CN110079833B - Method for refining high-purity metal vanadium from high-carbon coarse impurity vanadium - Google Patents
Method for refining high-purity metal vanadium from high-carbon coarse impurity vanadium Download PDFInfo
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- CN110079833B CN110079833B CN201910335366.7A CN201910335366A CN110079833B CN 110079833 B CN110079833 B CN 110079833B CN 201910335366 A CN201910335366 A CN 201910335366A CN 110079833 B CN110079833 B CN 110079833B
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- 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
Abstract
The invention provides a method for refining high-purity metal vanadium from high-carbon coarse impurity vanadium, belonging to the field of metallurgical chemical industry. The method for refining high-purity metal vanadium by using high-carbon coarse impurity vanadium comprises the following steps: firstly, pretreating crude vanadium to prepare an electrode, and then placing the electrode in molten salt at a concentration of 0.1-1.5A/cm2Constant current electrolysis for 30 min-30 minAfter 0min, continuously electrolyzing for not less than 10h at the voltage of a 0.2-1.5V tank until the cathode is deposited to obtain metal, and carrying out post-treatment on the product to obtain pure metal vanadium; the method combines constant current pre-electrolysis salt preparation and constant voltage electrolytic refining to obtain pure metal vanadium at the cathode, can refine high-carbon coarse vanadium, has wide adaptability to raw materials, reduces impurity introduction links in the electrolysis process, and has high purity of refined products; the refining process of the method also simplifies the high-risk and complex operation of the traditional method for preparing salt by using chlorine, reduces the strict requirement on equipment, and ensures that the electrolytic process is green and sustainable.
Description
Technical Field
The invention relates to a method for refining high-purity metal vanadium from high-carbon coarse impurity vanadium, belongs to the field of metallurgical chemical industry, and particularly relates to the field of molten salt electrolysis.
Background
With the continuous development of industrial technology in China, the breakthrough of the industrial bottleneck gradually becomes the current situation that various industries in China are in urgent need of solution. Pure metals, particularly vanadium metals, have wide applications in the fields of aerospace, electronic information, marine exploration, novel materials and the like, and for example, high-purity vanadium foil is the best shielding material. The vanadium metal source in China is mainly based on the smelting of vanadium titano-magnetite, which is low-grade composite paragenic ore, the difficulty of ore smelting is high, and the traditional smelting process of high-quality pure metal vanadium mainly comprises the following steps: (1) the method comprises the following steps of (1) a vacuum carbothermic reduction method, (2) a silicothermic reduction method, (3) a thermal decomposition method of vanadium nitride, (4) a step-by-step reduction method, and (5) a metallothermic reduction method of vanadium oxide or chloride, wherein the aluminothermic reduction of the vanadium oxide is the most common method, and the methods generally have the defects of industrial discharge, serious resource waste, severe operation, low product purity, long flow path and the like. The idea of preparing pure vanadium based on direct electrolysis of coarse vanadium has great advantages. Based on the method, the patent discloses a novel method for electrorefining coarse miscellaneous vanadium.
In recent years, the molten salt electrolysis technology is known as a novel green sustainable metallurgy method, for the electrolytic smelting of vanadium metal, liu geissu has proposed in the 'research of low-chromium high-purity metal vanadium production process' that crude vanadium containing 95% of vanadium is prepared by using crude vanadium oxide as a raw material and adding aluminum fine powder to refine to obtain high-purity vanadium, but the aluminum fine powder added in the process can bring unknown impurities, the requirement on the crude vanadium oxide is also great, and especially the removal rate of impurities such as chromium, iron, aluminum and the like is not high; in addition, the electrolysis process usually uses chlorine firstlyGas preparation of VCl2The electrolyte can reach the refining condition of cathode deposition vanadium, and various requirements limit the product purity and cause the consequences of high operation difficulty and low current efficiency. In the novel method for refining coarse impurity vanadium, disclosed by the patent, the adaptability to raw materials is wide, and the intermediate preparation of VCl is saved2And refining the high-difficulty high-risk link to obtain pure vanadium metal. Liuwei and the like are reviewed in the optimization analysis of the process for preparing pure ferroalloy by refining high-carbon ferroalloy through molten salt electrolysis based on molten salt electrolysis technology refining, wherein the vanadium metal is described, vanadium carbide is used as a raw material, but VCl is prepared by using chlorine gas2And is added into the molten salt, the preparation process has serious pollution, poor safety and strict requirements on equipment; the refining process of the ferroalloy aims to realize codeposition among metals, dissolution of impurity elements and the like, and has an essential difference from the mechanism of refining pure metals. Therefore, the method for refining high-purity metal vanadium from high-carbon coarse impurity vanadium disclosed by the patent is simple to operate, has wide adaptability to raw materials and has the development advantage of pure vanadium refining.
Disclosure of Invention
Compared with the traditional pure vanadium metal treatment process, the method for refining high-purity metal vanadium from high-carbon coarse and impure vanadium provided by the invention has the advantages of wide raw material adaptability, low operation difficulty, wide molten salt preparation range and no need of chlorine for preparing VCl2The refining process is green and sustainable, and the purity of the pure vanadium metal product is high.
In order to achieve the purpose, the technical scheme provided by the method is as follows:
a method for refining high-purity metal vanadium from high-carbon coarse impurity vanadium comprises the following refining steps:
(a) crushing and grinding high-carbon coarse vanadium raw materials with the V content of 60-75 percent and the C content of 5-20 percent into powder, and forming the powder on a high-pressure powder forming tablet press under the pressure of 50-150MPa
Drying the block in a vacuum drying oven for later use.
(b) Placing blocky high-carbon coarse impurity vanadium blocky particles in a porous anode hanging basketTaking molten alkali metal molten salt as electrolyte, and carrying out electrolytic refining in a corundum crucible under inert atmosphere in the whole process; after the furnace temperature is increased to 500-800 ℃, immersing the prepared anode hanging basket and the cathode into molten salt for electrolysis, wherein the electrolysis is carried out at the first time at the rate of 0.1-1.5A/cm2The constant current density electrolysis is carried out for 30min to 300min for pre-electrolysis salt preparation, and then the electrolysis is carried out for more than 10h at the constant cell voltage of 0.2V to 1.5V.
(c) After the electrolysis is finished, the anode hanging basket and the cathode are lifted, the inert atmosphere protection is stopped after the furnace temperature is cooled to the room temperature, the cathode is taken out, the cathode product is separated, and the cathode product is repeatedly washed by dilute hydrochloric acid/deionized water after being treated in water bath ultrasound for 10min to 120min to obtain high-purity metal vanadium.
Preferably, the crude vanadium raw material in the step (a) is mainly composed of VxCy、VxOy、Al2O3、C、SiO2And other impurities;
the raw material of the coarse impurity vanadium contains, by mass, 60-75% of V, 5-20% of C, 5-15% of O, 1-3% of Al, 1-5% of Si and 0.1-2% of other impurity elements;
preferably, the anode hanging basket is made of any one of a molybdenum net, a nickel net, a tungsten net and a titanium net, and the aperture is 0.25-0.075 mm. The cathode can be any one of a molybdenum sheet, a nickel sheet, a stainless steel sheet and a vanadium sheet.
Preferably, the temperature of the electrolytic furnace in the step (b) is controlled at 650-750 ℃.
Preferably, the electrolyte molten salt may be one or more of sodium chloride, potassium chloride, cesium chloride, magnesium chloride, lithium chloride, calcium chloride, sodium fluoride, potassium fluoride, magnesium fluoride, lithium fluoride, calcium fluoride, and cesium fluoride.
Preferably, the pre-electrolysis current density in the step (b) is 0.5-1.2A/cm2The electrolysis time is 60min to 180 min.
Preferably, the voltage of the constant potential electrolytic cell in the step (b) is 0.4-1.0V, and the electrolytic time is not less than 15 h.
Compared with the prior art, the method has the following advantages:
according to the method, the high-carbon coarse and mixed vanadium is directly used as a raw material, based on a molten salt electrolysis technology, alkali metal chloride or fluoride is used as an electrolyte, a self-assembled electrolysis anode is adopted, salt preparation by constant current pre-electrolysis and constant voltage electrolysis refining are combined, pure metal vanadium is obtained at a cathode, the high-carbon coarse and mixed vanadium can be refined, the adaptability to the raw material is wide, the impurity introduction link in the electrolysis process is reduced, and the purity of a refined product is high; the refining process of the method also simplifies the high-risk and complex operation of the traditional method for preparing salt by using chlorine, and reduces the strict requirement on equipment.
Drawings
FIG. 1 is an XRD spectrum of a high-carbon crude miscellaneous vanadium raw material;
FIG. 2 is a diagram of a refined product;
figure 3 XRD spectrum of the refined product.
Detailed Description
For a more clear illustration of the invention, the following examples are given:
example 1:
according to the mass fraction, a crude miscellaneous vanadium raw material with 70.8 percent of V, 18.5 percent of C, 5.5 percent of O, 1.5 percent of Al, 2.2 percent of Si and 1.5 percent of other impurity elements is pressed into a sample with phi 5mm × 5mm under the pressure of 50MPa by a high-pressure forming sample press, 25 grains of the crude miscellaneous vanadium block are placed in a nickel net hanging basket with the porosity of 0.212mm, NaCl and KCl eutectic salt are selected as electrolyte, a molybdenum sheet is selected as cathode, and the concentration of the molybdenum sheet is 0.75A/cm at 650 DEG C2The current density is electrolyzed for 90min, then the electrolysis is continued for 25h with the constant potential of the bath voltage of 0.2V, the cathode and the anode are lifted, after the furnace temperature is cooled to the room temperature, the cathode product is treated by ultrasonic for 10min, and then the metal vanadium with the purity of 99.5 percent is obtained after the cathode product is repeatedly washed for 5 times by dilute hydrochloric acid and deionized water.
Example 2:
according to the mass fraction, a crude miscellaneous vanadium raw material with 75 percent of V, 5 percent of C, 14.0 percent of O, 3.0 percent of Al, 2.0 percent of Si and 2.0 percent of other impurity elements is pressed into a sample with phi 5mm × 5mm under the pressure of 100MPa by a high-pressure forming sample press, 30 crude miscellaneous vanadium blocks are placed in a 0-grain position075mm porosity molybdenum mesh basket; CsCl, KCl and MgCl salt are selected as electrolytes, a nickel sheet is selected as a cathode, and the temperature is 1.1A/cm at 750 DEG C2The current density is electrolyzed for 65min, then the electrolysis is continued for 30h with the constant potential of the bath voltage of 0.65V, the cathode and the anode are lifted, after the furnace temperature is cooled to the room temperature, the cathode product is treated by ultrasonic for 110min, and then the metal vanadium with the purity of 99.9 percent is obtained after the cathode product is repeatedly washed for 5 times by dilute hydrochloric acid and deionized water.
Example 3:
according to the mass fraction, a crude miscellaneous vanadium raw material with 67.4 percent of V, 14.3 percent of C, 14.5 percent of O, 2.6 percent of Al, 1.1 percent of Si and 0.1 percent of other impurity elements is pressed into a sample with phi 5mm × 5mm under the pressure of 150MPa by a high-pressure forming sample press, 45 grains of the crude miscellaneous vanadium block are placed in a nickel net hanging basket with the porosity of 0.18mm, LiCl and KCl eutectic salt are selected as electrolyte, a molybdenum sheet is selected as cathode, and 0.5A/cm is taken at the temperature of 500 DEG2The current density is electrolyzed for 170min, then the constant potential electrolysis is carried out for 30h under the constant cell voltage of 0.8V, the cathode and the anode are lifted, after the furnace temperature is cooled to the room temperature, the cathode product is treated by ultrasonic for 100min, and then the metal vanadium with the purity of 99.8 percent is obtained after the cathode product is repeatedly washed for 5 times by dilute hydrochloric acid and deionized water.
Example 4:
according to the mass fraction, a crude miscellaneous vanadium raw material with the V content of 60%, the C content of 20%, the O content of 15%, the Al content of 2%, the Si content of 1.0% and the content of other impurity elements of 2% is pressed into a sample with the diameter of 5mm × 5mm under a high-pressure forming sample press under the pressure of 100MPa, 30 crude miscellaneous vanadium blocks are placed in a molybdenum net hanging basket with the porosity of 0.075mm, LiCl, KCl and MgCl salt are selected as electrolytes, a vanadium sheet is selected as a cathode, and the concentration of the vanadium sheet is 0.1A/cm at the temperature of 750 DEG C2The current density is electrolyzed for 300min, then the electrolysis is continued for 30h with the constant potential of the bath voltage of 0.65V, the cathode and the anode are lifted, after the furnace temperature is cooled to the room temperature, the cathode product is treated by ultrasonic for 80min, and then the metal vanadium with the purity of 99.6 percent is obtained after the cathode product is repeatedly washed for 5 times by dilute hydrochloric acid and deionized water.
Example 5:
taking the V content as 70 percent, the C content as 10 percent, the O content as 10 percent and the Al content as 1.0 percent of the Si content by mass fraction2.0 percent of coarse miscellaneous vanadium raw material with the content of other impurity elements of 2.0 percent is pressed into a sample with the diameter of 5mm × 5mm under the pressure of 80MPa by a high-pressure forming sample press, 40 particles of coarse miscellaneous vanadium blocks are taken and placed in a molybdenum net hanging basket with the porosity of 0.25mm, LiCl, KCl and MgCl salt are selected as electrolytes, a vanadium sheet is selected as a cathode, and the concentration of the vanadium sheet is 1.5A/cm at the temperature of 800 DEG C2The current density is electrolyzed for 30min, then the electrolysis is continued for 10h with the constant potential of the bath voltage of 1.5V, the cathode and the anode are lifted, after the furnace temperature is cooled to the room temperature, the cathode product is treated by ultrasonic for 100min, and then the metal vanadium with the purity of 99.7 percent is obtained after the cathode product is repeatedly washed for 5 times by dilute hydrochloric acid and deionized water.
It should be noted that, according to the above embodiments of the present invention, those skilled in the art can fully implement the full scope of the present invention as defined by the independent claims and the dependent claims, and implement the processes and methods as the above embodiments; and the invention has not been described in detail so as not to obscure the present invention.
The above description is only a part of the embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (6)
1. A method for refining high-purity metal vanadium from high-carbon coarse impurity vanadium is characterized by comprising the following preparation steps:
(a) crushing and grinding the high-carbon coarse vanadium raw material into powder, and forming the powder on a high-pressure powder forming tablet press under the pressure of 50-150MPa
Drying the block in a vacuum drying oven for later use;
(b) placing blocky high-carbon coarse vanadium impurity blocks in a porous anode hanging basket, taking molten alkali metal molten salt as electrolyte, and carrying out electrolytic refining in a corundum crucible under inert atmosphere in the whole process; after the furnace temperature is increased to 500-800 ℃, immersing the prepared anode hanging basket and the cathode into molten salt for electrolysis, wherein the electrolysis is carried out at the first time at the rate of 0.1-1.5A/cm2Constant current density ofPerforming pre-electrolysis for salt preparation for 30-300 min, and then performing electrolysis for more than 10h at a constant bath voltage of 0.2-1.5V;
(c) after the electrolysis is finished, lifting the anode hanging basket and the cathode, stopping inert atmosphere protection after the furnace temperature is cooled to room temperature, taking out the cathode, separating a cathode product, treating in water bath ultrasound for 10-120 min, and repeatedly cleaning with dilute hydrochloric acid and deionized water to obtain high-purity metal vanadium;
the coarse miscellaneous vanadium raw material in the step (a) is mainly composed of VxCy、VxOy、Al2O3、C、SiO2And other impurities;
the high-carbon coarse impurity vanadium raw material comprises, by mass, 60% -75% of V, 5% -20% of C, 5% -15% of O, 1% -3% of Al, 1% -5% of Si and 0.1% -2% of other impurity elements.
2. The method for refining high-purity metal vanadium by using high-carbon coarse miscellaneous vanadium according to claim 1, characterized by comprising the following steps of: the anode hanging basket is made of any one of a molybdenum net, a nickel net, a tungsten net and a titanium net, and the aperture is 0.25-0.075 mm; the cathode is any one of a molybdenum sheet, a nickel sheet, a stainless steel sheet and a vanadium sheet.
3. The method for refining high-purity metal vanadium by using high-carbon coarse miscellaneous vanadium according to claim 1, characterized by comprising the following steps of: the temperature of the electrolytic furnace in the step (b) is controlled between 650 ℃ and 750 ℃.
4. The method for refining high-purity metal vanadium by using high-carbon coarse miscellaneous vanadium according to claim 1, characterized by comprising the following steps of: the electrolyte molten salt is one or more of sodium chloride, potassium chloride, cesium chloride, magnesium chloride, lithium chloride, calcium chloride, sodium fluoride, potassium fluoride, magnesium fluoride, lithium fluoride, calcium fluoride and cesium fluoride.
5. The method for refining high-purity metal vanadium by using high-carbon coarse miscellaneous vanadium according to claim 1, characterized by comprising the following steps of: the pre-electrolysis current density in the step (b) is 0.5-1.2A/cm2At the time of electrolysisThe time interval is 60-180 min.
6. The method for refining high-purity metal vanadium by using high-carbon coarse miscellaneous vanadium according to claim 1, characterized by comprising the following steps of: in the step (b), the voltage of the constant potential electrolytic bath is 0.4-1.0V, and the electrolytic time is not less than 15 h.
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| US3098021A (en) * | 1960-04-15 | 1963-07-16 | Union Carbide Corp | Process for producing ductile vanadium |
| US7410562B2 (en) * | 2003-08-20 | 2008-08-12 | Materials & Electrochemical Research Corp. | Thermal and electrochemical process for metal production |
| CN101343755B (en) * | 2008-08-20 | 2010-08-25 | 攀钢集团研究院有限公司 | Method for preparing metal vanadium |
| CN101649471B (en) * | 2009-09-23 | 2013-06-12 | 攀钢集团研究院有限公司 | Method for producing high purity vanadium metal |
| CN102978664B (en) * | 2011-09-05 | 2015-12-02 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of preparation method of vanadium metal and the vanadium metal obtained by the method |
| CN105714332B (en) * | 2016-04-15 | 2019-03-22 | 华北理工大学 | A kind of method of fused salt electro-deposition vanadium |
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