CN112251619B - Preparation method and device of vanadium metal - Google Patents
Preparation method and device of vanadium metal Download PDFInfo
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- CN112251619B CN112251619B CN202010955649.4A CN202010955649A CN112251619B CN 112251619 B CN112251619 B CN 112251619B CN 202010955649 A CN202010955649 A CN 202010955649A CN 112251619 B CN112251619 B CN 112251619B
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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
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
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- 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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Abstract
The invention relates to the technical field of metal vanadium preparation, and particularly discloses a preparation method and device of metal vanadium. The preparation method of the metal vanadium comprises the steps of heating and dehydrating a vanadium source under a vacuum condition, heating to 700-1000 ℃ in a molten salt medium and an inert gas atmosphere for reduction reaction, and washing and drying a material obtained by the reaction to obtain the metal vanadium. The device used in the preparation method of the metal vanadium comprises a vacuum reactor, a vacuum pump and a microwave heater. The metal vanadium prepared by the preparation method provided by the invention has the advantages of extremely high purity, single phase and uniform and regular particles, meets the requirements of high purity vanadium required in special fields such as aerospace, missile and the like, has the advantages of low energy consumption, simple process and short time, and effectively reduces the production cost and the production period of the high purity vanadium.
Description
Technical Field
The invention relates to the technical field of metal vanadium preparation, in particular to a method and a device for preparing metal vanadium.
Background
Vanadium metal is an important resource for the refining of alloy steel. The vanadium is added into alloy steel, so that the alloy steel has excellent mechanical properties such as high temperature resistance, low temperature resistance, wear resistance, impact resistance and the like. Vanadium plays an important role in various special alloy steels, tool steels, and structural steels. The vanadium not only greatly improves the strength of the alloy steel, but also obviously improves the capability of bearing special environmental changes.
There are many processes for producing vanadium metal, mainly comprising: (1) vacuum carbothermal reduction; (2) a silicothermic reduction process; (3) a thermal decomposition method of vanadium nitride; (4) a step reduction method; (5) The metallothermic reduction of vanadium oxides or chlorides, such as aluminum reduction, calcium reduction, magnesium reduction, etc., is most commonly used with vanadium oxides. However, the preparation methods of the metal vanadium have the problems of large heat loss, poor uniformity and stability of material reaction in the preparation process, high impurity content, high hardness, poor mechanical processing performance, difficult operation of the preparation process, easy environmental pollution, complex process equipment, high preparation cost and the like.
Disclosure of Invention
Aiming at the problems of high energy consumption, poor uniformity and stability of material reaction in the preparation process, high impurity content of the obtained metal vanadium, complex preparation flow, environmental pollution and high cost of the traditional preparation method of the metal vanadium, the invention provides the preparation method and the device of the metal vanadium.
In order to achieve the above purpose, the embodiment of the invention adopts the following technical scheme:
the preparation method of the metal vanadium comprises the steps of heating and dehydrating a vanadium source under a vacuum condition, heating to 700-1000 ℃ in a molten salt medium and an inert gas atmosphere for reduction reaction, and washing and drying a material obtained by the reaction to obtain the metal vanadium;
the molten salt is alkaline earth metal halide molten salt or mixture molten salt of alkaline earth metal halide and alkali metal halide.
Compared with the prior art, the preparation method of the metal vanadium provided by the invention has the advantages that the vanadium source is dehydrated under the vacuum condition, and the vanadium source is reduced under the special molten salt system and temperature, so that the metal vanadium simple substance can be obtained in a short time, the purity of the obtained metal vanadium is extremely high, the phase is single, the particles are uniform and regular, and the requirements of high-purity vanadium required in the special fields of aerospace, missile and the like are met. The preparation method of the metal vanadium has the advantages of low energy consumption, simple process and instant synthesis, and effectively reduces the production cost and the production period of the high-purity vanadium.
Preferably, the vanadium source is at least one of vanadium oxide, vanadate and ammonium metavanadate, wherein the vanadium oxide can be selected from V 2 O 5 Or V 2 O 3 The vanadate may be calcium vanadate, sodium vanadate or ammonium vanadate.
Preferably, the molten salt is a calcium chloride molten salt.
Preferably, the molten salt is a mixture molten salt of sodium chloride and calcium chloride, and the mass ratio of the sodium chloride to the calcium chloride is 1:5-10.
Preferably, the mass of the vanadium source corresponds to 5-12% of the mass of the molten salt.
Preferably, the temperature of the heating dehydration is 200-500 ℃, the vacuum degree is minus 60 to minus 72mmHg, and the time is 2-4 hours.
Preferably, the heating rate is 20-120 ℃/min.
Preferably, the inert gas is argon.
Preferably, the pressure of the reduction reaction is 0.15-0.25MPa.
Preferably, the time of the reduction reaction is 4-8 hours.
Preferably, the heating and the warming are performed by means of microwave heating.
The heating reduction is carried out in a microwave heating mode, so that the efficiency of the reduction reaction can be further improved, the energy consumption is reduced, the uniformity of the reaction of each part of the reaction materials is increased, and the purity of the metal vanadium is further improved.
Preferably, the reduction is carried out by adding a metal reducing agent, which may be sodium, magnesium or aluminum.
Preferably, the reduction reaction is electrolytic reduction by adding graphene as an anode and a vanadium source as a cathode.
Preferably, the washing method is to wash the material obtained by the reaction with dilute hydrochloric acid, distilled water and alcohol in sequence and filter.
Preferably, the material obtained by the reaction is cooled to below 30 ℃ in inert gas and then subjected to the washing process.
The invention also provides a device for the preparation method of the metal vanadium, which comprises a vacuum reactor, a vacuum pump and a microwave heater; the vacuum reactor is used for containing materials required by the reaction; the vacuum pump is communicated with the vacuum reactor and used for controlling the vacuum degree in the vacuum reactor; the microwave heater is sleeved on the outer wall of the vacuum reactor and is used for controlling the temperature of materials required by the reaction in the vacuum reactor through microwave heating.
The specific flow of preparing the metal vanadium by the device used by the preparation method of the metal vanadium provided by the invention is as follows: after adding the vanadium source and the molten salt into the vacuum reactor for mixing, opening the vacuum pump to enable the vacuum reactor to reach a preset vacuum degree, and then opening the microwave heater to heat and dehydrate the vanadium source; and after the dehydration process is finished, introducing inert gas into the vacuum reactor, heating the vanadium source and the molten salt to 700-1000 ℃ through the microwave heater for reduction reaction, and washing and drying the material obtained by the reaction to obtain the metal vanadium.
Compared with the prior art, the device provided by the invention is sleeved with the microwave heater outside the vacuum reactor, and the temperature in the vacuum reactor is controlled in a microwave heating mode, so that the problem of uneven reaction of reaction materials caused by larger temperature control deviation in the reaction process is solved, the impurity content in the reacted metal vanadium is further reduced, the purity of the metal vanadium is further improved, the device has a simple structure, the dehydration and reduction process can be realized by one set of device, the operation is convenient, the microwave heating energy utilization rate can reach more than 90%, the energy consumption is low, and the environmental pollution is reduced.
Drawings
FIG. 1 is an SEM (scanning electron microscope) morphology diagram of vanadium metal obtained in example 1 of the present invention;
FIG. 2 is an X-ray diffraction pattern of vanadium metal obtained in example 1;
FIG. 3 is a SEM image of vanadium metal obtained in example 2 of the present invention;
FIG. 4 is an X-ray diffraction pattern of vanadium metal obtained in example 2;
FIG. 5 is an SEM image of vanadium metal obtained in example 3 of the present invention;
FIG. 6 is an X-ray diffraction pattern of vanadium metal obtained in example 3;
FIG. 7 is a schematic structural view of an apparatus for preparing vanadium metal in example 5;
wherein, 1, a vacuum reactor; 2. a vacuum pump; 3. a microwave heater.
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.
Example 1
10g of V 2 O 5 And (3) carrying out microwave heating to 200 ℃ for 2 hours under the condition of vacuum degree of-60 mmHg, then carrying out microwave heating in an argon atmosphere with the pressure of 0.15MPa by taking 200g of calcium chloride fused salt as a reaction medium, heating to 700 ℃ at the speed of 20 ℃/min, adding sodium simple substance, carrying out reduction reaction for 4 hours, after the reduction reaction is finished, continuously cooling the material obtained by the reaction to 25 ℃ in the argon atmosphere, and washing, filtering and drying the material obtained by the reaction by using dilute hydrochloric acid, distilled water and alcohol in sequence to obtain the vanadium metal.
An SEM (scanning electron microscope) morphology chart obtained by carrying out SEM on the obtained metal vanadium is shown in figure 1; the obtained vanadium metal was subjected to X-ray diffraction analysis, and the obtained X-ray diffraction pattern was shown in FIG. 2.
The purity of the metal vanadium obtained in this example was 99.38% and the vanadium yield was 90.1% (the vanadium yield is the mass percentage of the vanadium content in the obtained metal vanadium to the total amount of vanadium in the vanadium source).
Example 2
And (3) heating 16g of sodium vanadate to 300 ℃ for dehydration for 3 hours under the condition of vacuum degree of-65 mmHg, then heating by microwaves in an argon atmosphere with pressure of 0.2MPa by taking 200g of calcium chloride fused salt as a reaction medium, heating to 800 ℃ at the speed of 50 ℃/min, adding magnesium simple substance for carrying out reduction reaction for 6 hours, continuously cooling the material obtained by the reaction to 25 ℃ in the argon atmosphere after the reduction reaction is finished, washing the material obtained by the reaction by dilute hydrochloric acid, distilled water and alcohol in sequence, filtering and drying to obtain the metal vanadium.
An SEM (scanning electron microscope) morphology chart obtained by carrying out SEM on the obtained metal vanadium is shown in figure 3; the obtained vanadium metal was subjected to X-ray diffraction analysis, and the obtained X-ray diffraction pattern was shown in FIG. 4.
The purity of the metal vanadium obtained in the embodiment is 99.90% and the vanadium yield is 90.3% through detection.
Example 3
And (3) carrying out microwave heating on 20g of ammonium metavanadate to 500 ℃ for 4 hours under the condition of vacuum degree of 72mmHg, then taking 200g of molten salt of a mixture of sodium chloride and calcium chloride (the mass ratio of sodium chloride to calcium chloride is 1:8) as a reaction medium, carrying out microwave heating in an argon atmosphere with the pressure of 0.25MPa, heating to 1000 ℃ at the speed of 200 ℃/min, adding a magnesium simple substance, carrying out reduction reaction for 8 hours, after the reduction reaction is finished, continuously cooling the material obtained by the reaction to 25 ℃ in the argon atmosphere, and washing, filtering and drying the material obtained by the reaction with dilute hydrochloric acid, distilled water and alcohol in sequence to obtain the metal vanadium.
An SEM (scanning electron microscope) morphology chart obtained by carrying out SEM on the obtained metal vanadium is shown in figure 5; the obtained vanadium metal was subjected to X-ray diffraction analysis, and the obtained X-ray diffraction pattern was shown in FIG. 6.
The purity of the metal vanadium obtained in the embodiment is 99.64% and the vanadium yield is 90.5% through detection.
Example 4
And (3) heating 16g of sodium vanadate to 300 ℃ for dehydration for 3 hours under the condition of vacuum degree of-65 mmHg, then heating by microwaves in an argon atmosphere with pressure of 0.2MPa by taking 200g of calcium chloride fused salt as a reaction medium, heating to 800 ℃ at the speed of 50 ℃/min, inserting a graphene electrode rod as an anode, taking sodium vanadate as a cathode, carrying out electrolytic reduction for 6 hours at 800 ℃, after the reduction reaction is finished, continuously cooling the material obtained by the reaction to 25 ℃ in the argon atmosphere, and washing, filtering and drying the material obtained by the reaction by dilute hydrochloric acid, distilled water and alcohol in sequence to obtain the metal vanadium.
The purity of the metal vanadium obtained in this example was 99.91% and the vanadium yield was 90.0% as detected.
Example 5
The present embodiment provides an apparatus for preparing vanadium metal, as shown in fig. 7, which includes a vacuum reactor 1, a vacuum pump 2 and a microwave heater 3; the vacuum reactor 1 is used for containing materials required by the reaction; the vacuum pump 2 is communicated with the vacuum reactor 1 and is used for controlling the vacuum degree in the vacuum reactor 1; the microwave heater 3 is sleeved on the outer wall of the vacuum reactor 1 and is used for controlling the temperature of materials required by the reaction in the vacuum reactor 1 through microwave heating.
Example 6
The apparatus of example 4 was used to prepare vanadium metal, in particular: after 16g of sodium vanadate and 200g of calcium chloride molten salt are added into a vacuum reactor 1, a vacuum pump 2 is started to enable the vacuum degree in the vacuum reactor 1 to reach-65 mmHg, and then a microwave heater 3 is started to heat a vanadium source to 300 ℃ for dehydration for 3 hours; introducing argon into the vacuum reactor 1 after the dehydration process is finished, controlling the pressure in the vacuum reactor 1 to be 0.2MPa, heating a vanadium source and molten salt to 800 ℃ at a speed of 50 ℃/min through a microwave heater 3, adding sodium simple substance for reaction for 6 hours, continuously cooling the material obtained by the reaction to 25 ℃ in an argon atmosphere, taking out the material obtained by the reaction, washing with dilute hydrochloric acid, distilled water and alcohol in sequence, filtering and drying to obtain the metal vanadium.
The purity of the metal vanadium obtained in the embodiment is 99.95% and the vanadium yield is 90.7% through detection.
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 (4)
1. A preparation method of vanadium metal is characterized in that: heating and dehydrating a vanadium source under a vacuum condition, heating to 700-1000 ℃ in a molten salt medium and under an inert gas atmosphere for reduction reaction, and washing and drying a material obtained by the reaction to obtain metal vanadium;
the heating rate is 20-120 ℃/min;
the reduction reaction is carried out by adding graphene as an anode and a vanadium source as a cathode;
the preparation method is carried out by the following devices:
the vacuum reactor is used for containing materials required by the reaction;
the vacuum pump is communicated with the vacuum reactor and used for controlling the vacuum degree in the vacuum reactor;
the microwave heater is sleeved on the outer wall of the vacuum reactor and is used for controlling the temperature of materials required by the reaction in the vacuum reactor through microwave heating;
the vanadium source is at least one of vanadate and ammonium metavanadate;
the molten salt is calcium chloride molten salt or a mixture of sodium chloride and calcium chloride, and the mass ratio of the sodium chloride to the calcium chloride is 1:5-10;
the temperature of the heating dehydration is 200-500 ℃, the vacuum degree is-60 to-72 mmHg, and the time is 2-4 hours.
2. The method for preparing vanadium metal according to claim 1, wherein: the mass of the vanadium source is equivalent to 5-12% of the mass of the molten salt.
3. The method for preparing vanadium metal according to claim 1, wherein: the inert gas is argon; and/or
The pressure of the reduction reaction is 0.15-0.25MPa; and/or
The time of the reduction reaction is 4-8h; and/or
The heating and the temperature raising process are performed by means of microwave heating.
4. The method for preparing vanadium metal according to claim 1, wherein: the washing method is that the materials obtained by the reaction are washed by dilute hydrochloric acid, distilled water and alcohol in sequence and filtered; and/or
And cooling the material obtained by the reaction in inert gas to below 30 ℃ and then carrying out the washing process.
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| CN202010955649.4A CN112251619B (en) | 2020-09-11 | 2020-09-11 | Preparation method and device of vanadium metal |
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| CN202010955649.4A CN112251619B (en) | 2020-09-11 | 2020-09-11 | Preparation method and device of vanadium metal |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB791151A (en) * | 1953-12-14 | 1958-02-26 | Horizons Titanium Corp | Fused salt bath for the electrodeposition of the polyvalent metals titanium, niobium, tantalum and vanadium |
| CN101343755A (en) * | 2008-08-20 | 2009-01-14 | 攀钢集团研究院有限公司 | Method for preparing metal vanadium |
| CN104404573A (en) * | 2014-12-18 | 2015-03-11 | 河北联合大学 | Preparation method of vanadium metal |
| CN109628731A (en) * | 2019-01-31 | 2019-04-16 | 河钢股份有限公司承德分公司 | A kind of method that short route processing extraction containing vanadium raw materials prepares vanadium and alloy powder |
-
2020
- 2020-09-11 CN CN202010955649.4A patent/CN112251619B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB791151A (en) * | 1953-12-14 | 1958-02-26 | Horizons Titanium Corp | Fused salt bath for the electrodeposition of the polyvalent metals titanium, niobium, tantalum and vanadium |
| CN101343755A (en) * | 2008-08-20 | 2009-01-14 | 攀钢集团研究院有限公司 | Method for preparing metal vanadium |
| CN104404573A (en) * | 2014-12-18 | 2015-03-11 | 河北联合大学 | Preparation method of vanadium metal |
| CN109628731A (en) * | 2019-01-31 | 2019-04-16 | 河钢股份有限公司承德分公司 | A kind of method that short route processing extraction containing vanadium raw materials prepares vanadium and alloy powder |
Non-Patent Citations (1)
| Title |
|---|
| 徐凯伦."三氧化二钒熔盐电脱氧制备金属钒的研究".《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2019,第B023-267页. * |
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