CN110699561B - Method for producing high-purity metal vanadium by adopting directional solidification - Google Patents
Method for producing high-purity metal vanadium by adopting directional solidification Download PDFInfo
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- CN110699561B CN110699561B CN201911101724.4A CN201911101724A CN110699561B CN 110699561 B CN110699561 B CN 110699561B CN 201911101724 A CN201911101724 A CN 201911101724A CN 110699561 B CN110699561 B CN 110699561B
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 81
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 63
- 239000002184 metal Substances 0.000 title claims abstract description 63
- 238000007711 solidification Methods 0.000 title claims abstract description 62
- 230000008023 solidification Effects 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 33
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 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 claims abstract description 18
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 18
- 238000002386 leaching Methods 0.000 claims abstract description 16
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012043 crude product Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical group [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003723 Smelting Methods 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 9
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 230000006698 induction Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 206010024769 Local reaction Diseases 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- PTXMVOUNAHFTFC-UHFFFAOYSA-N alumane;vanadium Chemical compound [AlH3].[V] PTXMVOUNAHFTFC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
-
- 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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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for producing high-purity metal vanadium by adopting directional solidification, which belongs to the technical field of vanadium metal smelting and comprises the following steps: heating a directional solidification furnace to 700-800 ℃, adding vanadium oxide for melting, feeding magnesium-aluminum alloy wires after the vanadium oxide is completely melted, starting directional solidification, stopping wire feeding and heating after the vanadium oxide is completely reacted, separating to obtain a vanadium crude product after a sample is cooled to room temperature, crushing the vanadium crude product, and leaching with dilute hydrochloric acid to obtain the high-purity vanadium metal. The invention takes vanadium oxide as raw material and magnesium-aluminum alloy Mg4Al3The reducing agent reduces the reaction temperature and obviously reduces the energy consumption; the production and separation processes are carried out simultaneously, so that the working procedures are reduced, and the production efficiency is improved; the purity of the prepared vanadium metal is higher than 98%.
Description
Technical Field
The invention belongs to the technical field of vanadium metal smelting, and particularly relates to a method for producing high-purity vanadium metal by adopting directional solidification.
Background
Vanadium is a silver gray lustrous metal with a density of 6.1g/cm3The melting point is 1890 ℃, the boiling point is 3000 ℃, the total content in the crust is arranged at the 22 th site of the metal, the metal is a high-melting-point rare metal, the metal is mainly intergrowth with other metal ores, and no independent vanadium ore is found so far. Vanadium is used as a valuable strategic resource and is widely applied to the fields of automobiles, aerospace, railways, bridges, fusion reactor vessels and the like.
The existing production method of metal vanadium mainly comprises the following steps: vacuum carbothermic method, silicothermic method, thermal decomposition method of vanadium nitride, stepwise reduction method, metallothermic method, etc. Among them, the metallothermic reduction method has attracted much attention because the reaction itself generates a lot of heat, and the required starting temperature is low, and the product purity is high. The reaction of the metallothermic reduction of the oxide is the basic displacement reaction, the principle of the choice of the reductant metal being that its standard formation free enthalpy is lower than that of the reduced metal oxide, and suitable elements for oxide reduction are silicon, magnesium, aluminium and calcium. Although the standard enthalpy of formation of lithium and beryllium oxides is low, the production of metallic lithium and beryllium is difficult and the cost of using it as a metallic reducing agent can be quite high. Silicon is not an ideal reducing agent in most cases because it has a strong tendency to form stable metal silicides and the problem of silicon removal is not easily solved. Because magnesium oxide has a high melting point, the heat released by the reaction of magnesium and metal oxide is generally insufficient to form solid metal; meanwhile, since magnesium boils at a lower temperature than calcium and aluminum, a closed vessel must be used to prevent loss of magnesium, which further limits the range of application of the magnesiothermic reduction process. Compared with the aluminothermic reduction method, the calthermic reduction method is not superior at present, and the main reasons are as follows: first, the reaction needs to be carried out in a closed vessel, with its inherent limitations on scale-up; second, calcium in its pure state is relatively expensive compared to aluminum. The aluminothermic process for producing pure vanadium metal generally comprises the steps of firstly carrying out aluminothermic reduction on vanadium oxide to generate vanadium-aluminum alloy, optionally carrying out reduction reaction in an open heat-resistant container, then carrying out high-temperature vacuum aluminum removal and electron beam melting on the vanadium-aluminum alloy to remove other residual impurities to obtain the pure vanadium metal, but the vacuum aluminum removal process needs a large amount of energy.
Disclosure of Invention
The invention aims to provide a method for producing high-purity vanadium metal by adopting directional solidification, which comprises the following steps:
heating a directional solidification furnace to 700-800 ℃, adding vanadium oxide for melting, feeding magnesium-aluminum alloy wires after the vanadium oxide is completely melted, starting directional solidification, stopping wire feeding and heating after the vanadium oxide is completely reacted, separating to obtain a vanadium crude product after a sample is cooled to room temperature, crushing the vanadium crude product, and leaching with dilute hydrochloric acid to obtain the high-purity vanadium metal.
In the method for producing high-purity vanadium metal by adopting directional solidification, the vanadium oxide is vanadium trioxide and/or vanadium pentoxide; and the protective gas in the directional solidification furnace is argon.
The method for producing the high-purity vanadium metal by adopting the directional solidification comprises the following steps that the temperature of a directional solidification furnace is 750-800 ℃; preferably, the temperature of the directional solidification furnace is 750 ℃.
Wherein, in the method for producing high-purity vanadium metal by adopting directional solidification, the weight percentage of aluminum in the magnesium-aluminum alloy wire is 40-60 percent; preferably, the magnesium-aluminum alloy wires are Mg4Al3Alloy wire with diameter of 3mm and density of 2.1g/cm3The linear density was 0.148 g/cm.
The method for producing high-purity vanadium metal by adopting directional solidification is characterized in that the wire feeding speed of the magnesium-aluminum alloy wire is 0.4-0.5 cm/min; preferably, the wire feeding speed of the magnesium-aluminum alloy wires is 0.43 cm/min.
According to the method for producing high-purity vanadium metal by adopting directional solidification, the wire feeding time of the magnesium-aluminum alloy wire is 2-6 hours.
According to the method for producing high-purity vanadium metal by adopting directional solidification, the wire feeding time of the magnesium-aluminum alloy wire is 2.2-3.6 hours.
According to the method for producing the high-purity vanadium metal by adopting the directional solidification, the reaction time of vanadium trioxide and the magnesium-aluminum alloy wire is 2.2-2.6 hours, and the reaction time of vanadium pentoxide and the magnesium-aluminum alloy wire is 3-3.6 hours.
The method for producing high-purity vanadium metal by adopting directional solidification is characterized by comprising the following steps: the directional solidification speed is 10-20 mm/h; preferably, the speed of the directional solidification is 10 mm/h; the diameter of the alloy cylindrical bar blank obtained after solidification is 20-30 mm; preferably 24 mm.
In the method for producing high-purity metal vanadium by adopting directional solidification, the separation refers to cutting and separating a vanadium crude product from a sample after observing the height of vanadium at the bottom of the sample; the crushing refers to crushing the crude vanadium product to 80-150 meshes; the concentration of the dilute sulfuric acid is 5-8 mol/L.
The invention has the beneficial effects that:
the invention takes vanadium oxide as a raw material,magnesium-aluminum alloy Mg4Al3The reducing agent reduces the reaction temperature and obviously reduces the energy consumption; the production and separation processes are carried out simultaneously, so that the working procedures are reduced, and the production efficiency is improved; the purity of the prepared vanadium metal is higher than 98%.
Detailed Description
Specifically, the method for producing high-purity vanadium metal by adopting directional solidification comprises the following steps:
heating a directional solidification furnace to 700-800 ℃, adding vanadium oxide for melting, feeding magnesium-aluminum alloy wires after the vanadium oxide is completely melted, starting directional solidification, stopping wire feeding and heating after the vanadium oxide is completely reacted, separating to obtain a vanadium crude product after a sample is cooled to room temperature, crushing the vanadium crude product, and leaching with dilute hydrochloric acid to obtain the high-purity vanadium metal.
In the process of the present invention, if the reaction temperature is too low, V2O5Not yet melted or too viscous, which would result in a reduced yield; if the reaction temperature is too high, energy loss is caused, and in addition, due to a large amount of exothermic reaction, magnesium volatilization can be caused if the reaction temperature is too high; therefore, the reaction temperature is set to be 700-800 ℃. In order to enable the purity of the prepared vanadium metal to be higher, the reaction temperature is set to be 750-800 ℃. Because the purity of the vanadium metal is not obviously improved due to too high temperature, the reaction temperature is set to 750 ℃ in consideration of comprehensive energy consumption.
If the content of aluminum in the magnesium-aluminum alloy used by the invention is too high, the local reaction temperature is too high, and alpha-Al is easily generated2O3If alpha-Al2O3Mixing into vanadium is not beneficial to separation; if the content of aluminum is too low, a high content of magnesium is easily volatilized due to a local reaction temperature which may be greater than the boiling point of magnesium, resulting in loss of magnesium. Therefore, the weight percentage of aluminum in the magnesium-aluminum alloy wire is 40-60 percent; preferably, the magnesium-aluminum alloy wires are Mg4Al3Alloy wire with diameter of 3mm and density of 2.1g/cm3The linear density was 0.148 g/cm.
In the process of the invention, if Mg4Al3For feeding threadToo fast, will result in too violent reaction, produce too much heat, will also result in the final total amount of wire feeding to increase, Al added more will form alloy with V, difficult to separate; if the wire feeding speed is too slow, the production efficiency is reduced, and even V is caused in severe cases2O5Depositing; therefore, the present invention converts Mg4Al3The wire feeding speed is set to be 0.4-0.5 cm/min; preferably, said Mg4Al3The wire feeding speed of (2) was 0.43 cm/min.
In the method, the directional solidification speed is too low, so that the production efficiency is reduced, the production time is prolonged, and unnecessary energy consumption is caused; if the directional solidification speed is too high, the reaction between the magnesium-aluminum alloy and vanadium oxide is increased, the local temperature is too high, the volatilization of magnesium is increased, and meanwhile, alpha-Al which is difficult to dissolve in acid is easily generated2O3. Therefore, the speed of directional solidification is 10-20 mm/h; preferably, the speed of the directional solidification is 10 mm/h.
The purity analysis of the vanadium metal prepared by the method can adopt the method in YB/T5328-2010 and the method in YB/T4218-2010.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Mg used in the following examples4Al3The filament diameter of the filament is 3mm and the density is 2.1g/cm3The linear density is 0.148g/cm, and the aluminum-magnesium alloy is prepared by melting and drawing of Jisheng brand magnesium-aluminum alloy powder, wherein the magnesium-aluminum alloy powder is purchased from Hebei Jisheng aluminum powder Limited company, and then is prepared by substitute processing and drawing of aluminum processing companies in northwest of the middle aluminum group, and the processing technological parameters are as follows: the extrusion temperature is 350 ℃, the preheating temperature of the die is 350 ℃, the extrusion speed is 15mm/s, and the diameter of the outlet of the die is 3 mm.
The heating ring of the induction heating furnace used in the following embodiments is provided with a function of moving up and down, and when the heating ring moves up, the lower unheated part is equivalent to direct air cooling, and has a considerable temperature gradient, so that the function of directional solidification can be realized.
Example 1
(1) Selecting V2O520g of vanadium as a starting material, Mg4Al3The filaments are reducing agents.
(2) Firstly, V is firstly2O5Placing the crucible into a graphite crucible, and then placing the crucible into an induction heating furnace.
(3) Argon gas is introduced as protective atmosphere, and the temperature is raised to 800 ℃.
(4) To V2O5And (3) completely melting, feeding magnesium aluminum alloy wires at 0.43cm/min, starting directional solidification at the speed of 10mm/h, and obtaining an alloy cylindrical bar blank with the diameter of 24mm after solidification.
(5) After 3h, the wire feed was stopped and then the heating was stopped.
(6) After the sample had cooled to room temperature, it was cut in half along the longitudinal centerline and the height of the vanadium at the bottom was observed by color.
(7) And (5) cutting the sample along the high transverse direction in the step (6) to separate the vanadium-containing part.
(8) Crushing the separated metal into particles (80-150 meshes), leaching at room temperature by 6mol/L HCl twice, using 80mL of the metal for one time, wherein the leaching time is 1h, and filtering and drying after the leaching is finished to obtain the high-purity metal vanadium.
(9) The method in the standard YB/T5328-2009 is used for detecting the total vanadium content, and the conversion purity is 98.6%.
Example 2
(1) Selecting V2O520g of vanadium as a starting material, Mg4Al3The filaments are reducing agents.
(2) Firstly, V is firstly2O5Placing the crucible into a crucible, and then placing the crucible into an induction heating furnace.
(3) Argon is introduced as protective atmosphere, and the temperature is raised to 750 ℃.
(4) To V2O5And (3) completely melting, feeding magnesium aluminum alloy wires at 0.43cm/min, starting directional solidification at the speed of 10mm/h, and obtaining an alloy cylindrical bar blank with the diameter of 24mm after solidification.
(5) After 3h, the wire feed was stopped and then the heating was stopped.
(6) After the sample had cooled to room temperature, it was cut in half along the longitudinal centerline and the height of the vanadium at the bottom was observed by color.
(7) And (5) cutting the sample along the high transverse direction in the step (6) to separate the vanadium-containing part.
(8) Crushing the separated metal into particles (80-150 meshes), leaching at room temperature by 6mol/L HCl twice, using 80mL of the metal for one time, wherein the leaching time is 1h, and filtering and drying after the leaching is finished to obtain the high-purity metal vanadium.
(9) The method in the standard YB/T5328-2009 is used for detecting the total vanadium content, and the conversion purity is 98.4%.
Example 3
(1) Selecting V2O520g of vanadium as a starting material, Mg4Al3The filaments are reducing agents.
(2) Firstly, V is firstly2O5Placing the crucible into a crucible, and then placing the crucible into an induction heating furnace.
(3) Argon gas is introduced as protective atmosphere, and the temperature is raised to 700 ℃.
(4) To V2O5And (3) completely melting, feeding magnesium aluminum alloy wires at 0.43cm/min, starting directional solidification at the speed of 10mm/h, and obtaining an alloy cylindrical bar blank with the diameter of 24mm after solidification.
(5) After 3h, the wire feed was stopped and then the heating was stopped.
(6) After the sample had cooled to room temperature, it was cut in half along the longitudinal centerline and the height of the vanadium at the bottom was observed by color.
(7) And (5) cutting the sample along the high transverse direction in the step (6) to separate the vanadium-containing part.
(8) Crushing the separated metal into particles (80-150 meshes), leaching at room temperature by 6mol/L HCl twice, using 80mL of the metal for one time, wherein the leaching time is 1h, and filtering and drying after the leaching is finished to obtain the high-purity metal vanadium.
(9) The method in the standard YB/T5328-2009 is used for detecting the total vanadium content, and the conversion purity is 90.2%.
Comparative example 1
(1) Selecting V2O520g of the vanadium raw material and an aluminum wire as a reducing agent.
(2) Firstly, V is firstly2O5Placing the crucible into a crucible, and then placing the crucible into an induction heating furnace.
(3) Argon is introduced as protective atmosphere, and the temperature is raised to 750 ℃.
(4) To V2O5And (3) completely melting, feeding an aluminum wire at 0.43cm/min, and simultaneously starting directional solidification at the speed of 10mm/h, wherein the diameter of the alloy cylindrical bar billet obtained after solidification is 24 mm.
(5) After 3h, the wire feed was stopped and then the heating was stopped.
(6) After the sample had cooled to room temperature, it was cut in half along the longitudinal centerline and the height of the vanadium at the bottom was observed by color.
(7) And (5) cutting the sample along the high transverse direction in the step (6) to separate the vanadium-containing part.
(8) Crushing the separated metal into particles (80-150 meshes), leaching at room temperature by 6mol/L HCl twice, using 80mL of the metal for one time, wherein the leaching time is 1h, and filtering and drying after the leaching is finished to obtain the high-purity metal vanadium.
(9) The method in the standard YB/T5328-2009 detects the amount of all-vanadium, and the reduced purity is 61.2 percent because of a large amount of alpha-Al2O3Mixed with vanadium and not dissolved by acid.
Claims (13)
1. The method for producing high-purity metal vanadium by adopting directional solidification is characterized by comprising the following steps:
heating a directional solidification furnace to 700-800 ℃, adding vanadium oxide for melting, feeding magnesium-aluminum alloy wires after the vanadium oxide is completely melted, starting directional solidification, stopping wire feeding and heating after the vanadium oxide is completely reacted, separating to obtain a vanadium crude product after a sample is cooled to room temperature, crushing the vanadium crude product, and leaching with dilute hydrochloric acid to obtain high-purity vanadium metal; the weight percentage of aluminum in the magnesium-aluminum alloy wire is 40-60%.
2. The method for producing high-purity vanadium metal by directional solidification according to claim 1, wherein: the vanadium oxide is vanadium trioxide and/or vanadium pentoxide; and the protective gas in the directional solidification furnace is argon.
3. The method for producing high-purity vanadium metal by directional solidification according to claim 1 or 2, wherein: the temperature of the directional solidification furnace is 750-800 ℃.
4. The method for producing high-purity vanadium metal by directional solidification according to claim 3, wherein: the temperature of the directional solidification furnace is 750 ℃.
5. The method for producing high-purity vanadium metal by directional solidification according to claim 2, wherein: the magnesium-aluminum alloy wire is Mg4Al3Alloy wire with diameter of 3mm and density of 2.1g/cm3The linear density was 0.148 g/cm.
6. The method for producing high-purity vanadium metal by directional solidification according to claim 5, wherein: the wire feeding speed of the magnesium-aluminum alloy wires is 0.4-0.5 cm/min.
7. The method for producing high-purity vanadium metal by directional solidification according to claim 6, wherein: the wire feeding speed of the magnesium-aluminum alloy wires is 0.43 cm/min.
8. The method for producing high-purity vanadium metal by directional solidification according to claim 2, wherein: the wire feeding time of the magnesium-aluminum alloy wires is 2-6 h.
9. The method for producing high-purity vanadium metal by directional solidification according to claim 8, wherein: the wire feeding time of the magnesium-aluminum alloy wires is 2.2-3.6 hours.
10. The method for producing high-purity vanadium metal by directional solidification according to claim 9, wherein: the reaction time of the vanadium trioxide and the magnesium-aluminum alloy wire is 2.2-2.6 hours, and the reaction time of the vanadium pentoxide and the magnesium-aluminum alloy wire is 3-3.6 hours.
11. The method for producing high-purity vanadium metal by directional solidification according to claim 1, wherein: the directional solidification speed is 10-20 mm/h; the diameter of the alloy cylindrical bar blank obtained after solidification is 20-30 mm.
12. The method for producing high purity vanadium metal by directional solidification according to claim 11, wherein: the directional solidification speed is 10 mm/h; the diameter of the alloy cylindrical bar billet obtained after solidification is 24 mm.
13. The method for producing high-purity vanadium metal by directional solidification according to claim 1, wherein: the separation refers to cutting and separating a crude vanadium product from a sample after observing the height of vanadium at the bottom of the sample; the crushing refers to crushing the crude vanadium product to 80-150 meshes; the concentration of the dilute hydrochloric acid is 5-8 mol/L.
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