CN110079833A - A kind of high-carbon slightly miscellaneous vanadium refining high-purity gold category vanadium method - Google Patents
A kind of high-carbon slightly miscellaneous vanadium refining high-purity gold category vanadium method Download PDFInfo
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- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
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Abstract
The present invention provides a kind of high-carbon slightly miscellaneous vanadium refining high-purity gold category vanadium methods, belong to field of metallurgy and chemical engineering.Slightly miscellaneous vanadium refining high-purity gold category vanadium method process is as follows for a kind of high-carbon: first by thick vanadium carry out pretreatment be prepared into electrode after, with 0.1~1.5A/cm in fuse salt2Electric current constant-current electrolysis 30min~300min, then 0.2~1.5V tank voltage continued electrolysis is no less than 10h and deposits to obtain metal to cathode again, and product is post-treated to obtain pure metal vanadium；This method in such a way that constant-potential electrolysis refining combines, is obtained pure metal vanadium in cathode, can refine high-carbon slightly miscellaneous vanadium by constant current preelectrolysis salt manufacturing, has wide to adaptability to raw material, is reduced electrolytic process impurity and is brought link into, refining product purity is high；The refining process of this method also simplifies high-risk many and diverse operation that tradition uses chlorine salt manufacturing, reduces the rigors to equipment, electrolytic process green is sustainable.
Description
Technical field
The present invention relates to a kind of high-carbon slightly miscellaneous vanadium refining high-purity gold category vanadium methods, belong to field of metallurgy and chemical engineering, and in particular to
Molten-salt electrolysis field.
Background technique
With the continuous development of China's industrial technology, it is urgently to be resolved that breakthrough industry bottleneck is increasingly becoming China's all trades and professions
Status.Pure metal especially vanadium metal has wide in fields such as aerospace, electronic information, seafari and new materials
Application, for example, high purity vanadium foil is best shielding material.China vanadium metal source is based primarily upon the smelting of vanadium titano-magnetite,
It is low-grade compositeon-silicon paragenetic, and mining and metallurgy difficulty is big, and the pure metal vanadium tradition smelting process of high-quality mainly has: (1) vacuum carbon
Thermal reduction, (2) silicothermic process, the thermal decomposition method of (3) vanadium nitride, (4) step-by-step reduction method, (5) barium oxide or chloride
Metallothermic processes, wherein the aluminothermic reduction with barium oxide is the most universal, the generally existing industrial discharge of above method is big, money
Source waste is serious, and operation is harsh, and product purity is not high, the drawbacks such as long flow path.And pure vanadium is prepared based on thick miscellaneous vanadium Direct Electrolysis
Thinking has very big advantage.Based on this, this patent discloses a kind of thick miscellaneous vanadium electrorefining new method.
In recent years, molten-salt electrolysis technology is acknowledged as a kind of sustainable novel metallurgical method of green, for vanadium metal
Electrolysis for production, Liu Shouxin once it is proposed that being in " research of low chromium high pure metal technique for producing vanadium " text with thick vanadium oxide
Raw material obtains high purity vanadium after being refined with addition of thick vanadium of the aluminium fine powder preparation containing vanadium 95%, but the aluminium fine powder of its process supplying can band
Enter unknown impuritie, also the requirement to thick vanadium oxide is very big, and the removal rate of the especially impurity such as chromium, iron, aluminium is not high；Another electrolytic process
It usually first has to prepare VCl using chlorine2Electrolyte, to reach cathode deposition vanadium refining condition, various requirements limit product
Purity, and cause the consequence that operation difficulty is high and current efficiency is low.In a kind of thick miscellaneous vanadium method for refining that this patent is announced,
It is wide to adaptability to raw material, and save middle preparation VCl2Highly difficult high-risk link, refining have obtained pure vanadium metal.Liu Wei etc. exists
It is carried out in " fused-salt electrolytic refining high-carbbon iron alloy prepares pure ferroalloy process optimization analysis " based on molten-salt electrolysis technology refining
Summary, wherein the description as described in vanadium metal, using vanadium carbide as raw material, but needs to prepare VCl using chlorine2, and enter molten
In salt, preparation process is seriously polluted, and safety is poor, to equipment requirement harshness；And the refining process for ferroalloy is to realize
The dissolution etc. of co-deposition and impurity element between metal has essential distinction with fine metal in mechanism.So this is specially
Slightly miscellaneous vanadium refining high-purity gold category vanadium method is easy to operate for a kind of high-carbon that benefit is announced, wide to adaptability to raw material and smart with pure vanadium
The advantages for development of refining.
Summary of the invention
A kind of high-carbon provided by the invention slightly miscellaneous vanadium refining high-purity gold category vanadium method handles work compared to traditional pure vanadium metal
Skill has adaptability to raw material wide, and operation difficulty is low, and fused salt preparation range is wide in range, does not need chlorine preparation VCl2, refining process is green
Color is sustainable, the advantages such as pure vanadium metal product purity height.
To achieve the above object, the technical solution that the method for the present invention provides are as follows:
Slightly miscellaneous vanadium refining high-purity gold category vanadium method, refinement step are as follows for a kind of high-carbon:
It (a) is 60%~75% by V content, slightly miscellaneous vanadium raw materials are crushed, are ground into powdery the high-carbon of C content 5%~20%,
It is shaped on high-pressure powder molding press with the pressure of 50-150MPaBlocks after, it is dry to be placed in vacuum
Drying for standby in dry case.
(b) by blocky high-carbon, slightly miscellaneous vanadium block grain is placed in porous anode hanging basket, using molten alkali metal fused salt as electrolyte,
The electrorefining in corundum crucible, whole process carry out under an inert atmosphere；After furnace temperature rises to 500~800 DEG C, by what is be ready for
Anode hanging basket and cathode, which are submerged in fused salt, to be electrolysed, first with 0.1~1.5A/cm2Constant current density electrolysis 30min~
300min carries out preelectrolysis salt manufacturing, is then electrolysed 10h or more with the constant tank voltage of 0.2~1.5V.
(c) after being electrolysed, anode hanging basket and cathode are lifted, stops inert atmosphere after furnace temperature is cooled to room temperature and protects
Shield, takes out cathode and separates cathode product, uses dilute hydrochloric acid/deionized water anti-after 10min~120min is handled in water bath sonicator
Multiple cleaning obtains high purity vanadium metal.
Preferably, the thick miscellaneous vanadium raw materials of step (a) are mainly by VxCy、VxOy、Al2O3、C、SiO2And other impurities composition；
Based on mass fraction, V content is 60%~75% to each element, C content 5%~20%, O content in thick miscellaneous vanadium raw materials
It is 5%~15%, Al content is that 1%~3%, Si content is 1%~5%, and other impurities constituent content is 0.1%~2%；
Preferably, anode hanging basket metal molybdenum net, nickel screen, tungsten net, any one in titanium net, and aperture 0.25~
0.075mm.Cathode can be molybdenum sheet, nickel sheet, stainless steel substrates, any one in vanadium piece.
Preferably, step (b) is electrolysed Control for Kiln Temperature at 650 DEG C~750 DEG C.
Preferably, electrolyte fused salt can be sodium chloride, potassium chloride, cesium chloride, magnesium chloride, lithium chloride, calcium chloride, fluorination
One or more of sodium, potassium fluoride, magnesium fluoride, lithium fluoride, calcirm-fluoride, cesium fluoride.
Preferably, preelectrolysis current density is 0.5~1.2A/cm in step (b)2, electrolysis time be 60min~
180min。
Preferably, 0.4~1.0V of potentiostatic deposition tank voltage, electrolysis time are no less than 15h in step (b).
Compared with prior art, the method for the invention has the advantage that as follows:
The present invention is directly using high-carbon, slightly miscellaneous vanadium is raw material, based on molten-salt electrolysis technology, with alkali metal chlorizated salt or fluorination
Salt is electrolyte, using the electrolytic anode of self assembly, refines the side combined with constant-potential electrolysis with constant current preelectrolysis salt manufacturing
Formula obtains pure metal vanadium in cathode, can refine high-carbon slightly miscellaneous vanadium, have to adaptability to raw material it is wide, reduce electrolytic process impurity
Bring link into, refining product purity is high；The refining process of this method also simplifies high-risk many and diverse behaviour that tradition uses chlorine salt manufacturing
Make, reduces the rigors to equipment.
Detailed description of the invention
Fig. 1 is the XRD spectra of high-carbon slightly miscellaneous vanadium raw materials；
Fig. 2 is refining product pictorial diagram；
Fig. 3 refines product XRD spectra.
Specific embodiment
For the clearer elaboration present invention, specific embodiment tell about as follows:
Embodiment 1:
Based on mass fraction, taking V content is 70.8%, C content 18.5%, O content 5.5%, Al content 1.5%
Si content is 2.2%, the thick miscellaneous vanadium raw materials that other impurities constituent content is 1.5%, in high-pressure molding pressure-like under 50MPa pressure
It is compressed to the sample of φ 5mm × 5mm under machine, thick miscellaneous vanadium block 25 is taken to be placed in 0.212mm porosity nickel screen hanging basket；It chooses
NaCl, KCl eutectic salts are electrolyte, and molybdenum sheet is cathode, with 0.75A/cm at 650 DEG C2Current density electrolysis 90min, so
Lift cathode and anode after continuing the tank voltage potentiostatic deposition 25h with 0.2V afterwards, after furnace temperature is cooled to room temperature, by cathode product
After being ultrasonically treated 10min, the vanadium metal that purity is 99.5% is obtained after cleaning 5 times repeatedly with dilute hydrochloric acid and deionized water.
Embodiment 2:
Based on mass fraction, taking V content is 75%, and C content 5%, O content 14.0%, Al content contains for 3.0%Si
Amount is 2.0%, the thick miscellaneous vanadium raw materials that other impurities constituent content is 2.0%, in high-pressure molding pressure-like machine under 100MPa pressure
Under be compressed to the sample of φ 5mm × 5mm, take thick miscellaneous vanadium block 30 to be placed in 0.075mm porosity molybdenum net hanging basket；It chooses
CsCl, KCl, MgCl salt are electrolyte, and nickel sheet is cathode, with 1.1A/cm at 750 DEG C2Current density electrolysis 65min, so
Lift cathode and anode after continuing the tank voltage potentiostatic deposition 30h with 0.65V afterwards, after furnace temperature is cooled to room temperature, by cathode product
After being ultrasonically treated 110min, the vanadium metal that purity is 99.9% is obtained after cleaning 5 times repeatedly with dilute hydrochloric acid and deionized water.
Embodiment 3:
Based on mass fraction, taking V content is 67.4%, C content 14.3%, O content 14.5%, and Al content is
2.6%Si content be 1.1%, other impurities constituent content be 0.1% thick miscellaneous vanadium raw materials, under 150MPa pressure high pressure at
It is compressed to the sample of φ 5mm × 5mm under type pressure-like machine, thick miscellaneous vanadium block 45 is taken to be placed in 0.18mm porosity nickel screen hanging basket；
Selection LiCl, KCl eutectic salts are electrolyte, and molybdenum sheet is cathode, with 0.5A/cm at 500 DEG C2Current density electrolysis
170min lifts anode and cathode after then proceeding to the tank voltage potentiostatic deposition 30h with 0.8V, will after furnace temperature is cooled to room temperature
After cathode product is ultrasonically treated 100min, the gold that purity is 99.8% is obtained after cleaning 5 times repeatedly with dilute hydrochloric acid and deionized water
Belong to vanadium.
Embodiment 4:
Based on mass fraction, taking V content is 60%, C content 20%, O content 15%, and Al content is 2%Si content
It is 1.0%, the thick miscellaneous vanadium raw materials that other impurities constituent content is 2% push under 100MPa pressure in high-pressure molding pressure-like machine
It is made as the sample of φ 5mm × 5mm, thick miscellaneous vanadium block 30 is taken to be placed in 0.075mm porosity molybdenum net hanging basket；Selection LiCl,
KCl, MgCl salt are electrolyte, and vanadium piece is cathode, with 0.1A/cm at 750 DEG C2Current density electrolysis 300min, then after
Continue to lift cathode and anode after the tank voltage potentiostatic deposition 30h of 0.65V, after furnace temperature is cooled to room temperature, by cathode product ultrasound
After handling 80min, the vanadium metal that purity is 99.6% is obtained after cleaning 5 times repeatedly with dilute hydrochloric acid and deionized water.
Embodiment 5:
Based on mass fraction, taking V content is 70%, and C content 10%, O content 10%, Al content contains for 1.0%Si
Amount is 2.0%, the thick miscellaneous vanadium raw materials that other impurities constituent content is 2.0%, under 80MPa pressure under high-pressure molding pressure-like machine
It is compressed to the sample of φ 5mm × 5mm, thick miscellaneous vanadium block 40 is taken to be placed in 0.25mm porosity molybdenum net hanging basket；Selection LiCl,
KCl, MgCl salt are electrolyte, and vanadium piece is cathode, with 1.5A/cm at 800 DEG C2Current density electrolysis 30min, then proceed to
To lift cathode and anode after the tank voltage potentiostatic deposition 10h of 1.5V, after furnace temperature is cooled to room temperature, at cathode product ultrasound
After managing 100min, the vanadium metal that purity is 99.7% is obtained after cleaning 5 times repeatedly with dilute hydrochloric acid and deionized water.
It should be noted that those skilled in the art are that this hair may be implemented completely according to the various embodiments described above of the present invention
Bright independent claims and the full scope of appurtenance, realize process and the same the various embodiments described above of method；And the present invention is not
It elaborates and partly belongs to techniques well known.
The above, part specific embodiment only of the present invention, but scope of protection of the present invention is not limited thereto, appoints
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of, should all cover by what those skilled in the art
Within protection scope of the present invention.
Claims (8)
1. a kind of high-carbon slightly miscellaneous vanadium refining high-purity gold category vanadium method, it is characterised in that preparation step is as follows:
It (a) is 60%~75% by V content, slightly miscellaneous vanadium raw materials are crushed, are ground into powdery the high-carbon of C content 5%~20%, with
The pressure of 50-150MPa is shaped on high-pressure powder molding pressBlocks after, be placed in vacuum drying
Drying for standby in case；
(b) by blocky high-carbon, slightly miscellaneous vanadium block grain is placed in porous anode hanging basket, using molten alkali metal fused salt as electrolyte, rigid
Electrorefining in beautiful crucible, whole process carry out under an inert atmosphere；After furnace temperature rises to 500~800 DEG C, the anode that will be ready for
Hanging basket and cathode, which are submerged in fused salt, to be electrolysed, first with 0.1~1.5A/cm2Constant current density electrolysis 30min~
300min carries out preelectrolysis salt manufacturing, is then electrolysed 10h or more with the constant tank voltage of 0.2~1.5V；
(c) after being electrolysed, anode hanging basket and cathode is lifted, stops inert atmosphere protection after furnace temperature is cooled to room temperature, takes
Cathode and cathode product is separated out, is cleaned repeatedly after handling 10min~120min in water bath sonicator with dilute hydrochloric acid/deionized water
Obtain high purity vanadium metal.
2. a kind of high-carbon according to claim 1 slightly miscellaneous vanadium refining high-purity gold category vanadium method, it is characterised in that: step (a)
Thick miscellaneous vanadium raw materials are mainly by VxCy、VxOy、Al2O3、C、SiO2And other impurities composition.
3. a kind of high-carbon according to claim 1 or 2 slightly miscellaneous vanadium refining high-purity gold category vanadium method, it is characterised in that: thick miscellaneous
Based on mass fraction, V content is 60%~75% to each element, C content 5%~20% in vanadium raw materials, and O content is 5%~15%,
Al content is that 1%~3%, Si content is 1%~5%, and other impurities constituent content is 0.1%~2%.
4. a kind of high-carbon according to claim 1 slightly miscellaneous vanadium refining high-purity gold category vanadium method, it is characterised in that: anode hanging basket
With any one in metal molybdenum net, nickel screen, tungsten net, titanium net, and 0.25~0.075mm of aperture；Cathode is molybdenum sheet, nickel sheet, no
Become rusty steel disc, any one in vanadium piece.
5. a kind of high-carbon according to claim 1 slightly miscellaneous vanadium refining high-purity gold category vanadium method, it is characterised in that: step (b)
Control for Kiln Temperature is electrolysed at 650 DEG C~750 DEG C.
6. a kind of high-carbon according to claim 1 slightly miscellaneous vanadium refining high-purity gold category vanadium method, it is characterised in that: electrolyte is molten
Salt is sodium chloride, potassium chloride, cesium chloride, magnesium chloride, lithium chloride, calcium chloride, sodium fluoride, potassium fluoride, magnesium fluoride, lithium fluoride, fluorine
Change one or more of calcium, cesium fluoride.
7. a kind of high-carbon according to claim 1 slightly miscellaneous vanadium refining high-purity gold category vanadium method, it is characterised in that: step (b)
Middle preelectrolysis current density is 0.5~1.2A/cm2, electrolysis time is 60min~180min.
8. a kind of high-carbon according to claim 1 slightly miscellaneous vanadium refining high-purity gold category vanadium method, it is characterised in that: step (b)
0.4~1.0V of middle potentiostatic deposition tank voltage, electrolysis time are no less than 15h.
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