CN109295310B - Method for preparing high-purity metal vanadium powder by metal gas-based reduction - Google Patents
Method for preparing high-purity metal vanadium powder by metal gas-based reduction Download PDFInfo
- Publication number
- CN109295310B CN109295310B CN201811157105.2A CN201811157105A CN109295310B CN 109295310 B CN109295310 B CN 109295310B CN 201811157105 A CN201811157105 A CN 201811157105A CN 109295310 B CN109295310 B CN 109295310B
- Authority
- CN
- China
- Prior art keywords
- metal
- purity
- powder
- vanadium
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- 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
- C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to a method for preparing high-purity metal vanadium powder by metal gas-based reduction, belonging to the field of metal thermal reduction preparation of metal vanadium. The invention solves the technical problem that the existing process for producing high-purity metal vanadium is complex, and the prepared metal vanadium is not metal vanadium powder generally. The invention discloses a method for preparing high-purity metal vanadium powder by metal gas-based reduction, which comprises the steps of taking vanadium oxide as a raw material, taking active metal as a reducing agent, contacting the active metal with the raw material in a gas form to carry out thermal reduction reaction, and pickling, filtering and drying a reaction product to obtain the high-purity metal vanadium powder. The method is simple to operate, the flow is short, the purity of the prepared high-purity metal vanadium powder is more than or equal to 98%, the granularity range is 1-200 mu m, the surface of the metal vanadium powder particle is porous, and the method can be applied to the fields of powder metallurgy, 3D printing and the like.
Description
Technical Field
The invention belongs to the field of metal thermal reduction preparation of metal vanadium, and particularly relates to a method for preparing high-purity metal vanadium powder by metal gas-based reduction.
Background
The vanadium metal has the excellent characteristics of high melting point, no magnetism, corrosion resistance, small fast neutron absorption interface and the like, and is widely applied to the fields of aerospace industry, electronic industry, superconducting alloy materials and the like. The existing method for producing metal vanadium is generally carried out in two steps, firstly, the vacuum carbothermic reduction method, the silicothermic reduction method, the thermal decomposition method of vanadium nitride, the step-by-step reduction method, the metallothermic reduction method of vanadium oxide or chloride (such as aluminum reduction, calcium reduction, magnesium reduction and the like) and the like are used for preparing metal vanadium containing certain impurity elements, namely primary metal vanadium (crude vanadium); then, the crude vanadium is refined by a molten salt electrolysis method, a vacuum refining method, an iodide thermal decomposition method, or the like to obtain high-purity vanadium metal.
The existing process for producing metal vanadium has the following two defects: firstly, the metal vanadium with relatively high purity can be obtained by two or more steps of processes, the process flow is long, the process is complex, and the production cost is high; and secondly, except for electrolytic refining, all the vanadium metal obtained by other refining processes is metal cast ingots, powdery vanadium metal cannot be obtained, and the application of the powdery vanadium metal in the fields of powder metallurgy, 3D printing and the like is irreplaceable for blocky vanadium metal. In addition, the production of metal vanadium powder by an electrolytic method has the technical bottlenecks of low efficiency, high oxygen content, difficult control of particle size, unstable quality and the like.
Patent document CN103498060A provides a method for preparing metal vanadium: mixing and compacting vanadium oxide and aluminum powder, igniting by using a metal wire under the protection of inert gas, and obtaining metal vanadium after the reaction is finished. The method is simple in process, the grade of the obtained vanadium is 94-97%, but the metal vanadium produced by the method is blocky, and the application field of the metal vanadium is limited. Patent document CN102978664A provides a method for preparing metal vanadium and metal vanadium prepared by the method: the method comprises the steps of electrolyzing molten salt under an electrolysis condition to obtain an electrolysis product containing a metal vanadium simple substance at a cathode. The method has simple process and can obtain high-purity metal vanadium, but the product obtained by the method is not metal powder, thereby limiting the application field of the method. Patent document CN102121123A provides a smelting process of vanadium metal: the method combines a microwave fluidized bed technology with an FFC electro-deoxidation technology, and prepares the metal vanadium by taking vanadium pentoxide as a raw material. The purity of the vanadium metal prepared by the method can reach above 995, but the method has long preparation process and relatively complicated process, and the product is not vanadium metal powder.
Disclosure of Invention
The invention solves the technical problem that the existing process for producing high-purity metal vanadium is complex, and the prepared metal vanadium is not metal vanadium powder generally.
The technical scheme for solving the problems is to provide a method for preparing high-purity metal vanadium powder by metal gas-based reduction, which comprises the following steps: in the form of powder V2O5As raw material, active metal isA reducing agent for volatilizing the active metal into gas and powder V under the conditions of vacuum degree of 1-100 Pa and temperature of 500-1200 DEG C2O5The contact is carried out for thermal reduction reaction, and the reaction product is acid-washed, filtered and dried to obtain the metal vanadium powder.
Wherein the active metal is at least one of Mg, Ca, K and Na.
Among them, preferably, the active metal is Mg.
Wherein the raw material powder V2O5The purity is more than 99.8%.
Wherein the mass ratio of the reducing agent to the vanadium oxide is 2-10: 1.
Wherein the temperature is controlled as follows, the temperature is raised to 500 ℃ at the speed of 5-10 ℃/min and is preserved for 1-3 hours, then the temperature is raised to 650-700 ℃ at the speed of 1-10 ℃/min and is preserved for 1-3 hours, the temperature is raised to 800-1200 ℃ at the speed of 1-10 ℃/min again, and the temperature is preserved for 4-10 hours.
And the step of acid washing comprises the steps of firstly soaking the reaction product cooled to room temperature in deionized water, then starting to add dilute hydrochloric acid, controlling the pH value to be 1-3, stopping adding the dilute hydrochloric acid when the pH value is not increased any more and keeping for 10-30 min.
Wherein the drying condition is that the drying is carried out for 4 to 8 hours at a temperature of between 90 and 120 ℃.
Wherein the purity of the prepared metal vanadium powder is more than or equal to 98 percent, the particle size range is 1-200 mu m, and the surface of the metal vanadium powder particle is porous.
The invention has the beneficial effects that:
according to the invention, vanadium oxide is used as a raw material, active metal is used as a reducing agent, the active metal is in contact reaction with the raw material in a gas form, and high-purity metal vanadium powder is obtained through acid washing, filtering and drying; the purity of the high-purity metal vanadium powder prepared by the method is more than or equal to 98%, the particle size range is 1-200 mu m, the surface of the metal vanadium powder particle is porous, and the high-purity metal vanadium powder can be applied to the fields of powder metallurgy, 3D printing and the like.
Drawings
FIG. 1 is the SEM surface morphology of the high-purity metal vanadium powder prepared in example 2.
Detailed Description
The invention provides a method for preparing high-purity metal vanadium powder by metal gas-based reduction, which comprises the following steps: in the form of powder V2O5Taking active metal as a reducing agent as a raw material, volatilizing the metal into gas and powdery V under the conditions of vacuum degree of 1-100 Pa and temperature of 500-1200 DEG C2O5And (3) carrying out reaction, and carrying out acid washing, filtering and vacuum drying on a reaction product to obtain the metal vanadium powder.
The vacuum degree is controlled to be 1-100 Pa, and different vacuum degrees can be adjusted through the addition amount of the reducing agent, so that the aim of the invention is achieved.
Wherein the active metal is at least one of Mg, Ca, K and Na.
Among them, Mg, Ca, K, and Na are active metals commonly used in thermal reduction reactions, and in consideration of effects and price, Mg is preferably used as the active metal. The reactions that occur at this point are as follows:
V2O5+5Mg(g)＝5MgO+2V
mg as a gas with V2O5The contact is carried out with thermal reduction reaction to realize gas-solid reaction, and no liquid is generated in the whole reaction process, so that the metal vanadium powder with small granularity and porous surface can be obtained without crushing after acid washing, filtering and drying.
Wherein the raw material powder V2O5The purity of (A) is more than 99.8%.
Wherein the reducing agent is reacted with V2O5The mass ratio of (A) to (B) is 2-10: 1.
Wherein the temperature is controlled as follows, the temperature is raised to 500 ℃ at the speed of 5-10 ℃/min and is preserved for 1-3 hours, then the temperature is raised to 650-700 ℃ at the speed of 1-10 ℃/min and is preserved for 1-3 hours, and the temperature is raised to 800-1200 ℃ at the speed of 1-10 ℃/min and is preserved for 4-10 hours. Lower temperature in the early stage, metal volatilizing into gas, and V2O5Thermal reduction reaction is carried out to convert the vanadium oxide into low-valence vanadium oxide, the melting point is raised, and then the temperature is raisedAnd (4) keeping the gas-solid reaction.
The pickling step comprises the steps of firstly soaking a reaction product cooled to room temperature in deionized water, then slowly adding dilute hydrochloric acid, detecting the pH value of the solution, controlling the pH value to be 1-3, continuously increasing the pH value due to continuous consumption of the dilute hydrochloric acid, and stopping adding the dilute hydrochloric acid and keeping the pH value for 10-30 min when the pH value is stable and is not increased any more. The acid washing is to remove metal oxides (MgO, CaO, K) from the reaction product2O、Na2O) and residual metals (Mg, Ca, K, Na).
Wherein the drying condition is that the drying is carried out for 4 to 8 hours at a temperature of between 90 and 120 ℃.
Wherein the purity of the prepared metal vanadium powder is more than or equal to 98 percent, the particle size range is 1-200 mu m, and the surface of the metal vanadium powder particle is porous.
Example 1
Weighing 50g of powdery high-purity vanadium pentoxide and 300g of magnesium metal, freely placing magnesium metal at the bottom of a crucible, uniformly paving the powdery high-purity vanadium pentoxide on a molybdenum distributor, suspending the powdery high-purity vanadium pentoxide in the crucible, and placing the powdery high-purity vanadium pentoxide and the molybdenum distributor in a vacuum furnace; vacuumizing to 10Pa, heating to 500 ℃, preserving heat for 2h, then heating to 680 ℃, preserving heat for 2h, and heating to 800 ℃ again, preserving heat for 4 h; cooling to room temperature, taking out a reaction product, soaking the reaction product in deionized water, slowly adding hydrochloric acid, adjusting the pH value of an acid solution to be 1, stopping adding dilute hydrochloric acid when the pH value is not increased any more when the pH value is stable, pickling for 30min, and filtering; finally, placing the mixture in a vacuum drying oven for drying, wherein the set temperature is 100 ℃, and the time is 8 hours; after drying, the metal powder vanadium is obtained, and the chemical components of the metal powder vanadium are shown in Table 1.
Table 1 example 1 composition table of metal vanadium powder
| Element(s) | O | Mg | Si | Al | V |
| Content/% | 0.3 | 0.12 | 0.08 | 0.14 | 99.16 |
Example 2
Weighing 100g of powdery high-purity vanadium pentoxide and 400g of magnesium metal, freely placing magnesium metal at the bottom of a crucible, uniformly paving the powdery high-purity vanadium pentoxide on a molybdenum distributor, suspending the powdery high-purity vanadium pentoxide in the crucible, and placing the powdery high-purity vanadium pentoxide and the molybdenum distributor in a vacuum furnace; vacuumizing to 10Pa, heating to 500 ℃, preserving heat for 2h, then heating to 680 ℃, preserving heat for 3h, and heating to 800 ℃ again, preserving heat for 5 h; cooling to room temperature, taking out a reaction product, soaking the reaction product in deionized water, slowly adding hydrochloric acid, adjusting the pH value of an acid solution to be 1, stopping adding dilute hydrochloric acid when the pH value is not increased any more when the pH value is stable, pickling for 30min, and filtering; finally, placing the mixture in a vacuum drying oven for drying, wherein the set temperature is 100 ℃, and the time is 8 hours; after drying, the metal powder vanadium is obtained, the chemical components of which are shown in Table 2, and the surface appearance of which is shown in figure 1.
Table 2 example 2 composition table of metal vanadium powder
| Element(s) | O | Mg | Al | Si | V |
| Content/% | 0.18 | 0.05 | 0.08 | 0.07 | 99.35 |
Claims (7)
1. The method for preparing high-purity metal vanadium powder by metal gas-based reduction is characterized by comprising the following steps of: in the form of powder V2O5Taking active metal as a reducing agent as a raw material, and volatilizing the active metal into gas and powder V under the conditions of vacuum degree of 1-100 Pa and temperature of 500-1200 DEG C2O5The contact is carried out for thermal reduction reaction, the reaction product is subjected to acid washing, filtering and drying to obtain metal vanadium powder, the purity of the metal vanadium powder is more than or equal to 98%, the particle size range is 1-200 mu m, the particle surface is porous, the reaction temperature is controlled as follows, the temperature is increased to 500 ℃ at the speed of 5-10 ℃/min, the temperature is kept for 1-3 hours, then the temperature is increased to 650-700 ℃ at the speed of 1-10 ℃/min, the temperature is kept for 1-3 hours, and the temperature is increased to 800-1200 ℃ at the speed of 1-10 ℃/min again, and the temperature is kept for 4-10 hours.
2. The method for preparing high-purity metal vanadium powder by metal gas-based reduction according to claim 1, characterized in that: the powder V2O5The purity is more than 99.8%.
3. The method for preparing high-purity metal vanadium powder by metal gas-based reduction according to claim 1, characterized in that: the active metal is at least one of Mg, Ca, K and Na.
4. The method for preparing high-purity metal vanadium powder by metal gas-based reduction according to claim 1, characterized in that: the active metal is Mg.
5. The method for preparing high-purity metal vanadium powder by metal gas-based reduction according to claim 1, characterized in that: the reducing agent and V2O5The mass ratio of (A) to (B) is 2-10: 1.
6. The method for preparing high-purity metal vanadium powder by metal gas-based reduction according to claim 1, characterized in that: and the step of acid washing comprises the steps of firstly soaking the reaction product in deionized water, then starting to add dilute hydrochloric acid, controlling the pH value to be 1-3, stopping adding the dilute hydrochloric acid when the pH value is stable and does not increase any more, and keeping for 10-30 min.
7. The method for preparing high-purity metal vanadium powder by metal gas-based reduction according to claim 1, characterized in that: the drying condition is that the drying is carried out for 4-8 hours at the temperature of 90-120 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811157105.2A CN109295310B (en) | 2018-09-30 | 2018-09-30 | Method for preparing high-purity metal vanadium powder by metal gas-based reduction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811157105.2A CN109295310B (en) | 2018-09-30 | 2018-09-30 | Method for preparing high-purity metal vanadium powder by metal gas-based reduction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109295310A CN109295310A (en) | 2019-02-01 |
| CN109295310B true CN109295310B (en) | 2020-08-04 |
Family
ID=65161434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811157105.2A Active CN109295310B (en) | 2018-09-30 | 2018-09-30 | Method for preparing high-purity metal vanadium powder by metal gas-based reduction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109295310B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110306061A (en) * | 2019-08-06 | 2019-10-08 | 攀钢集团研究院有限公司 | The method that vananum prepares vanadium metal |
| CN110284001A (en) * | 2019-08-06 | 2019-09-27 | 攀钢集团研究院有限公司 | The method that vanadium iron prepares vanadium metal |
| CN111957984B (en) * | 2020-08-25 | 2022-05-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of metal vanadium powder |
| CN113732297B (en) * | 2021-09-04 | 2023-06-23 | 湖南众鑫新材料科技股份有限公司 | High-purity vanadium purification process |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906546B (en) * | 2010-07-14 | 2012-11-28 | 承德天大钒业有限责任公司 | Method for preparing vanadium-aluminum alloy |
| CN101967567A (en) * | 2010-11-11 | 2011-02-09 | 攀钢集团钢铁钒钛股份有限公司 | Method for preparing metal vanadium |
| CN103498060B (en) * | 2013-09-03 | 2015-02-18 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing metal vanadium |
-
2018
- 2018-09-30 CN CN201811157105.2A patent/CN109295310B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109295310A (en) | 2019-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109295310B (en) | Method for preparing high-purity metal vanadium powder by metal gas-based reduction | |
| JP5526207B2 (en) | Titanium metal production method and titanium metal obtained using this method | |
| CN110227826B (en) | Method for preparing high-purity nano molybdenum powder | |
| CN109079151B (en) | Method for preparing ultra-coarse tungsten powder by high-temperature liquid-phase reduction of tungsten oxide | |
| US3415639A (en) | Method for the manufacture of tantalum and/or niobium powder | |
| JP2020519761A (en) | Method for producing refractory metal powder by multi-stage and advanced reduction | |
| CN104195355A (en) | Zirconium and method for preparing zirconium | |
| CN108044126B (en) | Method for preparing plate-shaped WC-Co composite powder by using waste hard alloy | |
| CN107904626A (en) | A kind of purification ultrafine titanium powder or Titanium Powder and preparation method thereof | |
| CN109022790A (en) | The method that metal gas-based reduction prepares metal vanadium powder | |
| CN110029220B (en) | Method for preparing metal chromium powder by reducing chromium oxide through two-step method | |
| CN108264048B (en) | Method for removing free carbon in transition metal carbide | |
| CN113699560A (en) | Method for preparing metal titanium by soluble anode electrolysis of fluorine-chlorine mixed molten salt system | |
| CN111363934B (en) | Magnesium-scandium alloy and preparation method thereof | |
| CN104099634B (en) | The preparation method of vanadium nitride | |
| CN108502852A (en) | A kind of method that selenium in copper anode mud is recycled in microwave sulfating roasting | |
| CN115304379B (en) | Anode material and preparation method thereof | |
| CN107746057B (en) | Preparation method of superfine molybdenum carbide | |
| CN114853018A (en) | Method for preparing tantalum carbide powder | |
| CN111558713B (en) | Oxygen reduction method for small-particle-size titanium powder | |
| JP4574826B2 (en) | How to recover tellurium | |
| CN107937710B (en) | Pyrolusite pyrogenic reduction method | |
| US3786133A (en) | Titanium carbide preparation | |
| CN105060295A (en) | Preparation method of TiC material with meso structure | |
| CN111020359A (en) | Alloy for improving strength of deformed steel bar and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 610306 Chengdu City, Chengdu, Sichuan, China (Sichuan) free trade test zone, Chengdu City, Qingbaijiang District, xiangdao Boulevard, Chengxiang Town, No. 1509 (room 13, A District, railway port mansion), room 1319 Patentee after: Chengdu advanced metal material industry technology Research Institute Co.,Ltd. Address before: 610306 Chengdu City, Chengdu, Sichuan, China (Sichuan) free trade test zone, Chengdu City, Qingbaijiang District, xiangdao Boulevard, Chengxiang Town, No. 1509 (room 13, A District, railway port mansion), room 1319 Patentee before: CHENGDU ADVANCED METAL MATERIAL INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. |