CN113106496A - Method for electrolyzing high-purity metal vanadium by vanadium-carbon-oxygen solid solution anode molten salt - Google Patents
Method for electrolyzing high-purity metal vanadium by vanadium-carbon-oxygen solid solution anode molten salt Download PDFInfo
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 55
- 239000002184 metal Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 46
- 150000003839 salts Chemical class 0.000 title claims abstract description 38
- 239000006104 solid solution Substances 0.000 title claims abstract description 24
- XSJUQOYGUPSJQG-UHFFFAOYSA-N [V].[O].[C] Chemical compound [V].[O].[C] XSJUQOYGUPSJQG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 claims abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 4
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 4
- 150000002500 ions Chemical group 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 claims abstract 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000001103 potassium chloride Substances 0.000 claims description 6
- 235000011164 potassium chloride Nutrition 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 235000011148 calcium chloride Nutrition 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 12
- 239000012535 impurity Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 7
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 230000005496 eutectics Effects 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000007670 refining Methods 0.000 description 4
- 238000005272 metallurgy Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 229910021549 Vanadium(II) chloride Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
- C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention provides a method for electrolyzing high-purity metal vanadium by using vanadium-carbon-oxygen solid solution anode molten salt, which comprises the following preparation processes: firstly, vanadium oxide and carbon or vanadium carbide are taken as raw materials, mixed according to the stoichiometric ratio of chemical reaction, then pressed to be formed, sintered at high temperature to prepare the vanadium carbon oxygen solid solution anode with metal conductivity, and in alkali metal or alkaline earth metal chloride molten salt, the temperature is 500-1000 ℃ and the A/cm is 0.1-1.02Electrolyzing for 10-25 h under constant current density; in the electrolysis process, vanadium in the solid solution anode is electrochemically dissolved into molten salt in a low-valence ion form and migrates to the cathode for electrochemical reduction to high-purity metal vanadium, and carbon and oxygen elements in the solid solution anode are spontaneously discharged in a gaseous form of carbon monoxide or carbon dioxide. The method has the advantages of short process flow, simple and convenient operation, loose requirements on process conditions and equipment, no introduction of foreign metal impurities, high product purity and no anode mud residue, and is a green, short-range and high-efficiency high-purity metal vanadiumA preparation method.
Description
Technical Field
The invention relates to a method for preparing high-purity vanadium metal by molten salt electrolysis, belongs to the field of metallurgy and chemical industry, and particularly relates to the field of molten salt electrolysis.
Background
Vanadium (V) belongs to a transition metal element of group VB, has a melting point as high as 1890 ℃, has good ductility, corrosion resistance and high hardness, and is a strategic key metal. The vanadium metal is called industrial monosodium glutamate and is widely applied to the fields of atomic energy, aerospace, metallurgy and energy. The quality requirement of the vanadium metal is increased along with the development of the industry. The industrial preparation process of the vanadium metal mainly comprises (1) a vacuum carbothermic reduction method, (2) a silicothermic reduction method, (3) a vanadium nitride thermal decomposition method, and (4) a metallothermic reduction method of vanadium oxide or chloride. The purity of the vanadium metal obtained by the method is low, and the obtained product still needs to be further refined and purified. The prior crude vanadium refining method mainly comprises the following steps: (1) an electron beam melting method, (2) a molten salt electrolysis method, (3) an iodide thermal decomposition method, (4) a solid-state electromigration method, and the like. However, these refining methods have problems of low recovery rate, low efficiency, high energy consumption, and the like, and thus increase the cost for industrially producing high-purity vanadium metal.
The molten salt electrolysis technology is a green sustainable metallurgy method, and has unique advantages for smelting high-purity vanadium metal. Yan bud (CN101649471,2010) discloses a method for preparing high-purity metal vanadium by using a soluble crude vanadium anode. Taking ferrovanadium with the vanadium mass fraction of 80 percent as an anode in NaCl-KCl-VCl2Electrolyzing in molten salt for 4h to obtain the purity>99.95% of high-purity vanadium. When the anode vanadium content was reduced to 50%, the remaining anode was a commercial product of ferrovanadium. The vanadium metal prepared by the method has high purity, but the requirement on raw materials is strict, the vanadium content is required to be more than 50%, and the vanadium yield is lower. Tripathy (High temp. Mater. Processes,2002,21(3):127-2Electrolyzing crude vanadium obtained by silicon thermal reduction in molten salt, and controlling proper current density to obtain dendritic vanadium metal with vanadium yield of 80%, wherein the vanadium metal still contains metal impurities such as Al, Cr, Fe, Ni and the like. Therefore, raw materials used for molten salt electrolysis are all crude metal vanadium, the crude metal vanadium is prepared by a high-temperature metal thermal reduction method generally, metal impurities are more and high in content, the problem of impurity metal codeposition in the electrolysis process is prominent, the purity of the metal vanadium is seriously reduced, the high-purity metal vanadium can be prepared and obtained only by further refining for multiple times, and the yield of the metal vanadium is low. Therefore, there is a need to design and develop new, short-range, high-efficiency, high-purity goldBelongs to the vanadium preparation technology.
Disclosure of Invention
The invention provides a method for electrolyzing high-purity metal vanadium by using vanadium-carbon-oxygen solid solution anode molten salt. Vanadium trioxide and carbon or vanadium carbide are used as raw materials to prepare a vanadium-carbon-oxygen solid solution anode, electrolysis is carried out in alkali metal chloride molten salt, vanadium element enters the molten salt as low-valent ions and migrates to a cathode region, electrochemical reduction is carried out to obtain metal vanadium which is deposited at the cathode, carbon and oxygen element are spontaneously discharged in the form of carbon monoxide or carbon dioxide, and no pollution is caused to a cathode product. No foreign metal impurities are introduced in the anode preparation process, and no anode mud residue is left after the electrolysis is finished.
In order to achieve the purpose, the technical scheme provided by the method is as follows:
a method for electrolyzing high-purity metal vanadium by vanadium-carbon-oxygen solid solution anode molten salt comprises the following steps:
(a) vanadium trioxide and carbon or vanadium trioxide and vanadium carbide powder are mixed according to the metering ratio of 1: 1-1: 5 or 1: 2-1: 8 respectively. And (3) performing compression molding on the mixture on a high-pressure powder molding tablet machine at the pressure of 50-150 MPa, and drying the sample in a vacuum drying oven for later use.
(b) Sintering the pressed sample at high temperature within the temperature range of 1200-1600 ℃ to form the soluble solid solution VC with metal conductivityxO1-x(x is more than 0 and less than 1) anode.
(c) Carrying out molten salt electrolysis in a corundum crucible under the protection of inert atmosphere by taking the prepared solid solution as an anode and molten alkali metal eutectic molten salt as electrolyte; after the furnace temperature is raised to 600-900 ℃, the anode and the cathode are immersed into the molten salt for electrolysis, and the concentration of the electrolyte is 0.2-0.8A/cm2The constant current density of (2) is electrolyzed for more than 15 h. And after the electrolysis is finished, lifting the anode and the cathode, stopping inert atmosphere protection after the furnace temperature is cooled to room temperature, taking out the cathode, separating a cathode product, treating for 10-150 min in water bath ultrasound, and respectively cleaning for not less than 3 times by using dilute hydrochloric acid and deionized water to obtain the metal vanadium with the purity of more than 99.6%.
Preferably, the cathode may be any one of a molybdenum sheet, a nickel sheet, and a stainless steel sheet.
Preferably, the temperature of the electrolytic furnace in the step (c) is controlled to be 600-900 ℃.
Preferably, the electrolyte molten salt may be one or more of sodium chloride, potassium chloride, cesium chloride, magnesium chloride, lithium chloride, calcium chloride, sodium fluoride, potassium fluoride, magnesium fluoride, lithium fluoride, calcium fluoride, and cesium fluoride.
Preferably, the current density of the electrolysis in the step (b) is 0.2-0.8A/cm2The electrolysis time is 15-20 h.
Compared with the prior art, the method has the following advantages:
(1) the method takes vanadium trioxide and carbon or vanadium trioxide and vanadium carbide as raw materials to prepare the soluble vanadium carbon oxygen solid solution anode, compared with a method for preparing a crude vanadium anode by a metal or nonmetal thermal reduction method, the method has the advantages that the process conditions and equipment requirements are more relaxed, no foreign metal impurities are introduced in the preparation process, and the purity of the metal vanadium obtained by subsequent electrolysis is higher;
(2) the method comprises the following steps of taking a soluble vanadium carbon oxygen solid solution as an anode, obtaining a metal vanadium product at a cathode, wherein the vanadium carbon oxygen anode as a raw material is separated from the cathode metal vanadium product by molten salt, and carbon and oxygen elements are spontaneously separated from the system in the form of carbon monoxide or carbon dioxide gas, so that impurity elements in the raw material cannot pollute the cathode product, and the purity of the metal vanadium is high;
(3) the method can directly prepare high-purity vanadium metal through molten salt electrolysis, does not need further refining and purification, has short process flow, simple and convenient operation, low energy consumption in the preparation process and no pollution, and is a green, short-range and high-efficiency method for preparing the vanadium metal.
Drawings
FIG. 1 shows the synthesized VCxO1-xXRD spectrum of solid solution;
FIG. 2 is an XRD spectrum of the electrolysis product;
FIG. 3 is a schematic diagram of an electrolytic product.
FIG. 4 is an SEM topography of the electrolysis product.
Detailed Description
For a more clear illustration of the invention, the following examples are given:
example 1:
taking V in mass fraction2O3And C powder with the mass ratio of 1:1 are mixed for 12h by using a planetary ball mill, the uniformly mixed raw materials are pressed into a sample with the diameter of 10mm multiplied by 10mm under the pressure of 90MPa, and then the sample is kept at the temperature of 1500 ℃ for 4h in a tube furnace under the protection of argon. The structure of the sample is shown in the attached figure I; NaCl and KCl eutectic salt are selected as electrolyte, a molybdenum sheet is selected as cathode, and the concentration of the electrolyte is 0.2A/cm at 750 DEG C2After the current density is electrolyzed for 15h, the cathode and the anode are lifted, after the furnace temperature is cooled to the room temperature, the cathode product is treated by ultrasonic for 80min, and then the metal vanadium with the purity of 99.6 percent is obtained after the cathode product is repeatedly washed for 6 times by dilute hydrochloric acid and deionized water.
Example 2:
taking V in mass fraction2O3And C powder with the mass ratio of 1:4 are mixed for 12h by using a planetary ball mill, the uniformly mixed raw materials are pressed into a sample with the diameter of 10mm multiplied by 10mm under the pressure of 100MPa, and then the sample is kept at 1600 ℃ for 4h in a tube furnace under the protection of argon. The structure of the sample is shown in the attached figure I; KCl and LiCl eutectic salt is selected as electrolyte, a nickel sheet is selected as cathode, and the concentration of the electrolyte is 0.4A/cm at 600 DEG C2After the current density is electrolyzed for 24h, the cathode and the anode are lifted, after the furnace temperature is cooled to the room temperature, the cathode product is treated by ultrasonic for 100min, and then the metal vanadium with the purity of 99.7 percent is obtained after the cathode product is repeatedly washed for 6 times by dilute hydrochloric acid and deionized water.
Example 3:
taking V in mass fraction2O3Mixing the VC powder and the powder with the mass ratio of 1:2 by using a planetary ball mill for 12 hours, pressing the uniformly mixed raw materials into a sample with the diameter of 10mm multiplied by 10mm under the pressure of 80MPa, and then preserving the heat of 1300 ℃ in a tube furnace under the protection of argon for 4 hours. The structure of the sample is shown in the attached figure I; selecting LiCl, KCl and CaCl2Eutectic salt as electrolyte, stainless steel sheet as cathode, and the temperature of the eutectic salt is 0.8A/cm at 700 deg.C2After the current density is electrolyzed for 20h, the cathode and the anode are lifted, after the furnace temperature is cooled to room temperature, the cathode product is treated by ultrasonic wave for 90min, and then the metal vanadium with the purity of 99.8 percent is obtained after the cathode product is repeatedly washed for 6 times by dilute hydrochloric acid and deionized water.
Example 4:
taking V in mass fraction2O3And VC powder in a mass ratio of 1:6,mixing for 12h by using a planetary ball mill, pressing the uniformly mixed raw materials into a sample with the diameter of 10mm multiplied by 10mm under the pressure of 150MPa, and then preserving heat for 4h at 1400 ℃ in a tube furnace protected by argon. The structure of the sample is shown in the attached figure I; selecting LiCl, NaCl and MgCl2Eutectic salt as electrolyte, nickel sheet as cathode, and the concentration of the eutectic salt is 0.5A/cm at 850 deg.C2After the current density is electrolyzed for 25h, the cathode and the anode are lifted, after the furnace temperature is cooled to room temperature, the cathode product is treated by ultrasonic wave for 120min, and then the metal vanadium with the purity of 99.7 percent is obtained after the cathode product is repeatedly washed for 6 times by dilute hydrochloric acid and deionized water.
Example 5:
taking V in mass fraction2O3Mixing the VC powder and the powder with the mass ratio of 1:8 by using a planetary ball mill for 12 hours, pressing the uniformly mixed raw materials into a sample with the diameter of 10mm multiplied by 10mm under the pressure of 120MPa, and then preserving the heat of 1200 ℃ for 4 hours in a tube furnace under the protection of argon. The structure of the sample is shown in the attached figure I; LiCl, CsCl and KCl eutectic salt are selected as electrolyte, a stainless steel sheet is selected as cathode, and the temperature is controlled at 900 ℃ and is 0.6A/cm2After the current density is electrolyzed for 18h, the cathode and the anode are lifted, after the furnace temperature is cooled to room temperature, the cathode product is treated by ultrasonic for 150min, and then the cathode product is repeatedly washed for 6 times by dilute hydrochloric acid and deionized water to obtain the vanadium metal with the purity of 99.8 percent.
It should be noted that, according to the above embodiments of the present invention, those skilled in the art can fully implement the full scope of the present invention as defined by the independent claims and the dependent claims, and implement the processes and methods as the above embodiments; and the invention has not been described in detail so as not to obscure the present invention.
The above description is only a part of the embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (6)
1. A method for electrolyzing high-purity metal vanadium by vanadium-carbon-oxygen solid solution anode molten salt is characterized by comprising the following steps:
(a) mixing vanadium trioxide with carbon or vanadium trioxide withMixing vanadium carbide powder according to the metering ratio of 1: 1-1: 5 or 1: 2-1: 8, molding under the pressure of 50-150 MPa, and preparing into conductive VC within the temperature range of 1200-1600 DEG CxO1-x(0 < x < 1) solid solution;
(b) by VCxO1-xThe solid solution is a soluble anode, and the VC is added at 500-1000 DEG CxO1-xImmersing the anode and the cathode into alkali metal or alkaline earth metal chloride or fluoride molten salt at a ratio of 0.1-1.0A/cm2Electrolyzing for 10-25 h at constant current, wherein the vanadium in the anode of the solid solution is V in the electrolytic process2+、V3+Electrochemically dissolving low-valence ions into molten salt, transferring the low-valence ions to a cathode for electrochemical reduction to obtain high-purity vanadium metal, and spontaneously discharging carbon and oxygen in a solid solution anode in a gaseous form of carbon monoxide or carbon dioxide;
(c) and after the electrolysis is finished, lifting the anode and the cathode, cooling the furnace to room temperature, taking out the cathode, separating a cathode product, performing water bath ultrasonic treatment for 10-120 min, and respectively cleaning with dilute hydrochloric acid and deionized water for not less than 3 times to obtain the metal vanadium with the purity of more than 99.6%.
2. The method for electrolyzing high-purity metal vanadium through the vanadium-carbon-oxygen solid solution anode molten salt according to claim 1, wherein the electrolysis temperature in the step (b) is 600-900 ℃.
3. The method for electrolyzing high-purity vanadium metal through vanadium-carbon-oxygen solid solution anode molten salt as claimed in claim 1, wherein the cathode is any one of molybdenum sheet, nickel sheet and stainless steel sheet.
4. The method for electrolyzing high-purity metal vanadium through the vanadium-carbon-oxygen solid solution anode molten salt according to claim 1, wherein the electrolyte molten salt is one or more of sodium chloride, potassium chloride, cesium chloride, magnesium chloride, lithium chloride, calcium chloride, sodium fluoride, potassium fluoride, magnesium fluoride, lithium fluoride, calcium fluoride and cesium fluoride.
5. According to the claimsThe method for electrolyzing high-purity metal vanadium by the vanadium-carbon-oxygen solid solution anode molten salt in the step 1 is characterized in that the range of the electrolysis current density in the step (b) is as follows: 0.2 to 0.8A/cm2。
6. The method for electrolyzing high-purity metal vanadium through the vanadium-carbon-oxygen solid solution anode molten salt according to claim 1, wherein the electrolysis time in the step (b) is 15-20 h.
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