CN114525552B - Device and method for preparing metal vanadium from vanadium alloy - Google Patents
Device and method for preparing metal vanadium from vanadium alloy Download PDFInfo
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- CN114525552B CN114525552B CN202210056650.2A CN202210056650A CN114525552B CN 114525552 B CN114525552 B CN 114525552B CN 202210056650 A CN202210056650 A CN 202210056650A CN 114525552 B CN114525552 B CN 114525552B
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- 229910000756 V alloy Inorganic materials 0.000 title claims abstract description 79
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 67
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 58
- 239000010431 corundum Substances 0.000 claims abstract description 58
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims abstract description 44
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims abstract description 42
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000460 chlorine Substances 0.000 claims abstract description 41
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 41
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 229910002804 graphite Inorganic materials 0.000 claims description 33
- 239000010439 graphite Substances 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 17
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 230000000149 penetrating effect Effects 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 3
- 238000003723 Smelting Methods 0.000 abstract description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 21
- 150000003839 salts Chemical class 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
Classifications
-
- 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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/04—Halides
-
- 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
-
- 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
-
- 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
- C25C7/06—Operating or servicing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention relates to the field of nonferrous metal smelting, in particular to a device and a method for preparing metal vanadium from vanadium alloy, wherein in the process of preparing vanadium from vanadium alloy, the interval between a second reactor and a first reactor is used for containing the vanadium alloy and chloride in a molten state; the corundum tube penetrates through the furnace cover and the second reactor through the first through hole and the second through hole, and chlorine is introduced into the material between the second reactor and the first reactor through the corundum tube, so that the material between the two reaction tanks can be kept in a fluidized state in the reaction process, and the chlorination rate of the vanadium alloy and the content of vanadium chloride obtained through preparation are obviously improved. In the electrolysis process of the second reactor, the first reactor can be prevented from being in direct contact with the cathode rod, namely the cathode and the anode, so that electrolysis failure is avoided, the cathode rod is protected, and electrolytic ions are only allowed to migrate to a deposition product on the cathode through the second through holes, so that other impurities are reduced to be in contact with the cathode, and the content of the impurities in the cathode is obviously reduced.
Description
Technical Field
The invention relates to the field of nonferrous metal smelting, in particular to a device and a method for preparing metal vanadium from vanadium alloy.
Background
The vanadium metal has the excellent characteristics of high melting point, corrosion resistance, good nuclear performance, easy processing deformation and the like, and is widely applied to the fields of superconductors, alloy materials, refractory materials, fuel additives, nuclear reactor protection materials and the like. At present, the preparation method of the metal vanadium mainly comprises a calorific reduction method and a magnesium chloride reduction method, the problems of difficult chlorine introduction, unstable chlorine, low content of prepared vanadium chloride and the like exist in the preparation process of an intermediate product vanadium chloride, meanwhile, the prepared vanadium contains interstitial elements of carbon, oxygen, nitrogen and hydrogen, has poor plasticity, and can obtain the metal vanadium with better purity after further purification and refining, and the preparation process is complex and has higher cost.
Disclosure of Invention
The device and the method for preparing the metal vanadium from the vanadium alloy are stable in chlorine introduction, high in chlorination rate of vanadium and high in purity of vanadium product.
In one aspect, the present invention provides an apparatus for preparing vanadium metal from a vanadium alloy, the apparatus for preparing vanadium chloride by reacting the vanadium alloy with chlorine and preparing vanadium metal by electrolysis of the vanadium chloride, the apparatus comprising:
the heating furnace comprises a furnace body and a furnace cover, wherein a first through hole communicated with the furnace body is formed in the furnace cover;
the device comprises a first reactor and a second reactor, wherein the second reactor is suitable for being arranged in the first reactor, a space for containing reaction materials is reserved between the second reactor and the first reactor when the second reactor is arranged in the first reactor, and a second through hole is formed in the bottom of the second reactor; and
the high-temperature-resistant pipe fitting and the cathode rod are suitable for penetrating through the first through hole, and the high-temperature-resistant pipe fitting is also suitable for penetrating through the second through hole;
when vanadium alloy reacts with chlorine to prepare vanadium chloride, the first reactor and the second reactor are arranged in the furnace body, vanadium alloy particles and chloride are filled in the first reactor and the second reactor at intervals and are heated and melted, the high-temperature-resistant pipe fitting penetrates through the first through hole and the second through hole, chlorine is introduced into the melted reactant through the high-temperature-resistant pipe fitting, and a molten mixture containing vanadium chloride is generated through reaction;
when vanadium chloride is electrolyzed to prepare vanadium metal, the cathode rod passes through the first through hole and is inserted into the molten mixture, the cathode rod is connected with the negative electrode of the power supply, the first reactor is connected with the positive electrode of the power supply to electrolyze vanadium chloride, and the vanadium metal is obtained on the cathode rod through an electrolysis process.
Preferably, the cathode rod is one of a molybdenum rod, an iron rod or an iron alloy rod.
Preferably, the diameter of the second through hole at the bottom of the second reactor is the same as the outer diameter of the high-temperature-resistant pipe fitting, and the diameter of the second through hole is 3-6 cm.
Preferably, the first reactor is a graphite crucible, the second reactor is a corundum crucible, and the high-temperature-resistant pipe fitting is a corundum pipe;
and a supporting ring is arranged around the inner wall of the first reactor, and the second reactor is limited on the supporting ring and forms a preset interval with the inner wall and the bottom of the first reactor.
Preferably, the distance between the side walls of the first reactor and the second reactor is controlled to be 2-5 cm, and the distance between the bottom and the first reactor is controlled to be 1-3 cm.
Preferably, the device further comprises an insulating sealing member sleeved on the high-temperature-resistant pipe fitting or the cathode rod and used for sealing between the high-temperature-resistant pipe fitting or the cathode rod and the furnace cover.
Compared with the prior art, the device for preparing the metal vanadium from the vanadium alloy has the following advantages:
in the process of preparing vanadium from vanadium alloy, the space between the first reactor and the second reactor is used for containing the vanadium alloy and chloride in a molten state; the high-temperature-resistant pipe fitting penetrates through the furnace cover and the second reactor through the first through hole and the second through hole, and chlorine is introduced into the material between the second reactor and the first reactor through the corundum pipe, so that the material between the two reactors can be kept in a fluidized state in the reaction process, and the chlorination rate of vanadium alloy and the content of vanadium chloride obtained through preparation are obviously improved.
In the electrolysis process of the second reactor provided by the invention, the first reactor can be prevented from being in direct contact with the cathode rod, namely the cathode and the anode, so that the electrolysis failure is avoided, the cathode rod is protected, the electrolysis ions are only allowed to migrate to the cathode through the second through holes to deposit products, other impurities are reduced to contact the cathode, and the content of the cathode impurities is obviously reduced. Meanwhile, the device is simple to operate and easy to control.
In another aspect, the present invention also provides a method for preparing metallic vanadium from a vanadium alloy, the method being performed by the apparatus, the method comprising the steps of:
adding vanadium alloy particles and chloride into a space between the first reactor and the second reactor, and heating and melting to obtain a first mixture, wherein the vanadium alloy particles can be immersed in the first mixture;
step two, introducing chlorine into the first mixture through the high-temperature-resistant pipe fitting passing through the first through hole and the second through hole to obtain a second mixture, wherein the second mixture contains vanadium chloride;
and thirdly, extracting the high-temperature-resistant pipe fitting, inserting the cathode rod into the second reactor through the second through hole, enabling the bottom of the cathode rod to be inserted into a second mixture flowing into the second reactor, connecting the cathode rod with a negative electrode of a power supply, connecting the first reactor with a positive electrode of the power supply, and carrying out electrolysis to obtain metal vanadium on the cathode rod.
According to the invention, on one hand, chlorine is introduced into the first mixture through the high-temperature-resistant pipe fitting, and the chlorine and the vanadium alloy form a fluidized bed in the molten salt, so that the contact area and the contact frequency of the chlorine and the vanadium alloy are increased, the utilization rate of the chlorine is improved, and the chlorination rate of the vanadium alloy in the molten salt and the content of vanadium chloride are obviously improved. On the other hand, in the electrolysis process, the first reactor is used as an anode, the cathode rod is inserted into molten salt in the second reactor, the second reactor can effectively protect the cathode rod, the cathode and anode are prevented from being in direct contact, the phenomenon of electrolysis failure is avoided, meanwhile, impurity ions in the molten salt are effectively prevented from contacting the cathode rod through the second reactor, vanadium ions obtained by electrolysis in the second mixture flow and migrate to the cathode rod through the second through holes of the second reactor, the content of impurities in vanadium is reduced, and the quality of vanadium is improved.
Preferably, in the first step, the vanadium content in the vanadium alloy is more than or equal to 90%, and the particle size of the vanadium alloy is 0.3-1.5 cm. The preferred vanadium alloy particle size can increase the contact area with chlorine and increase the reaction rate.
Preferably, in the first step, the chloride is at least one of lithium chloride, calcium chloride, sodium chloride or potassium chloride, and more preferably a mixture of potassium chloride and lithium chloride.
Preferably, in the second step, the pressure of introducing chlorine is 0.12-0.25 MPa, and the flow is 4.5-5.5 NL/min.
The optimized chlorine gas introducing pressure enables the chlorine gas to fully contact with the vanadium alloy, so that the utilization rate of the chlorine gas is increased, and the chlorination rate of the vanadium alloy is improved; the pressure and flow of the introduced chlorine are matched with the diameter of the second through hole, so that the utilization rate of the chlorine and the chlorination rate of the vanadium alloy are improved.
Preferably, in the third step, the distance between the bottom of the cathode rod and the second through hole of the second reactor is 2-3 cm.
The preferable distance not only ensures that the second reactor plays a role of protecting the cathode rod, but also ensures that the distance between the anode and the cathode is moderate, and ensures the reaction rate.
Preferably, in the third step, the voltage of the electrolysis is 0.6-1.5V.
Drawings
FIG. 1 is an apparatus for preparing vanadium chloride from vanadium alloy provided in example 1;
FIG. 2 is an apparatus for preparing vanadium metal from vanadium chloride provided in example 1;
reference numerals illustrate:
1-a heating furnace; 2-a first reactor; 3-a second reactor; 4-high temperature resistant pipe fittings; 4' -cathode rod; 5-insulating seal.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The traditional chloridizing method for producing vanadium chloride is to put metal vanadium or vanadium alloy into molten electrolyte, and introduce chlorine gas for reaction, so that the chlorine gas is difficult to introduce in the preparation process, the introduction of the chlorine gas is unstable, and the prepared vanadium chloride has low content, low utilization rate of the chlorine gas and the like. According to the invention, the position of the corundum tube is controlled to be constant, the pressure and the flow of the introduced chlorine gas are reasonably controlled, the stable reaction gas is ensured to be introduced into the molten salt, so that the chlorine gas and the vanadium alloy form a fixed fluidized bed in the molten salt, the chlorination rate of the vanadium alloy is improved, the corundum crucible plays a role in protecting the cathode and isolating, and meanwhile, the chlorine gas only flows out from the space between the two crucibles, and the utilization rate of the chlorine gas is improved. In addition, in the melting electrolysis process of the current preparation, the internal condition of the reaction device can not be seen under the vacuum condition, and the anode and cathode are easy to contact to cause electrolysis failure. In the electrolytic process, the corundum crucible provided by the invention can not only prevent the graphite crucible from being in direct contact with the cathode rod, namely the cathode and anode, avoid electrolytic failure and play a role in protecting the cathode rod, but also only allow electrolytic ions to migrate to a deposition product on the cathode through the second through holes, reduce other impurities to contact the cathode, obviously reduce the content of impurities in vanadium and improve the quality of vanadium.
The vanadium alloy used in the following examples mainly comprises the following components in percentage by mass: v93.5% and Al 5.6%.
Referring to fig. 1, an apparatus for preparing metal vanadium from a vanadium alloy according to the present invention is now described, wherein the apparatus is used for preparing vanadium chloride by reacting a vanadium alloy with chlorine gas and preparing metal vanadium by electrolyzing vanadium chloride, and comprises:
the heating furnace 1 comprises a furnace body and a furnace cover, wherein a first through hole communicated with the furnace body is formed in the furnace cover;
a first reactor 2 and a second reactor 3, wherein the second reactor 3 is suitable for being arranged in the first reactor 2, when the second reactor 3 is arranged in the first reactor 2, a space for containing reaction materials is reserved between the second reactor 3 and the first reactor 2, and a second through hole is arranged at the bottom of the second reactor 3; and
the high temperature resistant pipe fitting 4 and the cathode rod 4' are suitable for passing through the first through hole, and the high temperature resistant pipe fitting 4 is also suitable for passing through the second through hole;
when vanadium alloy reacts with chlorine to prepare vanadium chloride, the first reactor 2 and the second reactor 3 are placed in a furnace body, vanadium alloy particles and chloride are filled in the first reactor 2 and the second reactor 3 at intervals and are heated and melted, the high-temperature resistant pipe fitting 4 penetrates through the first through hole and the second through hole, chlorine is introduced into the melted reactant through the high-temperature resistant pipe fitting 4, and a molten mixture containing vanadium chloride is generated through reaction;
when vanadium chloride is electrolyzed to prepare vanadium metal, the cathode rod 4' passes through the first through hole and is inserted into the molten mixture, the cathode rod 4' is connected with the negative electrode of the power supply, the first reactor 2 is connected with the positive electrode of the power supply to electrolyze vanadium chloride, and the vanadium metal is obtained on the cathode rod 4 '.
The device for preparing the metal vanadium from the vanadium alloy provided by the invention has the following advantages:
during the preparation of vanadium from a vanadium alloy, the space between the first reactor 2 and the second reactor 3 is used to contain the vanadium alloy and the chloride in the molten state; the high-temperature resistant pipe fitting 4 penetrates through the furnace cover and the second reactor 3 through the first through hole and the second through hole, and chlorine is introduced into the material between the second reactor 3 and the first reactor 2 through the high-temperature resistant pipe fitting 4, so that the material between the two reactors can be kept in a fluidization state in the reaction process, and the chlorination rate of vanadium alloy and the content of vanadium chloride obtained through preparation are obviously improved.
In the electrolysis process of the second reactor 3 provided by the invention, the first reactor 2 can be prevented from being in direct contact with the cathode rod 4', namely the cathode and the anode, so that the electrolysis failure is avoided, the cathode rod 4' is protected, and the electrolysis ions are only allowed to migrate to a deposition product on the cathode through the second through holes, so that other impurities are reduced to contact the cathode, and the content of the cathode impurities is obviously reduced. Meanwhile, the device is simple to operate and easy to control.
As a specific embodiment, the cathode rod 4' is one of a molybdenum rod, an iron rod, and an iron alloy rod.
As a specific embodiment, the diameter of the second through hole at the bottom of the second reactor 3 is the same as the outer diameter of the high temperature resistant pipe fitting 4, wherein the diameter of the second through hole is 3-6 cm.
The diameter of the second through hole at the bottom of the second reactor 3 is controlled to be the same as the outer diameter of the high-temperature-resistant pipe fitting 4, so that chlorine can only flow out from between the first reactor 2 and the second reactor 3, a fluidization state is formed between the chlorine and the vanadium alloy in molten salt, the chlorine and the vanadium alloy are ensured to be fully contacted, the chlorination rate of the vanadium alloy is improved, meanwhile, the chlorine can be effectively prevented from flowing out from the second through hole of the second reactor 3, and the utilization rate of the chlorine is improved.
As a specific implementation mode, the first reactor 2 is a graphite crucible, the second reactor 3 is a corundum crucible, and the high-temperature-resistant pipe fitting 4 is a corundum pipe; a support ring is arranged around the inner wall of the first reactor 2, and the second reactor 3 is limited on the support ring and forms a preset interval with the inner wall and the bottom of the first reactor 2.
As a specific embodiment, the side wall spacing of the first reactor 2 and the second reactor 3 is controlled to be 2-5 cm, the bottom spacing is 1-3 cm, and the height of the first reactor 2 and the second reactor 3 is more than 20 cm.
If the sidewall spacing between the first reactor 2 and the second reactor 3 is too large, chlorine gas flows out from the side near the second reactor 3, so that the vanadium alloy far from the side of the second reactor 3 cannot contact and react with the chlorine gas, and the chlorination rate of the vanadium alloy is reduced. The bottom spacing can avoid the direct contact between the first reactor 2 and the second reactor 3, is beneficial to the outflow of chlorine from the second through holes, and forms a fluidized bed with vanadium alloy on two sides in molten salt.
As a specific embodiment, the device further comprises an insulating sealing member 5, wherein the insulating sealing member 5 is sleeved on the high-temperature-resistant pipe fitting 4 or the cathode rod 4', and is used for sealing between the high-temperature-resistant pipe fitting 4 or the cathode rod 4' and the furnace cover, and the insulating sealing member 5 is made of a graphite sealing gasket.
In summary, as one embodiment, the specific operation flow is as follows:
example 1:
the embodiment provides a device for preparing metal vanadium from vanadium alloy, which is used for preparing vanadium chloride by reacting the vanadium alloy with chlorine and preparing the metal vanadium by electrolyzing the vanadium chloride, and comprises the following components:
the heating furnace comprises a furnace body and a furnace cover, and a first through hole communicated with the furnace body is formed in the furnace cover;
the graphite crucible and the corundum crucible are characterized in that a supporting ring is arranged on the inner wall of the graphite crucible, the corundum crucible is arranged on the supporting ring, the distance between the corundum crucible and the side wall of the graphite crucible is controlled to be 3cm, the distance between the corundum crucible and the bottom is 2cm, the bottom of the corundum crucible is provided with a second through hole, specifically, the diameter of the graphite crucible is 18cm, the height of the corundum crucible is 22cm, the diameter of the corundum crucible is 12cm, and the height of the corundum crucible is 22cm; and
the corundum tube and the molybdenum rod are suitable for penetrating through the first through hole, and the corundum tube is also suitable for penetrating through the second through hole, wherein the outside diameters of the corundum tube and the second through hole are the same, and the outside diameter of the second through hole is 5cm;
the insulating sealing piece is sleeved on the corundum tube or the molybdenum rod and used for sealing between the corundum tube or the molybdenum rod and the furnace cover, and the insulating sealing piece is made of graphite.
When vanadium alloy reacts with chlorine to prepare vanadium chloride, the graphite crucible and the corundum crucible are arranged in the furnace body, vanadium alloy particles and chloride are filled in the graphite crucible and the corundum crucible at intervals, a corundum pipe penetrates through the first through hole and the second through hole, chlorine is introduced into the fused reactant through the corundum pipe, and the vanadium chloride is generated by reaction;
when vanadium chloride is electrolyzed to prepare vanadium metal, a molybdenum rod is inserted into the vanadium chloride through the first through hole, the distance between the bottom of the molybdenum rod and the second through hole of the corundum crucible is 3cm, the molybdenum rod is connected with the negative electrode of a power supply, the graphite crucible is connected with the positive electrode of the power supply to electrolyze the vanadium chloride, and the vanadium metal is obtained on the molybdenum rod.
The invention also provides a specific embodiment of a method for preparing metal vanadium from vanadium alloy, comprising the following steps:
example 2:
this example provides a method for preparing metallic vanadium from a vanadium alloy, using the apparatus of example 1, comprising the steps of:
step one, placing a graphite crucible into a heating furnace body, adding 200g of chloride into the graphite crucible, placing the corundum crucible into the graphite crucible, adding 200g of vanadium alloy particles and 800g of chloride between the graphite crucible and the corundum crucible, and heating and melting at 650 ℃ to obtain a first mixture, wherein the granularity of the vanadium alloy is 0.8-1.2 cm, and the mass ratio of the chloride is 1:1 and lithium chloride;
inserting a corundum tube into a second through hole of the corundum crucible, introducing chlorine into the first mixture through the corundum tube, controlling the pressure of the introduced chlorine to be 0.20MPa, the flow to be 5NL/min and the time to be 2.5h, and preparing a second mixture;
and thirdly, extracting the corundum tube, inserting the bottom of the molybdenum rod into a second mixture flowing into the corundum crucible for electrolysis, taking the molybdenum rod as a cathode, taking graphite as an anode, introducing 1V voltage under the protection of argon for melting electrolysis for 10 hours, and obtaining vanadium on the molybdenum rod.
The vanadium was washed with water to remove chloride, then treated with 2% hydrochloric acid, and detected and calculated to give a second mixture having a vanadium chloride content of 8.5% and a vanadium content of 99.26% by electrolysis.
Example 3:
this example provides a method for preparing metallic vanadium from a vanadium alloy, using the apparatus of example 1, comprising the steps of:
step one, placing a graphite crucible into a heating furnace body, adding 200g of chloride into the graphite crucible, placing the corundum crucible into the graphite crucible, adding 200g of vanadium alloy particles and 800g of chloride between the graphite crucible and the corundum crucible, and heating and melting at 630 ℃ to obtain a first mixture, wherein the granularity of the vanadium alloy is 0.8-1.2 cm, and the mass ratio of the chloride is 0.8:1 and sodium chloride;
inserting a corundum tube into a second through hole of the corundum crucible, introducing chlorine into the first mixture through the corundum tube, controlling the pressure of the introduced chlorine to be 0.15MPa, the flow to be 5.5NL/min and the time to be 2.5h, and preparing a second mixture;
and thirdly, extracting the corundum tube, inserting the bottom of the molybdenum rod into a second mixture flowing into the corundum crucible for electrolysis, taking the molybdenum rod as a cathode, taking graphite as an anode, introducing 1.2V voltage under the protection of argon for melting electrolysis for 10 hours, and obtaining vanadium on the molybdenum rod.
The vanadium was washed with water to remove chloride, then treated with 2% hydrochloric acid, and detected and calculated to give a second mixture having a vanadium chloride content of 9.3% and an electrolytic vanadium content of 99.44%.
Example 4:
this example provides a method for preparing metallic vanadium from a vanadium alloy, using the apparatus of example 1, comprising the steps of:
step one, placing a graphite crucible into a heating furnace body, adding 200g of chloride into the graphite crucible, placing the corundum crucible into the graphite crucible, adding 200g of vanadium alloy particles and 800g of chloride between the graphite crucible and the corundum crucible, and heating and melting at 660 ℃ to obtain a first mixture, wherein the granularity of the vanadium alloy is 1.0-1.5 cm, and the mass ratio of the chloride is 1:1 and lithium chloride;
inserting a corundum tube into a second through hole of the corundum crucible, introducing chlorine into the first mixture through the corundum tube, controlling the pressure of the introduced chlorine to be 0.25MPa, the flow to be 4.5NL/min and the time to be 2.5h, and preparing a second mixture;
and thirdly, extracting the corundum tube, inserting the bottom of the molybdenum rod into a second mixture flowing into the corundum crucible for electrolysis, taking the molybdenum rod as a cathode, taking graphite as an anode, introducing 0.8V voltage under the protection of argon for melting electrolysis for 10 hours, and obtaining vanadium on the molybdenum rod.
The vanadium is washed by water to remove chloride, then treated by 2% hydrochloric acid, and detected and calculated, the content of vanadium chloride in the molten salt of vanadium chloride in the embodiment is 8.1%, and the content of vanadium obtained by electrolysis is 99.18%.
Comparative example 1:
this comparative example replaces the corundum crucible with a second through hole with a corundum crucible without a through hole on the basis of example 2, and prepares metallic vanadium from vanadium alloy by using the device, comprising the following steps:
step one, placing a graphite crucible into a heating furnace body, adding 200g of chloride into the graphite crucible, placing a corundum crucible with no through hole at the bottom into the graphite crucible, adding 200g of vanadium alloy particles and 800g of chloride between the graphite crucible and the corundum crucible, and heating and melting at 650 ℃ to obtain a first mixture, wherein the granularity of the vanadium alloy is 0.8-1.2 cm, and the mass ratio of the chloride is 1:1 and lithium chloride;
inserting a corundum tube into the first mixture, introducing chlorine into the corundum tube, controlling the pressure of the introduced chlorine to be 0.20MPa, controlling the flow to be 5NL/min and the time to be 2.5 hours, and preparing a second mixture;
and step three, extracting the corundum tube, inserting the bottom of the molybdenum rod into the second mixture for electrolysis, taking the molybdenum rod as a cathode, taking graphite as an anode, introducing 1V voltage under the protection of argon for melting electrolysis for 10 hours, and obtaining vanadium on the molybdenum rod.
The vanadium was washed with water to remove chloride, then treated with 2% hydrochloric acid, and detected and calculated to give a second mixture having a vanadium chloride content of 4.1% and an electrolytic vanadium content of 96.5%.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (9)
1. An apparatus for preparing vanadium metal from a vanadium alloy, the apparatus being used for preparing vanadium chloride by reacting the vanadium alloy with chlorine and preparing vanadium metal by electrolyzing the vanadium chloride, the apparatus comprising:
the heating furnace comprises a furnace body and a furnace cover, wherein a first through hole communicated with the furnace body is formed in the furnace cover;
the device comprises a first reactor and a second reactor, wherein the second reactor is suitable for being arranged in the first reactor, a space for containing reaction materials is reserved between the second reactor and the first reactor when the second reactor is arranged in the first reactor, and a second through hole is formed in the bottom of the second reactor; and
the high-temperature-resistant pipe fitting and the cathode rod are suitable for penetrating through the first through hole, and the high-temperature-resistant pipe fitting is also suitable for penetrating through the second through hole;
when vanadium alloy reacts with chlorine to prepare vanadium chloride, the first reactor and the second reactor are arranged in the furnace body, vanadium alloy particles and chloride are filled in the first reactor and the second reactor at intervals and are heated and melted, the high-temperature-resistant pipe fitting penetrates through the first through hole and the second through hole, chlorine is introduced into the melted reactant through the high-temperature-resistant pipe fitting, and a molten mixture containing vanadium chloride is generated through reaction;
when vanadium chloride is electrolyzed to prepare vanadium metal, the cathode rod passes through the first through hole and is inserted into the molten mixture, the cathode rod is connected with the negative electrode of a power supply, the first reactor is connected with the positive electrode of the power supply to electrolyze the vanadium chloride, and the vanadium metal is obtained on the cathode rod through an electrolysis process;
the diameter of the second through hole at the bottom of the second reactor is the same as the outer diameter of the high-temperature-resistant pipe fitting, and the diameter of the second through hole is 3-6 cm.
2. The apparatus for preparing vanadium metal from vanadium alloy according to claim 1, wherein the first reactor is a graphite crucible, the second reactor is a corundum crucible, and the high temperature resistant pipe is a corundum pipe;
and a supporting ring is arranged around the inner wall of the first reactor, and the second reactor is limited on the supporting ring and forms a preset interval with the inner wall and the bottom of the first reactor.
3. The apparatus for preparing vanadium metal from vanadium alloy according to claim 1, wherein the sidewall interval between the first reactor and the second reactor inside is controlled to be 2-5 cm and the bottom interval is controlled to be 1-3 cm.
4. The apparatus for producing vanadium metal from vanadium alloy according to claim 1, further comprising an insulating seal fitted over the refractory tube or cathode rod for sealing between the refractory tube or cathode rod and the furnace cover.
5. A method for preparing metallic vanadium from a vanadium alloy, using the apparatus according to any one of claims 1 to 4, characterized in that it comprises the following steps:
adding vanadium alloy particles and chloride into a space between the first reactor and the second reactor, and heating and melting to obtain a first mixture, wherein the vanadium alloy particles can be immersed in the first mixture;
step two, introducing chlorine into the first mixture through the high-temperature-resistant pipe fitting passing through the first through hole and the second through hole to obtain a second mixture, wherein the second mixture contains vanadium chloride;
and thirdly, extracting the high-temperature-resistant pipe fitting, inserting the cathode rod into the second reactor through the second through hole, enabling the bottom of the cathode rod to be inserted into a second mixture flowing into the second reactor, connecting the cathode rod with a negative electrode of a power supply, connecting the first reactor with a positive electrode of the power supply, and carrying out electrolysis to obtain metal vanadium on the cathode rod.
6. The method for producing vanadium metal from vanadium alloy according to claim 5, wherein in the first step, the vanadium content in the vanadium alloy particles is not less than 90%, and the particle size of the vanadium alloy particles is 0.3 to 1.5cm.
7. The method of claim 5, wherein in step one, the chloride is at least one of lithium chloride, calcium chloride, sodium chloride, or potassium chloride.
8. The method for producing vanadium metal from vanadium alloy according to claim 5, wherein in the second step, the pressure of introducing chlorine gas is 0.12 to 0.25MPa.
9. The method for preparing vanadium metal from vanadium alloy according to claim 5, wherein in the third step, the distance between the bottom of the cathode rod and the second through hole of the second reactor is 2-3 cm; and/or
The voltage of the electrolysis is 0.6-1.5V.
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| JP2005048210A (en) * | 2003-07-30 | 2005-02-24 | Toshiba Corp | Method and apparatus for separating and recovering impurities in molten salt |
| CN101649471A (en) * | 2009-09-23 | 2010-02-17 | 攀钢集团研究院有限公司 | Method for producing high purity vanadium metal |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005048210A (en) * | 2003-07-30 | 2005-02-24 | Toshiba Corp | Method and apparatus for separating and recovering impurities in molten salt |
| CN101649471A (en) * | 2009-09-23 | 2010-02-17 | 攀钢集团研究院有限公司 | Method for producing high purity vanadium metal |
| 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 |
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| 熔融盐电解精炼法制取金属钒;朴昌林;《稀有金属》;第5-8页 * |
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