment energy absorber and aircraft, airship, guided missile, and can be used as the additive of the high energy fuels of rocket, guided missile, jet airplane.Vanadium metal is the additive of steel alloy in metallurgical industry, also is used to make refractory materials and special glass, unicircuit, antenna etc.In addition, vanadium metal has good nuclear physics performance, is the treasured of nuclear industry, is the preferred materials of neutron reflector in the reactor.
Producing vanadium metal has many kinds of technologies, and for example electron-bombardment method, electrolytic refining process are smelted in magnesium-sodium reduction vanadium trichloride, sealing, also have technologies such as calcium reduction, vacuum carbon reduction, iodide thermolysis in addition.
The method of the production vanadium metal of main flow is a thermite process at present.The available following reaction of the reaction of thermite reduction Vanadium Pentoxide in FLAKES is represented:
3V
2O
5+2Al＝3V
2O
4+Al
2O
3
3V
2O
4+2Al＝3V
2O
3+Al
2O
3
3V
2O
3+2Al＝6VO+Al
2O
3
3VO+2Al＝3V+Al
2O
3
Thermite process is produced vanadium two kinds of technologies, and a kind of is to carry out in airtight steel bomb container, with highly purified V
2O
5After adding reactor with the mixture of aluminium powder, reactor is vacuumized and cleans for several times with helium, vacuumize afterwards again, by being embedded in the resistance wire heating starting reaction in the reactant, the resultant that obtains will be transformed into highly purified vanadium through the high-temperature vacuum method then; Another is to carry out in the container that opens wide, with purified V
2O
5, aluminium powder and industrial grade the CaO thorough mixing after add reactor, the magnesium rod that is placed on the compound by burning starts reaction, in case start, reaction can be finished rapidly, obtaining containing the thick vanadium of impurity such as aluminium, is that raw material carries out fused salt electrolysis and promptly obtains high purity vanadium with thick vanadium at last.
Produce vanadium with thermite process following several shortcoming arranged:
Because it is very high that the reaction pair material purity in the encloses container requires, and use a large amount of aluminium powders, and will handle through high-temperature vacuum, production cost is higher;
The reaction pair material purity of open container is less demanding, but also needs a large amount of aluminium powders, and cost is also higher, and because container is uncovered, can cause bigger pollution to environment;
This method is batch production, can not satisfy industrialized production.
It is the lower chloride that utilizes than reduction vanadium such as more active metal of vanadium such as sodium magnesium that vanadium metal is produced in metallothermic reduction, because the lower chloride of vanadium is not easy to obtain, causes the production cost of this method higher.
Summary of the invention
The present invention is by providing a kind of method of producing vanadium metal, one or more in the above-mentioned technical problem have been overcome, this method may further comprise the steps: with the oxide compound of vanadium and the carbonaceous reducing agent of simple substance form is raw material, generates VC according to the oxide compound of vanadium and the carbonaceous reducing agent reaction of simple substance form
mO
nMix to form compound with the stoichiometric ratio of the chemical reaction of CO, and with compound compression moulding, 0＜m≤1,0＜n≤1 wherein, m≤n; In 800 ℃～1600 ℃ temperature range, make the compound reaction of compression moulding, generate VC with conductivity
mO
nWith VC
mO
nAs consumable anode, with electro-conductive material as negative electrode, thereby halogenide molten salt system or their combination with alkali-metal halogenide molten salt system, alkaline-earth metal are formed electrolyzer as electrolytic solution, in 400 ℃～1000 ℃ temperature range, carry out electrolysis, in electrolytic process, carbon that consumable anode is contained and oxygen form gas CO, CO
2Or O
2Emit, vanadium enters electrolytic solution and obtains vanadium metal in cathodic deposition with the ionic form simultaneously.
According to an aspect of the present invention, the oxide compound of described vanadium can comprise V
2O
5, V
2O
4, VO
2And V
2O
3In at least a, determine stoichiometric ratio according to the reaction equation of following correspondence:
V
2O
5+(5+2m-2n)C＝2VC
mO
n+(5-2n)CO↑
V
2O
4+(4+2m-2n)C＝2VC
mO
n+(4-2n)CO↑
VO
2+(2+m-n)C＝VC
mO
n+(2-n)CO↑
V
2O
3+(3+2m-2n)C＝2VC
mO
n+(3-2n)CO↑。
The pressure of compound compression moulding can be 10MPa～100MPa.Can under vacuum condition, make the compound reaction of compression moulding, described VC
mO
nResistivity can be 0.001 Ω cm～0.1 Ω cm.
According to an aspect of the present invention, described alkali-metal halogenide molten salt system can be alkali-metal muriate eutectic molten salt system, and the halogenide molten salt system of described alkaline-earth metal can be the muriate eutectic molten salt system of alkaline-earth metal.The electro-conductive material of negative electrode can be carbon steel, titanium, molybdenum, vanadium or their alloy.Anode initial current density during electrolysis can be 0.05A/cm
2～1.5A/cm
2, be preferably 0.05A/cm
2～0.5A/cm
2, negative electrode initial current density is 0.10A/cm
2～1.5A/cm
2, be preferably 0.10A/cm
2～0.5A/cm
2
According to an aspect of the present invention, this method also comprises: be the ionogen that 0.5%～5% hydrochloric acid eccysis vanadium metal is mingled with concentration after electrolysis is finished, use the distilled water wash vanadium metal to the filtrate halogen-free ionic again.
Therefore, have according to the method for production vanadium metal of the present invention that energy consumption is low, cost is low, the advantage of non-environmental-pollution.In addition, electrolytic process does not have the anode sludge in theory and produces, and can continuous production.
Embodiment
Now, will the method for production vanadium metal according to the present invention be described in detail.
At first, be raw material with the oxide compound of vanadium and the carbonaceous reducing agent of simple substance form, (be VC according to the oxide compound of vanadium and the carbonaceous reducing agent reaction generation vanadium oxide/vanadium carbide of simple substance form
mO
n, 0＜m≤1,0＜n≤1 wherein, the m≤n) and the stoichiometric ratio of the chemical reaction of CO are mixed and are formed compound, and with compound compression moulding.
According to the method for production vanadium metal of the present invention, can use a kind of oxide compound of vanadium, for example V
2O
5, V
2O
4, VO
2Or V
2O
3, also can use the mixture of multiple barium oxide, for example by V
2O
5, V
2O
4, VO
2And V
2O
3In the mixture of multiple composition.Can be with various barium oxide products (as various technical pures, chemical pure, analytical pure, V that top grade is pure
2O
5, V
2O
4, VO
2And V
2O
3Product) form the oxide compound of described vanadium is provided.Can provide described carbonaceous reducing agent with the form of graphite, refinery coke, coke, hard coal, carbon black etc., that is, carbonaceous reducing agent is a carbon simple substance contained in graphite, refinery coke, coke, hard coal, the carbon black.The oxide compound of described vanadium and carbonaceous reducing agent all can be powder, but the invention is not restricted to this, for example can be pellet.
As mentioned above, generate VC according to the oxide compound of vanadium and the carbonaceous reducing agent reaction of simple substance form
mO
n(0＜m≤1,0＜n≤1, the stoichiometry of the chemical reaction of m≤n) and CO is recently mixed the oxide compound of vanadium and the carbonaceous reducing agent of simple substance form.Specifically, the oxide compound at vanadium is V
2O
5, V
2O
4, VO
2And V
2O
3One of situation under, determine stoichiometric ratio according to the reaction equation of following correspondence:
V
2O
5+(5+2m-2n)C＝2VC
mO
n+(5-2n)CO↑
V
2O
4+(4+2m-2n)C＝2VC
mO
n+(4-2n)CO↑
VO
2+(2+m-n)C＝VC
mO
n+(2-n)CO↑
V
2O
3+(3+2m-2n)C＝2VC
mO
n+(3-2n)CO↑。
Oxide compound at vanadium is V
2O
5, V
2O
4, VO
2And V
2O
3In the situation of mixture of multiple composition under, can determine the consumption of carbonaceous reducing agent according to each components contents and above reaction equation in the weight of mixture, the mixture, promptly determine stoichiometric ratio, this is conspicuous to those skilled in the art.
The pressure of compound compression moulding is preferably 10MPa～100MPa, but the invention is not restricted to this, for example can adopt pressure greater than 100MPa.The shape that the compound of being made up of the oxide compound and the carbonaceous reducing agent of vanadium is pressed into can be for block, tabular etc., but this shape is unrestricted, as long as this shape is applicable to the anode that uses in the electrolyzer.
Then, in 800 ℃～1600 ℃ temperature range, make the compound reaction of compression moulding, generate VC with conductivity
mO
n, 0＜m≤1,0＜n≤1 wherein, m≤n.Because the reaction of the carbonaceous reducing agent of the oxide compound of vanadium and simple substance form generates VC
mO
nWith the chemical reaction of CO for producing the reaction of gas, so, preferably under vacuum condition, make the compound reaction of compression moulding in order to make reaction carry out fully and to shorten the reaction times; Yet, the invention is not restricted to this, for example can under normal pressure, carry out this reaction.
The reaction times of this reaction is unrestricted, those skilled in the art can according to temperature of reaction and/vacuum tightness in the reaction vessel determines the reaction times.Specifically, when temperature of reaction and/or vacuum tightness are higher, can control the reaction times shorter; When temperature of reaction and/or vacuum tightness are low, can control the reaction times longer.That is to say that can decision generate VC
mO
nFactor be temperature of reaction, 800 ℃～1600 ℃ can guarantee VC
mO
nGeneration, those skilled in the art can determine the suitable reaction times so that react completely and carry out according to temperature of reaction and/or vacuum tightness.
According to above step, prepared VC
mO
nResistivity be 0.001 Ω cm～0.1 Ω cm.Therefore, according to the present invention, by preparing VC not being higher than under 1600 ℃ the temperature
mO
n, make energy consumption lower.
Then, with the VC of above-mentioned preparation
mO
nAs consumable anode, with a kind of electro-conductive material as negative electrode, thereby halogenide molten salt system or their combination with alkali-metal halogenide molten salt system, alkaline-earth metal are formed electrolyzer as electrolytic solution, carry out electrolysis in 400 ℃～1000 ℃ temperature range.Here, the electro-conductive material that negative electrode adopts can be metallic substance, for example carbon steel, titanium, molybdenum, vanadium or their alloy.But the material of negative electrode is not limited thereto, if its conductivity good and not with its on sedimentary vanadium vigorous reaction.Preferably, adopt the fluoride molten salt system of the molten chloride system of alkali-metal molten chloride system, alkaline-earth metal, alkali-metal fluoride molten salt system, alkaline-earth metal or their combination as electrolytic solution.More preferably, adopt the muriate eutectic molten salt system of alkali-metal muriate eutectic molten salt system, alkaline-earth metal or their combination as electrolytic solution.For example, electrolytic solution can be NaCl-KCl, NaCl-KCl-MgCl
2, LiCl-KCl, NaCl-KCl-CaCl
2, KCl-MgCl
2, KCl-CaCl
2, NaCl-BeCl
2, NaCl-NaF, NaF-KF, NaF-MgF
2, in the LiCl-LiF molten salt system one or more.
Therefore, in electrolytic process, carbon that consumable anode is contained and oxygen form gas CO, CO
2Or O
2Emit, vanadium enters electrolytic solution and obtains vanadium metal in cathodic deposition with the ionic form simultaneously.In electrolytic process, can reclaim the gas that is produced, not produce environmental pollution.
Anode initial current density during electrolysis is 0.05A/cm
2～1.5A/cm
2, be preferably 0.05A/cm
2～0.5A/cm
2Negative electrode initial current density during electrolysis is 0.10A/cm
2～1.5A/cm
2, be preferably 0.10A/cm
2～0.5A/cm
2If current density is too little, then the electrodeposition rate of vanadium metal is too slow; If current density is too big, then the groove of electrolyzer is pressed too highly, so control cathode and anodic initial current density are in above-mentioned scope.
Carried out the regular hour during section when electrolysis, those skilled in the art can judge electrolytic finishing according to settling on sedimental adhesion condition and the negative electrode on the negative electrode and the distance between the anode.That is to say that the judgement that electrolysis is finished is known to those skilled in the art.
According to the method for production vanadium metal of the present invention, electrolytic process can carry out continuously, for example can realize continuous production by anode and negative electrode in the continuous replacing electrolyzer.By using VC
mO
nAs consumable anode directly electrolysis in the halogenide molten salt system, the method for production vanadium metal of the present invention has significantly reduced cost with respect to thermite process, magnesium-traditional methods such as sodium reduction vanadium trichloride.
After electrolysis is finished, taking out negative electrode from electrolytic solution, and make deposits cool on the negative electrode to room temperature, is the ionogen that 0.5%～5% hydrochloric acid eccysis settling is mingled with concentration at first, uses the distilled water wash settling to the filtrate halogen-free ionic again.In the process with the salt acid elution, the settling on the negative electrode is easy to split away off from negative electrode, in this case, collects the settling that comes off with collection device.Selectively, can make settling and cathodic disbonding or rap negative electrode with tripping device to make settling and cathodic disbonding, collect the settling that comes off, use hydrochloric acid and distilled water wash settling then as mentioned above respectively with collection device.Settling after the washing is carried out chemical analysis, and the result shows that sedimental content of vanadium is greater than 99%.
The following examples have illustrated the present invention in further detail.Yet, should be appreciated that the present invention is not subjected to the restriction of these embodiment.
Embodiment 1:
Get m=n=0.5, according to by reaction equation V
2O
5+ 5C=V
2The stoichiometric ratio of CO+4CO ↑ definite is mixed powdery Vanadium Pentoxide in FLAKES product (analytical pure) and Graphite Powder 99 product (analytical pure) formation compound, and with the pressure of 10MPa with the compound briquetting, the resistivity that records the compound after the compacting is 96 Ω cm.
Then,, the compound of briquetting was reacted 5 hours, obtain block materials VC under 1400 ℃ the temperature and under the air pressure at 230Pa
mO
n, recording its resistivity is 0.05 Ω cm.Therefore, compare block materials VC with the compound of compacting before the afterreaction
mO
nConductivity significantly improve.
Calculate according to reacted rate of weight loss, as can be known the VC for preparing among this embodiment
mO
nAtom proportioning form be V
2CO.
V with above-mentioned preparation
2CO as negative electrode, forms electrolyzer with the NaCl-KCl molten salt system as electrolytic solution with carbon steel as consumable anode, carries out electrolysis under 800 ℃ temperature, and anodic initial current density is 0.2A/cm
2, the initial current density of negative electrode is 0.4A/cm
2After electrolysis is finished, taking out negative electrode from electrolytic solution, to room temperature, is the ionogen that the hydrochloric acid eccysis settling of 2% (mass percent) is mingled with concentration with the deposits cool on the negative electrode at first, and being washed with distilled water to filtrate does not again have chlorion, the final drying settling.
The above-mentioned dry settling of crossing is carried out chemical analysis, and the result shows that its content of vanadium is greater than 99% (mass percent).
Embodiment 2:
Get m=n=0.5, according to by reaction equation V
2O
3+ 3C=V
2The stoichiometric ratio of CO+2CO ↑ definite is mixed powdery vanadous oxide product (analytical pure) and Graphite Powder 99 product (analytical pure) formation compound, and with the pressure of 100MPa with the compound briquetting, the resistivity that records the compound after the compacting is 63 Ω cm.
Then,, the compound of briquetting was reacted 5 hours, obtain block materials VC under 1200 ℃ the temperature and under the air pressure at 90Pa
mO
n, recording its resistivity is 0.04 Ω cm.Therefore, compare block materials VC with the compound of compacting before the afterreaction
mO
nConductivity significantly improve.
Calculate according to reacted rate of weight loss, as can be known the VC for preparing among this embodiment
mO
nAtom proportioning form be V
2CO.
V with above-mentioned preparation
2CO is as consumable anode, with carbon steel as negative electrode, with NaCl-KCl-MgCl
2Molten salt system is formed electrolyzer as electrolytic solution, carries out electrolysis under 660 ℃ temperature, and anodic initial current density is 0.1A/cm
2, the initial current density of negative electrode is 1.0A/cm
2After electrolysis is finished, taking out negative electrode from electrolytic solution, to room temperature, is the ionogen that the hydrochloric acid eccysis settling of 2% (mass percent) is mingled with concentration with the deposits cool on the negative electrode at first, and being washed with distilled water to filtrate does not again have chlorion, the final drying settling.
The above-mentioned dry settling of crossing is carried out chemical analysis, and the result shows its content of vanadium greater than 99% (mass percent), and the above-mentioned dry settling of crossing is a dendrite.
Embodiment 3:
Get m=n=0.5, according to by reaction equation V
2O
4+ 4C=V
2The stoichiometric ratio of CO+3CO ↑ definite is mixed powdery vanadium tetraoxide product (analytical pure) and Graphite Powder 99 product (analytical pure) formation compound, and with the pressure of 10MPa with the compound briquetting, the resistivity that records the compound after the compacting is 85 Ω cm.
Then,, the compound of briquetting was reacted 3 hours, obtain block materials VC under 1400 ℃ the temperature and under the air pressure at 20Pa
mO
n, recording its resistivity is 0.02 Ω cm.Therefore, compare block materials VC with the compound of compacting before the afterreaction
mO
nConductivity significantly improve.
Calculate according to reacted rate of weight loss, as can be known the VC for preparing among this embodiment
mO
nAtom proportioning form be V
2CO.
V with above-mentioned preparation
2CO as negative electrode, forms electrolyzer with the LiCl-KCl molten salt system as electrolytic solution with carbon steel as consumable anode, carries out electrolysis under 500 ℃ temperature, and anodic initial current density is 0.2A/cm
2, the initial current density of negative electrode is 1.0A/cm
2After electrolysis is finished, taking out negative electrode from electrolytic solution, to room temperature, is the ionogen that the hydrochloric acid eccysis settling of 1% (mass percent) is mingled with concentration with the deposits cool on the negative electrode at first, and being washed with distilled water to filtrate does not again have chlorion, the final drying settling.
The above-mentioned dry settling of crossing is carried out chemical analysis, and the result shows that its content of vanadium is greater than 99% (mass percent).
Embodiment 4:
Get m=0.5, n=1 is according to by reaction equation 2VO
2+ 3C=V
2CO
2The stoichiometric ratio of+2CO ↑ definite is mixed powdery vanadium dioxide product (analytical pure) and Graphite Powder 99 product (analytical pure) formation compound, and with the pressure of 10MPa with the compound briquetting, the resistivity that records the compound after the compacting is 81 Ω cm.
Then,, the compound of briquetting was reacted 5 hours, obtain block materials V under 1500 ℃ the temperature and under the air pressure at 270Pa
2CO
2, recording its resistivity is 0.02 Ω cm.Therefore, compare block materials V with the compound of compacting before the afterreaction
2CO
2Conductivity significantly improve.
Calculate according to reacted rate of weight loss, as can be known the VC for preparing among this embodiment
mO
nAtom proportioning form be V
2CO
2
V with above-mentioned preparation
2CO
2As consumable anode, with the titanium rod as negative electrode, with NaCl-KCl-CaCl
2Molten salt system is formed electrolyzer as electrolytic solution, carries out electrolysis under 850 ℃ temperature, and anodic initial current density is 0.1A/cm
2, the initial current density of negative electrode is 0.4A/cm
2After electrolysis is finished, taking out negative electrode from electrolytic solution, to room temperature, is the ionogen that the hydrochloric acid eccysis settling of 1% (mass percent) is mingled with concentration with the deposits cool on the negative electrode at first, and being washed with distilled water to filtrate does not again have chlorion, the final drying settling.
The above-mentioned dry settling of crossing is carried out chemical analysis, and the result shows that its content of vanadium is greater than 99% (mass percent).
Therefore, according to the present invention, at first prepare VC at the oxide compound and the carbonaceous reducing agent that are not higher than under 1600 ℃ the temperature by vanadium
mO
n, utilize VC then
mO
nAs anode directly electrolysis in the halogenide molten salt system, thus can be with less energy-consumption, the highly purified vanadium metal of low cost production.In addition, this method technology environmental protection, non-environmental-pollution; Electrolytic process does not have the anode sludge in theory and produces, and can continuous production.
The invention is not restricted to the foregoing description, without departing from the present invention, can carry out various changes and modifications.
Claims (10)
1, a kind of method of producing vanadium metal is characterized in that may further comprise the steps:
With the oxide compound of vanadium and the carbonaceous reducing agent of simple substance form is raw material, generates VC according to the oxide compound of vanadium and the carbonaceous reducing agent reaction of simple substance form
mO
nMix to form compound with the stoichiometric ratio of the chemical reaction of CO, and with compound compression moulding, 0＜m≤1,0＜n≤1 wherein, m≤n;
In 800 ℃～1600 ℃ temperature range, make the compound reaction of compression moulding, generate VC with conductivity
mO
n
With VC
mO
nAs consumable anode, with electro-conductive material as negative electrode, thereby form electrolyzer with the halogenide molten salt system of alkali-metal halogenide molten salt system, alkaline-earth metal or their combination as electrolytic solution, in 400 ℃～1000 ℃ temperature range, carry out electrolysis,
In electrolytic process, carbon that consumable anode is contained and oxygen form gas CO, CO
2Or O
2Emit, vanadium enters electrolytic solution and obtains vanadium metal in cathodic deposition with the ionic form simultaneously.
2, the method for production vanadium metal as claimed in claim 1 is characterized in that, the oxide compound of described vanadium comprises V
2O
5, V
2O
4, VO
2And V
2O
3In at least a, determine stoichiometric ratio according to the reaction equation of following correspondence:
V
2O
5+(5+2m-2n)C＝2VC
mO
n+(5-2n)CO↑
V
2O
4+(4+2m-2n)C＝2VC
mO
n+(4-2n)CO↑
VO
2+(2+m-n)C＝VC
mO
n+(2-n)CO↑
V
2O
3+(3+2m-2n)C＝2VC
mO
n+(3-2n)CO↑。
3, the method for production vanadium metal as claimed in claim 1 is characterized in that, is 10MPa～100MPa with the pressure of compound compression moulding.
4, the method for production vanadium metal as claimed in claim 1 is characterized in that, makes the compound reaction of compression moulding under vacuum condition.
5, the method for production vanadium metal as claimed in claim 1 is characterized in that, described VC
mO
nResistivity be 0.001 Ω cm～0.1 Ω cm.
6, the method for production vanadium metal as claimed in claim 1, it is characterized in that, described alkali-metal halogenide molten salt system is alkali-metal muriate eutectic molten salt system, and the halogenide molten salt system of described alkaline-earth metal is the muriate eutectic molten salt system of alkaline-earth metal.
7, the method for production vanadium metal as claimed in claim 1 is characterized in that, described electro-conductive material is carbon steel, titanium, molybdenum, vanadium or their alloy.
8, the method for production vanadium metal as claimed in claim 1 is characterized in that, the anode initial current density during electrolysis is 0.05A/cm
2～1.5A/cm
2, negative electrode initial current density is 0.10A/cm
2～1.5A/cm
2
9, the method for production vanadium metal as claimed in claim 1 is characterized in that, the anode initial current density during electrolysis is 0.05A/cm
2～0.5A/cm
2, negative electrode initial current density is 0.10A/cm
2～0.5A/cm
2
10, the method for production vanadium metal as claimed in claim 1, it is characterized in that, described method also comprises: be the ionogen that 0.5%～5% hydrochloric acid eccysis vanadium metal is mingled with concentration after electrolysis is finished, use the distilled water wash vanadium metal to the filtrate halogen-free ionic again.
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|---|---|---|---|
| CN2008102130254A CN101343755B (en) | 2008-08-20 | 2008-08-20 | Method for preparing metal vanadium |
| PCT/CN2009/072803 WO2010020142A1 (en) | 2008-08-20 | 2009-07-17 | Method for producing metal vanadium |
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|---|---|---|---|
| CN2008102130254A CN101343755B (en) | 2008-08-20 | 2008-08-20 | Method for preparing metal vanadium |
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| CN101343755B CN101343755B (en) | 2010-08-25 |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010020142A1 (en) * | 2008-08-20 | 2010-02-25 | 攀钢集团研究院有限公司 | Method for producing metal vanadium |
| CN102121123A (en) * | 2011-04-18 | 2011-07-13 | 北京科技大学 | Vanadium metal smelting process |
| CN102912379A (en) * | 2012-10-25 | 2013-02-06 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing metal titanium |
| CN102925930A (en) * | 2012-10-25 | 2013-02-13 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for producing metal titanium from titaniferous material |
| CN102969521A (en) * | 2012-12-10 | 2013-03-13 | 贵州省岑巩县银峰矿业有限公司 | Method for preparing positive electrode electrolyte of vanadium battery |
| CN102978664A (en) * | 2011-09-05 | 2013-03-20 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of metal vanadium and metal vanadium obtained by same |
| CN104060107A (en) * | 2013-09-11 | 2014-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal vanadium or vanadium alloy preparation method |
| CN105018970A (en) * | 2014-04-24 | 2015-11-04 | 东北大学 | Method for preparing vanadium metal through thermoelectric reduction in molten fluoride system |
| CN110079833A (en) * | 2019-04-24 | 2019-08-02 | 北京科技大学 | A kind of high-carbon slightly miscellaneous vanadium refining high-purity gold category vanadium method |
| CN111364065A (en) * | 2020-03-05 | 2020-07-03 | 中国原子能科学研究院 | Method for preparing uranium by utilizing uranium oxide |
| CN112251619A (en) * | 2020-09-11 | 2021-01-22 | 河钢承德钒钛新材料有限公司 | Preparation method and device of metal vanadium |
| CN113106496A (en) * | 2021-03-31 | 2021-07-13 | 北京科技大学 | Method for electrolyzing high-purity metal vanadium by vanadium-carbon-oxygen solid solution anode molten salt |
| CN113416984A (en) * | 2021-06-09 | 2021-09-21 | 华北理工大学 | Method for preparing metallic iron by utilizing soluble anode electrolysis |
| CN114481230A (en) * | 2022-02-25 | 2022-05-13 | 北京科技大学 | High-density hafnium-carbon-oxygen solid solution, preparation method thereof and method for preparing metal hafnium through electrolysis |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7410562B2 (en) * | 2003-08-20 | 2008-08-12 | Materials & Electrochemical Research Corp. | Thermal and electrochemical process for metal production |
| US7794580B2 (en) * | 2004-04-21 | 2010-09-14 | Materials & Electrochemical Research Corp. | Thermal and electrochemical process for metal production |
| CN100415940C (en) * | 2005-05-08 | 2008-09-03 | 北京科技大学 | Pure titanium production from titanium monoxide/titanium carbide soluble solid anode electrolysis |
| CN101343755B (en) * | 2008-08-20 | 2010-08-25 | 攀钢集团研究院有限公司 | Method for preparing metal vanadium |
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2008
- 2008-08-20 CN CN2008102130254A patent/CN101343755B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010020142A1 (en) * | 2008-08-20 | 2010-02-25 | 攀钢集团研究院有限公司 | Method for producing metal vanadium |
| CN102121123A (en) * | 2011-04-18 | 2011-07-13 | 北京科技大学 | Vanadium metal smelting process |
| CN102121123B (en) * | 2011-04-18 | 2012-05-09 | 北京科技大学 | Vanadium metal smelting process |
| CN102978664A (en) * | 2011-09-05 | 2013-03-20 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of metal vanadium and metal vanadium obtained by same |
| CN102978664B (en) * | 2011-09-05 | 2015-12-02 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of preparation method of vanadium metal and the vanadium metal obtained by the method |
| CN102925930B (en) * | 2012-10-25 | 2015-11-25 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of titaniferous material produces the method for metal titanium |
| CN102912379A (en) * | 2012-10-25 | 2013-02-06 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing metal titanium |
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| US9963796B2 (en) | 2012-10-25 | 2018-05-08 | Pangang Group Panzhihua Iron & Steel Research Institute Co., Ltd. | Method of producing titanium metal with titanium-containing material |
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| CN104060107B (en) * | 2013-09-11 | 2015-08-05 | 攀钢集团攀枝花钢铁研究院有限公司 | The preparation method of a kind of vanadium metal or vanadium alloy |
| CN104060107A (en) * | 2013-09-11 | 2014-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal vanadium or vanadium alloy preparation method |
| CN105018970A (en) * | 2014-04-24 | 2015-11-04 | 东北大学 | Method for preparing vanadium metal through thermoelectric reduction in molten fluoride system |
| CN105018970B (en) * | 2014-04-24 | 2017-11-10 | 东北大学 | A kind of method that thermoelectricity reduction prepares vanadium metal in fluoride smelt salt |
| CN110079833A (en) * | 2019-04-24 | 2019-08-02 | 北京科技大学 | A kind of high-carbon slightly miscellaneous vanadium refining high-purity gold category vanadium method |
| CN111364065A (en) * | 2020-03-05 | 2020-07-03 | 中国原子能科学研究院 | Method for preparing uranium by utilizing uranium oxide |
| CN112251619A (en) * | 2020-09-11 | 2021-01-22 | 河钢承德钒钛新材料有限公司 | Preparation method and device of metal vanadium |
| CN112251619B (en) * | 2020-09-11 | 2023-08-04 | 河钢承德钒钛新材料有限公司 | Preparation method and device of vanadium metal |
| CN113106496A (en) * | 2021-03-31 | 2021-07-13 | 北京科技大学 | Method for electrolyzing high-purity metal vanadium by vanadium-carbon-oxygen solid solution anode molten salt |
| CN113416984A (en) * | 2021-06-09 | 2021-09-21 | 华北理工大学 | Method for preparing metallic iron by utilizing soluble anode electrolysis |
| CN114481230A (en) * | 2022-02-25 | 2022-05-13 | 北京科技大学 | High-density hafnium-carbon-oxygen solid solution, preparation method thereof and method for preparing metal hafnium through electrolysis |
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| WO2010020142A1 (en) | 2010-02-25 |
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