CN110629046B - Method and device for producing vanadium metal by carbothermic reduction - Google Patents
Method and device for producing vanadium metal by carbothermic reduction Download PDFInfo
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- CN110629046B CN110629046B CN201910982597.7A CN201910982597A CN110629046B CN 110629046 B CN110629046 B CN 110629046B CN 201910982597 A CN201910982597 A CN 201910982597A CN 110629046 B CN110629046 B CN 110629046B
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 79
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 60
- 239000002184 metal Substances 0.000 title claims abstract description 60
- 230000009467 reduction Effects 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 108
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 65
- 238000003723 Smelting Methods 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 34
- 239000001301 oxygen Substances 0.000 claims abstract description 34
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 33
- 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 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 27
- 238000007670 refining Methods 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 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 22
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 229910002090 carbon oxide Inorganic materials 0.000 claims abstract description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 42
- 239000010439 graphite Substances 0.000 claims description 42
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000003825 pressing Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- -1 vanadium oxide compound Chemical class 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 150000002927 oxygen compounds Chemical class 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- 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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/04—Refining by applying a vacuum
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method and a device for producing vanadium metal by carbon reduction, wherein the method comprises the following steps: (1) mixing vanadium oxide and carbon raw materials for reduction smelting to obtain low-valence vanadium oxide and/or low-valence vanadium carbide; (2) crushing the low-valence vanadium oxide and/or low-valence vanadium carbide obtained in the step (1), and detecting the contents of carbon and oxygen; (3) and (3) according to the test result of the step (2), mixing carbon or vanadium oxide, mixing to obtain a mixture, carrying out vacuum refining on the mixture, and cooling to obtain a metal vanadium product. The method and the device can reduce energy consumption, reduce refractory consumption and production cost, and have the advantages of simple process flow, less investment amount and less occupied area, and the purity of the produced pure metal vanadium can reach more than 98%.
Description
Technical Field
The invention belongs to the technical field of chemical metallurgy production of vanadium metal, relates to a method for producing vanadium metal, and particularly relates to a method and a device for producing vanadium metal by carbothermic reduction.
Background
Vanadium is an important alloying element, mainly used in the steel industry. The vanadium-containing steel has the advantages of high strength, high toughness, good wear resistance and the like, so the vanadium-containing steel is widely applied to industries such as machinery, automobiles, shipbuilding, electronic technology, railways, aviation, bridges, national defense industry and the like, in addition, the oxide of vanadium becomes one of the best catalysts in the chemical industry and is called chemical bread, and thus the vanadium is also an important strategic metal. The vanadium metal has the characteristics of ductility, hard quality, non-magnetism and the like; has the capability of resisting hydrochloric acid and sulfuric acid, and has better gas resistance, salt resistance and water corrosion resistance than most stainless steels.
The pure vanadium metal is generally produced by subjecting V to high pressure with potassium2O5Is reduced to obtain due to potassiumAre easily oxidized and dangerous; or reduction of V with coke2O5The obtained vanadium metal has low purity, and the vanadium metal obtained by carbon reduction is generally about 94 percent at present; or obtaining vanadium-aluminum alloy by using an aluminothermic reduction method, dealuminizing the vanadium-aluminum alloy at high temperature and in vacuum to obtain crude metal vanadium with the vanadium content of 94-97%, and mostly producing the high-purity metal vanadium by using an electronic vertical smelting method, wherein the electronic vertical smelting furnace is extremely high in price and high in cost due to small using amount; or the electrolytic method is used for producing the metal vanadium, the electrolytic process has more working procedures, complex process and more technical point control.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a method and a device for producing metal vanadium by carbothermic reduction, which can reduce energy consumption, refractory material consumption and production cost, and have the advantages of simple process flow, less investment amount, less occupied area and high purity of the produced pure metal vanadium up to more than 98 percent.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the objects of the present invention is to provide a method for producing vanadium metal by carbon reduction, which comprises the following steps:
(1) mixing vanadium oxide and carbon raw materials for reduction smelting to obtain low-valence vanadium oxide and/or low-valence vanadium carbide;
(2) crushing the low-valence vanadium oxide and/or low-valence vanadium carbide obtained in the step (1), and detecting the contents of carbon and oxygen;
(3) and (3) according to the test result of the step (2), mixing carbon or vanadium oxide, mixing to obtain a mixture, carrying out vacuum refining on the mixture, and cooling to obtain a metal vanadium product.
As a preferable technical scheme of the invention, the vanadium oxide compound in the step (1) is vanadium pentoxide.
Preferably, the particle size of the vanadium oxide compound in step (1) is 40 to 200 mesh, such as 50 mesh, 60 mesh, 70 mesh, 80 mesh, 90 mesh, 100 mesh or 110 mesh, but not limited to the recited values, and other values within the range are also applicable, preferably 80 to 120 mesh. The purity of the vanadium pentoxide is more than or equal to 99.5 wt%.
Preferably, the carbon raw material in the step (1) is graphite.
Preferably, the particle size of the carbon raw material in the step (1) is 80 to 300 meshes, such as 100 meshes, 120 meshes, 150 meshes, 180 meshes, 200 meshes or 250 meshes, but not limited to the recited values, and other values not recited in the range of the values are also applicable, and preferably 120 to 200 meshes. The purity of the graphite is more than or equal to 99.9 wt%;
preferably, the molar ratio of carbon element to oxygen element in the vanadium oxide compound and the carbon source in step (1) is 1.1-1.2: 1, such as 1.11:1, 1.12:1, 1.13:1, 1.14:1, 1.15:1, 1.16:1, 1.17:1, 1.18:1 or 1.19, but not limited to the recited values, and other values not recited in the range of values are also applicable.
As a preferred embodiment of the present invention, the degree of vacuum in the reduction smelting in the step (1) is not more than 10Pa, such as 9Pa, 8Pa, 5Pa, 2Pa, 1Pa, 0.5Pa or 0.1Pa, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the reduction smelting in the step (1) comprises three stages, wherein the smelting temperature in the first stage is 550-650 ℃, the smelting temperature in the second stage is 650-1100 ℃, and the smelting temperature in the third stage is 1100-1500 ℃.
The first stage may be at 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃ or 640 ℃, the second stage may be at 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ or 1000 ℃, and the third stage may be at 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃, 1400 ℃ or 1450 ℃, but not limited to the values listed above, and other values not listed above within the ranges of the values are also applicable.
In the invention, the specific method of the three steps of the reduction smelting in the step (1) comprises the following steps:
a: the vacuum degree is below 10 Pa; the heating rate is 4 ℃/min when the temperature is between room temperature and 550 ℃; 550 to 65The temperature rise process at 0 ℃ takes 1h, and V is within the temperature2O5Reducing and discharging gas; keeping the temperature at 650 ℃ for 1h, wherein V is in the process2O5Is completely reduced to V2O4；
b: the vacuum degree is below 1 Pa; the temperature rise rate is 4 ℃/min at 650-900 ℃; the temperature rise rate of 900-1100 ℃ is 2 ℃/min, gas is discharged in the process, so the temperature rise rate is slow, the gas is discharged, and the temperature is kept at 1100 ℃ for 30 min; the product is mainly V2O3；
c: the vacuum degree is below 0.1 Pa; the heating rate of 1100-1400 ℃ is 4 ℃/min; and preserving heat at 1400-1500 ℃, preferably 1450 ℃ for 2h to obtain the crude vanadium with vanadium content of 85-90% and oxygen as a main impurity.
Preferably, the mixed oxygen compound and carbon raw material are pressed into balls before the reduction smelting in the step (1). The mixing time is 2-6 h, and the preferable time is 4 h. The pressure used in the ball pressing process is 15-25 MPa, and preferably 20 MPa.
In a preferred embodiment of the present invention, the particle size of the crushed vanadium suboxides and/or vanadium subcarbides in step (2) is 40 to 200 mesh, such as 50 mesh, 60 mesh, 70 mesh, 80 mesh, 90 mesh, 100 mesh, or 110 mesh, but the invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
As a preferable technical scheme of the invention, the molar ratio of the carbon element to the oxygen element after the carbon or vanadium-oxygen compound is prepared in the step (3) is 1: 1.
In the invention, the content of the carbon element and the oxygen element detected in the step (2) is used for determining whether the raw material obtained after the reduction smelting in the step (1) is excessive in the carbon element or excessive in the oxygen element, and if the oxygen element is excessive, the carbon raw material is added for carbon matching operation, so that the excessive oxygen element is consumed; if the carbon element is excessive, the operation of preparing vanadium oxide is carried out, vanadium pentoxide or vanadium trioxide is added, and the redundant carbon element is consumed.
As a preferable technical scheme of the invention, the mixture obtained in the step (3) is pressed into tablets or balls before vacuum smelting.
In the invention, water or polyvinyl alcohol with the total mass of 1-1.5% is added as a binder before the mixture is made into tablets or pressed into balls in the step (3). The pressing pressure is 25-35 MPa, preferably 30 MPa.
In a preferred embodiment of the present invention, the temperature of the vacuum refining in the step (3) is 1700 to 1780 ℃, for example 1710 ℃, 1720 ℃, 1730 ℃, 1740 ℃, 1750 ℃, 1760 ℃, or 1770 ℃, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable. Preferably 1730-1760 ℃ and the heating rate is 4 ℃/min.
Preferably, the vacuum refining time in step (3) is 3 to 6 hours, such as 3.5 hours, 4 hours, 4.5 hours, 5 hours or 5.5 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the vacuum degree of the vacuum refining in the step (3) is not more than 0.1 Pa.
Preferably, the crushing in step (2) is performed under vacuum.
As a preferred technical scheme of the invention, the cooling method in the step (3) comprises natural cooling and/or inert atmosphere flow cooling.
Preferably, the inert atmosphere comprises any one or a combination of at least two of argon, helium or nitrogen.
Preferably, the target temperature for cooling in step (3) is 20 to 50 ℃, such as 25 ℃, 30 ℃, 35 ℃, 40 ℃ or 45 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
As a preferred technical scheme of the invention, the method for producing the vanadium metal by carbon reduction comprises the following steps:
(1) mixing vanadium pentoxide with the particle size of 40-200 meshes and graphite with the particle size of 80-300 meshes according to the molar ratio of carbon element to oxygen element of 1.1-1.2: 1, pressing the mixture into balls, and carrying out reduction smelting under the vacuum degree of not more than 10Pa, wherein the reduction smelting comprises three stages, the smelting temperature of the first stage is 550-650 ℃, the smelting temperature of the second stage is 650-1100 ℃, and the smelting temperature of the third stage is 1100-1500 ℃, so that low-valence vanadium oxide and/or low-valence vanadium carbide are obtained;
(2) crushing the low-valence vanadium oxide and/or low-valence vanadium carbide obtained in the step (1) to 40-200 meshes, and detecting the content of carbon and oxygen;
(3) and (3) according to the test result of the step (2), mixing carbon or vanadium-oxygen compound until the molar ratio of the carbon element to the oxygen element is 1:1, mixing to obtain a mixture, pressing the obtained mixture into tablets or balls, and carrying out vacuum refining on the mixture under the vacuum degree of not more than 0.1Pa, wherein the temperature of the vacuum refining is 1700-1780 ℃, the time is 3-6 h, and naturally cooling and/or cooling in inert atmosphere flow to 20-50 ℃ to obtain a metal vanadium product.
The second purpose of the invention is to provide a device used in the method for producing vanadium metal by carbon reduction, wherein the device is a crucible used for reduction smelting in the step (1) and vacuum refining in the step (3), the crucible comprises a graphite drum and a graphite crucible, at least one of two openings of the graphite drum is provided with an inner interface, an opening of the graphite crucible is provided with an outer interface, and the graphite drum and the graphite crucible are connected with the outer interface through the inner interface.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the invention provides a method for producing vanadium metal by carbon reduction, which is precisely controlled in the temperature rise process, is beneficial to reducing impurities in the product, and the content of vanadium in the product can reach 99.29 percent to the maximum;
(2) the invention provides a method for producing vanadium metal by carbon reduction, wherein raw materials and equipment are common materials, local materials are favorably obtained, the carbon-oxygen ratio is low in the batching process, the main reason is that a crucible is made of graphite material, a small amount of reaction is carried out during secondary reduction, and vanadium oxide does not participate in the reaction during primary reduction;
(3) the invention provides a device for producing vanadium metal by carbon reduction, which is an improvement on a graphite crucible, and has the advantages of recycling and saving resources.
Drawings
FIG. 1 is a schematic structural diagram of a crucible for producing vanadium metal by carbon reduction provided by the invention;
in the figure: 1-graphite barrel, 2-inner interface of graphite barrel, 3-outer interface of graphite crucible, 4-graphite crucible.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
the structure of the crucible used in the embodiment of the invention is shown in fig. 1, the crucible comprises a graphite drum 1 and a graphite crucible 4, an inner interface 2 is arranged at least one of two openings of the graphite drum 1, an outer interface 3 is arranged at the opening of the graphite crucible 4, and the graphite drum 1 and the graphite crucible 4 are connected through the inner interface 2 and the outer interface 3.
Example 1
The embodiment provides a method for producing vanadium metal by carbon reduction, which comprises the following steps:
(1) mixing vanadium pentoxide with the granularity of 40 meshes and graphite with the granularity of 80 meshes according to the molar ratio of carbon element to oxygen element of 1.1:1, pressing the mixture into balls, and carrying out reduction smelting to obtain low-valence vanadium oxide or low-valence vanadium carbide;
(2) crushing the low-valence vanadium oxide and/or low-valence vanadium carbide obtained in the step (1) to 40 meshes, and detecting the contents of carbon and oxygen;
(3) and (3) according to the test result of the step (2), using graphite to prepare carbon until the molar ratio of the carbon element to the oxygen element is 1:1, mixing to obtain a mixture, pressing the obtained mixture into balls, and carrying out vacuum refining on the mixture under the vacuum degree of 0.1Pa, wherein the temperature of the vacuum refining is 1700 ℃, the heating rate is 4 ℃/min, and the time is 6h, and naturally cooling to 20 ℃ to obtain the metal vanadium product.
The vanadium content in the finally prepared metal vanadium product is 99.12%.
Example 2
The embodiment provides a method for producing vanadium metal by carbon reduction, which comprises the following steps:
(1) mixing vanadium pentoxide with the granularity of 200 meshes and graphite with the granularity of 300 meshes according to the molar ratio of carbon element to oxygen element of 1.2:1, pressing the mixture into balls, and carrying out reduction smelting to obtain low-valence vanadium carbide or low-valence vanadium carbide;
(2) crushing the low-valence vanadium oxide and/or low-valence vanadium carbide obtained in the step (1) to 200 meshes, and detecting the contents of carbon and oxygen;
(3) and (3) according to the test result of the step (2), preparing vanadium pentoxide until the molar ratio of the carbon element to the oxygen element is 1:1, mixing to obtain a mixture, pressing the obtained mixture into balls, carrying out vacuum refining on the mixture under the vacuum degree of 0.1Pa, wherein the temperature of the vacuum refining is 1780 ℃, the heating rate is 4 ℃/min, the time is 3h, and carrying out argon flowing cooling to 50 ℃ to obtain a metal vanadium product.
The vanadium content of the finally prepared metal vanadium product is 99.03%.
Example 3
The embodiment provides a method for producing vanadium metal by carbon reduction, which comprises the following steps:
(1) mixing vanadium pentoxide with the granularity of 80 meshes and graphite with the granularity of 120 meshes according to the molar ratio of carbon element to oxygen element of 1.15:1, pressing the mixture into balls, and carrying out reduction smelting to obtain low-valence vanadium oxide or low-valence vanadium carbide;
(2) crushing the low-valence vanadium oxide and/or low-valence vanadium carbide obtained in the step (1) to 50 meshes, and detecting the contents of carbon and oxygen;
(3) and (3) according to the test result of the step (2), preparing vanadium pentoxide until the molar ratio of the carbon element to the oxygen element is 1:1, mixing to obtain a mixture, pressing the obtained mixture into balls, carrying out vacuum refining on the mixture under the vacuum degree of 0.1Pa, wherein the temperature of the vacuum refining is 1730 ℃, the heating rate is 4 ℃/min, the time is 5h, and carrying out argon flow cooling to 50 ℃ to obtain a metal vanadium product.
The vanadium content of the finally prepared metal vanadium product is 99.08 percent.
Example 4
The embodiment provides a method for producing vanadium metal by carbon reduction, which comprises the following steps:
(1) mixing vanadium pentoxide with the granularity of 120 meshes and graphite with the granularity of 200 meshes according to the molar ratio of carbon element to oxygen element of 1.18:1, pressing the mixture into balls, and carrying out reduction smelting to obtain low-valence vanadium oxide or low-valence vanadium carbide;
(2) crushing the low-valence vanadium oxide and/or low-valence vanadium carbide obtained in the step (1) to 100 meshes, and detecting the contents of carbon and oxygen;
(3) and (3) according to the test result of the step (2), using graphite to prepare carbon until the molar ratio of the carbon element to the oxygen element is 1:1, mixing to obtain a mixture, pressing the obtained mixture into balls, and carrying out vacuum refining on the mixture under the vacuum degree of 0.1Pa, wherein the temperature of the vacuum refining is 1760 ℃, the heating rate is 4 ℃/min, and the time is 4h, and naturally cooling to 20 ℃ to obtain the metal vanadium product.
The vanadium content in the finally prepared metal vanadium product is 99.24%.
Example 5
The embodiment provides a method for producing vanadium metal by carbon reduction, which comprises the following steps:
(1) mixing vanadium pentoxide with the granularity of 100 meshes and graphite with the granularity of 150 meshes according to the molar ratio of carbon element to oxygen element of 1.18:1, pressing the mixture into balls, and carrying out reduction smelting to obtain low-valence vanadium oxide or low-valence vanadium carbide;
(2) crushing the low-valence vanadium oxide and/or low-valence vanadium carbide obtained in the step (1) to 100 meshes, and detecting the contents of carbon and oxygen;
(3) and (3) according to the test result of the step (2), using graphite to carry out carbon matching until the molar ratio of the carbon element to the oxygen element is 1:1, mixing to obtain a mixture, pressing the obtained mixture into balls, carrying out vacuum refining on the mixture under the vacuum degree of 0.1Pa, wherein the temperature of the vacuum refining is 1750 ℃, the heating rate is 4 ℃/min, and the time is 4.5h, and naturally cooling to 25 ℃ to obtain the metal vanadium product.
The vanadium content of the finally prepared metal vanadium product is 99.29%.
In the embodiment 1-5 of the present invention, the reduction smelting method in step (1) includes:
a: the vacuum degree is 10 Pa; the heating rate is 4 ℃/min when the temperature is between room temperature and 550 ℃; the temperature rise process at 550-650 ℃ takes 1h, and the temperature is kept at 650 ℃ for 1 h;
b: the vacuum degree is 1Pa, the heating rate of 650-900 ℃ is 4 ℃/min, the heating rate of 900-1100 ℃ is 2 ℃/min, and the temperature is kept at 1100 ℃ for 30 min;
c: the vacuum degree is 0.1Pa, the heating rate of 1100 ℃ to 1400 ℃ is 4 ℃/h, and the temperature is kept for 2h at 1450 ℃ to obtain the crude vanadium.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (17)
1. A method for producing vanadium metal by carbothermic reduction, said method comprising the steps of:
(1) mixing vanadium oxide and carbon raw materials for reduction smelting to obtain low-valence vanadium oxide and/or low-valence vanadium carbide;
(2) crushing the low-valence vanadium oxide and/or low-valence vanadium carbide obtained in the step (1), and detecting the contents of carbon and oxygen;
(3) according to the test result of the step (2), mixing carbon or vanadium oxide, mixing to obtain a mixture, carrying out vacuum refining on the mixture, and cooling to obtain a metal vanadium product;
the reduction smelting in the step (1) comprises three stages, wherein the smelting temperature in the first stage is 550-650 ℃, the smelting temperature in the second stage is 650-1100 ℃, and the smelting temperature in the third stage is 1100-1500 ℃;
the temperature of the vacuum refining in the step (3) is 1700-1780 ℃;
the heating rate of the vacuum refining in the step (3) is 4 ℃/min;
the particle size of the crushed low-valence vanadium oxide and/or low-valence vanadium carbide in the step (2) is 40-200 meshes;
the crushing in the step (2) is carried out under the vacuum condition;
the specific method of the three steps of the reduction smelting in the step (1) comprises the following steps:
a: the vacuum degree is below 10 Pa; the heating rate is 4 ℃/min when the temperature is between room temperature and 550 ℃; the temperature rise process at 550-650 ℃ takes 1h, and V is within the temperature2O5Reducing and discharging gas; keeping the temperature at 650 ℃ for 1h, wherein V is in the process2O5Is completely reduced to V2O4；
b: the vacuum degree is below 1 Pa; the temperature rise rate is 4 ℃/min at 650-900 ℃; the temperature rise rate of 900-1100 ℃ is 2 ℃/min, and gas is released in the process, soThe gas is discharged at a slow heating speed, and the temperature is kept at 1100 ℃ for 30 min; the product is mainly V2O3；
c: the vacuum degree is below 0.1 Pa; the heating rate of 1100-1400 ℃ is 4 ℃/min; and preserving the heat at 1400-1500 ℃ to obtain crude vanadium with vanadium content of 85-90% and oxygen as a main impurity;
the reduction smelting in the step (1) and the vacuum refining in the step (3) are carried out in a crucible, the crucible comprises a graphite barrel and a graphite crucible, an inner interface is arranged at least one of two openings of the graphite barrel, an outer interface is arranged at an opening of the graphite crucible, and the graphite barrel and the graphite crucible are connected through the inner interface and the outer interface.
2. The carbothermic method of producing vanadium metal of claim 1, wherein said vanadium oxide compound of step (1) is vanadium pentoxide.
3. The carbothermic production method of vanadium metal of claim 1, wherein the vanadium-oxygen compound of step (1) has a particle size of 40 to 200 mesh.
4. The method for producing vanadium metal by carbothermic reduction according to claim 1, wherein said carbon raw material of step (1) is graphite.
5. The method for producing vanadium metal by carbothermic reduction according to claim 1, wherein the particle size of the carbon raw material in step (1) is 80-300 mesh.
6. The carbothermic method for producing vanadium metal of claim 1, wherein the molar ratio of carbon to oxygen in the vanadium oxide compound and the carbon source in step (1) is 1.1-1.2: 1.
7. The carbothermic production method of vanadium metal of claim 1, wherein the degree of vacuum of said reduction smelting in step (1) is not more than 10 Pa.
8. The carbothermic method of producing vanadium metal of claim 1, wherein said combined oxygen compound and carbon feedstock is pressed into pellets prior to said reduction smelting in step (1).
9. The carbothermic method for producing vanadium metal of claim 1, wherein the molar ratio of carbon to oxygen in step (3) is 1: 1.
10. The carbothermic method for producing vanadium metal of claim 1, wherein said mixture obtained in step (3) is pressed into tablets or balls before said vacuum smelting.
11. The method for producing vanadium metal by carbothermic reduction according to claim 1, wherein the time for vacuum refining in step (3) is 3-6 hours.
12. The carbothermic method for producing metallic vanadium according to claim 1, wherein the vacuum degree of the vacuum refining of step (3) is not greater than 0.1 Pa.
13. The carbothermic method of producing vanadium metal of claim 1, wherein said cooling of step (3) comprises natural cooling and/or inert atmosphere flow cooling.
14. The carbothermic method of producing vanadium metal of claim 13, wherein said inert atmosphere comprises any one or a combination of at least two of argon, helium, or nitrogen.
15. The method for producing vanadium metal by carbothermic reduction according to claim 1, wherein the target temperature of the cooling in the step (3) is 20 to 50 ℃.
16. The method for producing vanadium metal by carbothermic reduction according to claim 1, wherein said method comprises the steps of:
(1) mixing vanadium pentoxide with the particle size of 40-200 meshes and graphite with the particle size of 80-300 meshes according to the molar ratio of carbon element to oxygen element of 1.1-1.2: 1, pressing the mixture into balls, and carrying out reduction smelting under the vacuum degree of not more than 10Pa, wherein the reduction smelting comprises three stages, the smelting temperature of the first stage is 550-650 ℃, the smelting temperature of the second stage is 650-1100 ℃, and the smelting temperature of the third stage is 1100-1500 ℃, so that low-valence vanadium oxide and/or low-valence vanadium carbide are obtained;
(2) crushing the low-valence vanadium oxide and/or low-valence vanadium carbide obtained in the step (1) to 40-200 meshes, and detecting the content of carbon and oxygen;
(3) and (3) according to the test result of the step (2), mixing carbon or vanadium-oxygen compound until the molar ratio of the carbon element to the oxygen element is 1:1, mixing to obtain a mixture, pressing the obtained mixture into tablets or balls, and carrying out vacuum refining on the mixture under the vacuum degree of not more than 0.1Pa, wherein the temperature of the vacuum refining is 1700-1780 ℃, the time is 3-6 h, and naturally cooling and/or cooling in inert atmosphere flow to 20-50 ℃ to obtain a metal vanadium product.
17. The device used in the method for producing vanadium metal by carbothermic reduction according to claim 1, wherein the device is a crucible used for the reduction smelting in the step (1) and the vacuum refining in the step (3), the crucible comprises a graphite barrel and a graphite crucible, at least one of two openings of the graphite barrel is provided with an inner interface, an opening of the graphite crucible is provided with an outer interface, and the graphite barrel and the graphite crucible are connected through the inner interface and the outer interface.
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| CA1099521A (en) * | 1976-04-09 | 1981-04-21 | Donald R. Macrae | Method of producing vanadium |
| CN203187775U (en) * | 2013-04-08 | 2013-09-11 | 阳光能源（青海）有限公司 | Detachable graphite crucible |
| WO2015081775A1 (en) * | 2013-12-05 | 2015-06-11 | 中国科学院过程工程研究所 | Method for comprehensively using high-chromium-content vanadium-titanium magnetite concentrate |
| CN205556853U (en) * | 2016-03-09 | 2016-09-07 | 徐州工业职业技术学院 | But ingot casting crucible of split |
| WO2018184067A1 (en) * | 2017-04-05 | 2018-10-11 | Tng Limited | A method for preparing a leach feed material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1099521A (en) * | 1976-04-09 | 1981-04-21 | Donald R. Macrae | Method of producing vanadium |
| CN203187775U (en) * | 2013-04-08 | 2013-09-11 | 阳光能源（青海）有限公司 | Detachable graphite crucible |
| WO2015081775A1 (en) * | 2013-12-05 | 2015-06-11 | 中国科学院过程工程研究所 | Method for comprehensively using high-chromium-content vanadium-titanium magnetite concentrate |
| CN205556853U (en) * | 2016-03-09 | 2016-09-07 | 徐州工业职业技术学院 | But ingot casting crucible of split |
| WO2018184067A1 (en) * | 2017-04-05 | 2018-10-11 | Tng Limited | A method for preparing a leach feed material |
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