CN107142382A - Utilize the method for capacitive deionization technology separation and concentration tetravalence vanadium - Google Patents
Utilize the method for capacitive deionization technology separation and concentration tetravalence vanadium Download PDFInfo
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- CN107142382A CN107142382A CN201710283415.8A CN201710283415A CN107142382A CN 107142382 A CN107142382 A CN 107142382A CN 201710283415 A CN201710283415 A CN 201710283415A CN 107142382 A CN107142382 A CN 107142382A
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- vanadium
- capacitive deionization
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
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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 belongs to hydrometallurgy vanadium extraction field, and in particular to a kind of method of utilization capacitive deionization technology separation and concentration tetravalence vanadium, comprise the following steps：(1) carbon material and acid phosphine type extractant are mixed, obtains load carbon material (2) and mixed carbon material, binding agent, solvent is loaded by a certain percentage, uniformly spray (smearing) and obtain battery lead plate behind colelctor electrode surface, drying；(3) it is placed in battery lead plate is parallel in capacitive deionization module, connects dc source, then pH is passed through capacitive deionization module and carries out adsorption treatment for 1.2~3 tetravalence vanadium solution；(4) after the completion of adsorbing, the both positive and negative polarity of short circuit or reversal connection battery lead plate is passed through dilute sulfuric acid, carries out desorption process, finally gives rich vanadium liquid.The present invention have it is simple to operate, energy expenditure is small, medicament usage amount is few and advantages of environment protection.
Description
Technical field
The invention belongs to hydrometallurgy vanadium extraction field, and in particular to one kind utilizes capacitive deionization technology separation and concentration tetravalence
The method of vanadium.
Background technology
Capacitive deionization method is a kind of technology of new utilization electrical method desalination, and it is widely used in desalinization, work
Agricultural water desalination and domestic water desalination.Such as Publication No. CN104909439A patent describes a kind of brine waste
Electro-adsorption demineralization method, by carrying out the effect that Electro Sorb processing reaches desalination to brine waste.But capacitive deionization technology lacks
The weary application in terms of resource recycling.
Bone coal is that China is distinctive a kind of containing vanadium resource, and it is always grinding for scholars that vanadium is cleanly and efficiently extracted from bone coal
Study carefully focus.Direct process for extracting vanadium by acid leaching is one of widely used technique in current extracting vanadium from stone coal field, and the technique has leaching rate
The low advantage of high, energy consumption.During direct acidleach, most of vanadium in pickle liquor generally exists in the form of tetravalence vanadium.By
Content of vanadium is relatively low in bone coal, and vanadium concentration is generally relatively low in vanadium extraction pickle liquor, and foreign ion is more and content is high, is unfavorable for follow-up
Precipitation operation.Publication No. CN104018011A patent describes a kind of production method of vanadic anhydride, by extracting, washing
Wash, be stripped, acid ammonium salt precipitation, washing precipitate and six processes of calcining obtain vanadic anhydride product, wherein utilizing extraction
It is key link therein to take, wash, being stripped three steps separating-purifying vanadium from pickle liquor, and this process operation is complicated, and
A large amount of extractants are used, cost is higher, the loss for inevitably occurring extractant in production process in addition is dirty to environment
Dye is larger.
Traditional solvent extraction and separation, which is enriched with the separation process containing vanadium solution, has used a large amount of extractants, complex operation,
Cost is higher, and the loss of extractant is inevitably resulted from production process, and environmental pollution is larger.
The content of the invention
Because it is an object of the invention to provide a kind of simple to operate, energy consumption is low, dosing is less, environment-friendly vanadium point
From beneficiation technologies, the purpose of the separation and concentration vanadium from containing vanadium solution is reached.
To achieve the above object, the technical solution adopted by the present invention is comprised the concrete steps that：Utilize capacitive deionization technology point
From the method for enrichment tetravalence vanadium, it is characterised in that be the step of methods described：
(1) load carbon material is prepared：Carbon material and extractant are pressed into solid-to-liquid ratio (g/mL) 1:10~100 mixing, ultrasound is stirred
1~3h is mixed, speed of agitator is 40~70r/min, through separation of solid and liquid, by pure water of the solid of gained with 10~15 times of solid masses
Washed, the solid after washing is then dried in vacuo 3~7h at 40~65 DEG C, obtain loading carbon material；
(2) battery lead plate is prepared：The load carbon material obtained in step (1) is taken, load carbon material quality 9%~17% is added
Binding agent, according still further to load carbon material and organic solvent solid-to-liquid ratio (g/mL) 1:3~8 add organic solvent, ultrasonic agitation 1
~2h, speed of agitator is 120~130r/min, obtains loading carbon materials slurry body, then support materials slurry is uniformly sprayed or applied
Colelctor electrode two sides is put on, colelctor electrode is then dried in vacuo 3~5h at 40~65 DEG C, battery lead plate is obtained；
(3) processing contains vanadium solution：Multi-group electrode plate is placed in capacitive deionization module by 0.3~0.7cm of spacing is parallel,
Battery lead plate arranged in parallel is respectively turned on dc source both positive and negative polarity, direct current power source voltage is set as 0.5~1.7V, then
Pending vanadium solution containing tetravalence is passed through into capacitive deionization module to be handled, control vanadium solution containing tetravalence is in parallel electrode plate
Between flow velocity be 20~60cm/min, the vanadium solution containing tetravalence of outflow capacitive deionization module is passed through capacitive deionization module and entered again
Row circular treatment；(4) desorption of tetravalence vanadium：After battery lead plate reaches adsorption saturation, tetravalence will be contained in capacitive deionization module
Vanadium solution emptying, then battery lead plate short circuit or the reversal connection of dc source both positive and negative polarity will be connected to respectively, then pass to 8% (v/v's)
Dilute sulfuric acid is into capacitive deionization module, and the solution of outflow capacitive deionization module is passed through capacitive deionization module and circulated again
Desorption processing, obtains rich vanadium liquid.
By such scheme, the carbon material in the step (1) is activated carbon, carbon aerogels, CNT, mesoporous carbon, carbon
One or more of mixing in nanofiber.
By such scheme, the extractant in the step (1) is acid phosphine type kind of extractants, the extractant volume fraction
For
10%~30%, the solvent for diluting extractant is the one or more in ethanol, ether, acetone, petroleum ether.
By such scheme, the acid phosphine type kind of extractants of described extraction is one or more of mixed in P204, P507, P508
Close.
By such scheme, the binding agent described in step (2) is one kind in Kynoar, polytetrafluoroethylene (PTFE), solvent
For one kind in dimethyl acetamide, dimethylformamide, ethanol, current collection extremely high purity graphite piece or coated titanium electrode plate.
By such scheme, described pH containing vanadium solution is that vanadium exists with the cationic form of four valence states in 1.2~3, solution,
Vanadium concentration (in terms of element) be 500~3000mg/L, foreign ion concentration of iron be 50~5000mg/L, aluminum concentration be 500~
10000mg/L, phosphorus concentration (in terms of element) 50~1000mg/L.
The present invention is combined extraction with capacitive deionization technology, proposes a kind of new separation and concentration tetravalence from containing vanadium solution
The method of vanadium, by the capacitive deionization technology of the battery lead plate based on the loaded extractant acted on Characteristic Adsorption to molten containing vanadium
Liquid is handled, and reaches the purpose of separation and concentration vanadium.Its concrete principle is：In containing vanadium solution, tetravalence vanadium is with cationic form
In the presence of, phosphorus exists with anionic form, and under DC electric field effect, different charged ions shift to different battery lead plates respectively,
Realize that vanadium is separated with phosphorus.In addition, the extractant loaded on battery lead plate can be to VO2+Strong selective adsorption capacity is produced, meanwhile,
In electric field, load electrode plate surface can form the ion of electric double layer, the different quantity of electric charge of electric double layer absorption and hydrated ionic radius
Ability it is different, and containing the Al in vanadium solution3+、Fe3+、VO2+The quantity of electric charge and hydrated ionic radius there is larger difference, make
Selection absorption can also be carried out to vanadium by obtaining load electrode plate, so as to finally realize the separation of vanadium and foreign ion.
The beneficial effects of the present invention are：Present invention is primarily based on load carbon material electrode capacitance deionization to containing vanadium solution
The Adsorption of middle different ions reaches the purpose that separation and concentration is carried out to vanadium.The present invention is due to using capacitive deionization side
Method, thus it is shorter with flow, and the characteristics of simple to operate, the carbon electrode of loaded extractant has well to vanadium and foreign ion
Separating effect；Power-on voltage is only 0.5~1.7V in processing procedure, and adsorption process non-oxidation reduction reaction, therefore energy consumption is low；Inhale
Attached processing procedure need not use chemical reagent, therefore reagent consumption amount is smaller, environmentally friendly.
Brief description of the drawings
Fig. 1 is a kind of process flow diagram of the invention.
Embodiment
The invention will be further described with reference to the accompanying drawings and detailed description, not to the limit of its protection domain
System：
Embodiment 1：
A kind of method of utilization capacitive deionization technology separation and concentration tetravalence vanadium, specific steps such as Fig. 1 of its handling process
It is shown.
(1) load type active carbon is prepared：10g activated carbon is added in the P204 that 100mL volume fractions are 10~15%, 40
~50r/min 1~1.5h of ultrasonic agitation, through separation of solid and liquid, the solid of gained is washed with the pure water of 10~11.5 times of solid masses
Wash, the solid after washing is then dried in vacuo 3~4h at 40~50 DEG C, obtain loading P204 activated carbon；
(2) battery lead plate is prepared：The 5g supported active carbon powders obtained in step (2) are taken, 0.45~0.5g bonding is added
Agent Kynoar (PVDF), 15~25mL solvent dimethyl acetamide (DMAC), 120r/min ultrasonic agitations 1h is born
Activated carbon slurry is carried, then load type active carbon slurry is sprayed on the two sides of colelctor electrode high purity graphite piece, then by colelctor electrode 55
3~3.5h is dried in vacuo at~65 DEG C, battery lead plate is obtained；
(3) processing contains vanadium solution：By 5 groups, (being positive and negative polarities per component) battery lead plate is placed in so that pole plate spacing 0.5cm is parallel
In capacitive deionization module, battery lead plate arranged in parallel is respectively turned on dc source both positive and negative polarity, setting dc source electricity
Press as 1.5V, be passed through capacitive deionization module by pending containing vanadium solution and handled, control is containing vanadium solution in parallel pole
Flow velocity between plate is 20~35cm/min, and flow out capacitive deionization module is passed through the progress of capacitive deionization module again containing vanadium solution
Circular treatment, the volume containing vanadium solution is 1000mL, and vanadium concentration is 2590mg/L, and concentration of iron is 1327mg/L, and aluminum concentration is
5879mg/L, phosphorus concentration 423mg/L, pH containing vanadium solution are 1.2.
(4) desorption of tetravalence vanadium：After battery lead plate reaches adsorption saturation, it will be arranged in capacitive deionization module containing vanadium solution
Only, battery lead plate short circuit or the reversal connection of dc source both positive and negative polarity then respectively will be connected to, then again 8% (v/v) dilute sulfuric acid is passed through
Into capacitive deionization module, the solution of outflow capacitive deionization module is passed through capacitive deionization module and carried out at circulation desorption again
Reason, obtains rich vanadium liquid.
The present embodiment is as shown in the table to disposition containing vanadium solution.
Embodiment 2：
A kind of method of utilization capacitive deionization technology separation and concentration tetravalence vanadium, specific steps such as Fig. 1 of its handling process
It is shown：
(1) load CNT is prepared：10g CNT is added into the P507 that 100ml volume fractions are 15~22%
In, 50~60r/min, 1.5~2h of ultrasonic agitation, through separation of solid and liquid, by pure water of the solid of gained with 12~13 times of solid masses
Washed, the solid after washing is then dried in vacuo 4.5~5.5h at 50~60 DEG C, obtain loading P507 carbon nanometer
Pipe.
(2) battery lead plate is prepared：The 5g obtained in step (2) is taken to load CNT, the binding agent for adding 0.5~0.6g gathers
Vinylidene (PVDF), 25~30mL solvent dimethyl acetamide (DMAC), 125r/min ultrasonic agitations 1.5h is loaded
CNT slurry, then load CNT slurry is sprayed on the two sides of colelctor electrode coated titanium electrode, then colelctor electrode is existed
3.5~4.7h is dried in vacuo at 48~55 DEG C, battery lead plate is obtained.
(3) processing contains vanadium solution：By 6 groups, (being positive and negative polarities per component) battery lead plate is placed in so that pole plate spacing 0.3cm is parallel
In capacitive deionization module, battery lead plate arranged in parallel is respectively turned on dc source both positive and negative polarity, setting dc source electricity
Press as 1.3V, be passed through capacitive deionization module by pending containing vanadium solution and handled, control is containing vanadium solution in parallel pole
Flow velocity between plate is 35~50cm/min, and flow out capacitive deionization module is passed through the progress of capacitive deionization module again containing vanadium solution
Circular treatment, the volume containing vanadium solution is 1500mL, and vanadium concentration is 1574mg/L, and concentration of iron is 2024mg/L, and aluminum concentration is
6540mg/L, phosphorus concentration is 466mg/L, and pH containing vanadium solution is 1.8.
(4) desorption of tetravalence vanadium：After battery lead plate reaches adsorption saturation, it will be arranged in capacitive deionization module containing vanadium solution
Only, battery lead plate short circuit or the reversal connection of dc source both positive and negative polarity then respectively will be connected to, then again 8% (v/v) dilute sulfuric acid is passed through
Into capacitive deionization module, the solution of outflow capacitive deionization module is passed through capacitive deionization module and carried out at circulation desorption again
Reason, obtains rich vanadium liquid.
The present embodiment is as shown in the table to disposition containing vanadium solution.
Embodiment 3：
A kind of method of utilization capacitive deionization technology separation and concentration tetravalence vanadium, specific steps such as Fig. 1 of its handling process
It is shown：
(1) load carbon nano-fiber is prepared：By 10g carbon nano-fiber, it is 22~30% to add 100ml volume fractions
In P508,60~70r/min, 2~3h of ultrasonic agitation are pure with 13~15 times of solid masses by the solid of gained through separation of solid and liquid
Water is washed, and the solid after washing is then dried in vacuo into 5.5~7h at 40~50 DEG C, obtains loading P508 carbon nanometer
Fiber.
(2) battery lead plate is prepared：Take the 5g obtained in step (2) to load carbon nano-fiber, add 0.6~0.85g bonding
Agent Kynoar (PVDF), 30~40mL solvent dimethylacetamide ammonia (DMAC), 130r/min ultrasonic agitation 2h are born
Extractant material slurry is carried, then loaded extractant material slurry is sprayed on the two sides of colelctor electrode high purity graphite piece, then will collection
Electrode is dried in vacuo 4.7~5h at 55~65 DEG C, obtains battery lead plate.
(3) processing contains vanadium solution：By 10 groups, (being positive and negative polarities per component) battery lead plate is placed in so that pole plate spacing 0.7cm is parallel
In capacitive deionization module, battery lead plate arranged in parallel is respectively turned on dc source both positive and negative polarity, setting dc source electricity
Press as 1.7V, be passed through capacitive deionization module by pending containing vanadium solution and handled, control is containing vanadium solution in parallel loads
Flow velocity between battery lead plate is 50~60cm/min, and flow out capacitive deionization module is passed through capacitive deionization module again containing vanadium solution
Circular treatment is carried out, the volume of extracting vanadium from stone coal pickle liquor is 1000mL, and vanadium concentration is 550mg/L, and concentration of iron is 1915mg/L, aluminium
Concentration is 1307mg/L, and phosphorus concentration 120mg/L, pH containing vanadium solution are 2.5.
(4) desorption of tetravalence vanadium：After battery lead plate reaches adsorption saturation, it will be arranged in capacitive deionization module containing vanadium solution
Only, battery lead plate short circuit or the reversal connection of dc source both positive and negative polarity then respectively will be connected to, then again 8% (v/v) dilute sulfuric acid is passed through
Into capacitive deionization module, the solution of outflow capacitive deionization module is passed through capacitive deionization module and carried out at circulation desorption again
Reason, obtains rich vanadium liquid.
The present embodiment is as shown in the table to pickle liquor disposition
Using above-mentioned technical proposal, present invention is primarily based on load carbon material electrode capacitance deionization to containing vanadium (IV) solution
The Adsorption of middle different ions reaches the purpose that separation and concentration is carried out to vanadium.The present invention is due to using capacitive deionization side
Method, thus it is shorter with flow, and the characteristics of simple to operate, the carbon electrode of loaded extractant has well to vanadium and foreign ion
Separating effect；Power-on voltage is only 0.5~1.7V in processing procedure, and adsorption process non-oxidation reduction reaction, therefore energy consumption is low；Inhale
Attached processing procedure need not use chemical reagent, therefore reagent consumption amount is smaller, environmentally friendly.
Claims (6)
1. utilize the method for capacitive deionization technology separation and concentration tetravalence vanadium, it is characterised in that be the step of methods described：
(1) load carbon material is prepared：Carbon material and extractant are pressed into solid-to-liquid ratio (g/mL) 1:10~100 mixing, ultrasonic agitation 1~
3h, speed of agitator is 40~70r/min, through separation of solid and liquid, and the solid of gained is carried out with the pure water of 10~15 times of solid masses
Washing, is then dried in vacuo 3~7h by the solid after washing at 40~65 DEG C, obtains loading carbon material；
(2) battery lead plate is prepared：The load carbon material obtained in step (1) is taken, the viscous of load carbon material quality 9%~17% is added
Agent is tied, according still further to the solid-to-liquid ratio (g/mL) 1 of load carbon material and organic solvent:3~8 addition organic solvents, ultrasonic agitation 1~
2h, speed of agitator is 120~130r/min, obtains loading carbon materials slurry body, then support materials slurry is uniformly sprayed or smeared
On colelctor electrode two sides, colelctor electrode is then dried in vacuo 3~5h at 40~65 DEG C, battery lead plate is obtained；
(3) processing contains vanadium solution：Multi-group electrode plate is placed in capacitive deionization module by 0.3~0.7cm of spacing is parallel, will be flat
The battery lead plate of row arrangement is respectively turned on dc source both positive and negative polarity, is set direct current power source voltage as 0.5~1.7V, then will be treated
The vanadium solution containing tetravalence of processing is passed through capacitive deionization module and handled, and control vanadium solution containing tetravalence is between parallel electrode plate
Flow velocity is 20~60cm/min, and the vanadium solution containing tetravalence of outflow capacitive deionization module is passed through capacitive deionization module and followed again
Ring processing；
(4) desorption of tetravalence vanadium：After battery lead plate reaches adsorption saturation, the vanadium solution containing tetravalence in capacitive deionization module is arranged
Only, battery lead plate short circuit or the reversal connection of dc source both positive and negative polarity then respectively will be connected to, the dilute sulfuric acid for then passing to 8% (v/v) is arrived
In capacitive deionization module, the solution of outflow capacitive deionization module is passed through capacitive deionization module and carried out at circulation desorption again
Reason, obtains rich vanadium liquid.
2. the method for the utilization capacitive deionization technology separation and concentration tetravalence vanadium as described in claim 1, it is characterised in that described
Carbon material in step (1) is one or more of in activated carbon, carbon aerogels, CNT, mesoporous carbon, carbon nano-fiber
Mixing.
3. the method for the utilization capacitive deionization technology separation and concentration tetravalence vanadium as described in claim 1, it is characterised in that described
Extractant in step (1) is acid phosphine type kind of extractants, and the extractant volume fraction is 10%~30%, for diluting extraction
The solvent for taking agent is the one or more in ethanol, ether, acetone, petroleum ether.
4. the method for the utilization capacitive deionization technology separation and concentration tetravalence vanadium as described in claim 3, it is characterised in that described
The acid phosphine type kind of extractants of extraction be one or more of mixing in P204, P507, P508.
5. the method for the utilization capacitive deionization technology separation and concentration tetravalence vanadium as described in claim 1, it is characterised in that step
(2) binding agent described in is one kind in Kynoar, polytetrafluoroethylene (PTFE), and solvent is dimethyl acetamide, dimethyl methyl
One kind in acid amides, ethanol, current collection extremely high purity graphite piece or coated titanium electrode plate.
6. the method for the utilization capacitive deionization technology separation and concentration tetravalence vanadium as described in claim 1, it is characterised in that described
PH containing vanadium solution be 1.2~3, vanadium exists with the cationic form of four valence states in solution, vanadium concentration (in terms of element) is 500~
3000mg/L, foreign ion concentration of iron is 50~5000mg/L, and aluminum concentration is 500~10000mg/L, phosphorus concentration (in terms of element)
50~1000mg/L.
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|---|---|---|---|---|
| CN1184162A (en) * | 1996-12-06 | 1998-06-10 | 湖南省安化县东坪钒冶炼厂 | Vanadium pentoxide extracting method from stone coal vanadium ore |
| CN101078063A (en) * | 2007-06-29 | 2007-11-28 | 陈匡周 | Method for leaching vanadium from stone-like coal by oxidation transformation |
| CN105219959A (en) * | 2015-11-06 | 2016-01-06 | 武汉理工大学 | Adopt the method for Solvent-Impregnated Resins isolation of purified extracting vanadium from stone coal pickling liquor |
| CN105603191A (en) * | 2016-03-10 | 2016-05-25 | 武汉理工大学 | Pretreatment method for deacidification and impurity removal of acid leaching liquid of vanadium extracted from stone coal |
| CN106006735A (en) * | 2016-05-16 | 2016-10-12 | 武汉理工大学 | Method for preparing vanadium trioxide through bone coal vanadium extracting vanadium-rich liquid |
| CN106191439A (en) * | 2016-08-12 | 2016-12-07 | 武汉理工大学 | A kind of method of extracting vanadium from stone coal pickle liquor separating-purifying vanadium |
-
2017
- 2017-04-26 CN CN201710283415.8A patent/CN107142382B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1184162A (en) * | 1996-12-06 | 1998-06-10 | 湖南省安化县东坪钒冶炼厂 | Vanadium pentoxide extracting method from stone coal vanadium ore |
| CN101078063A (en) * | 2007-06-29 | 2007-11-28 | 陈匡周 | Method for leaching vanadium from stone-like coal by oxidation transformation |
| CN105219959A (en) * | 2015-11-06 | 2016-01-06 | 武汉理工大学 | Adopt the method for Solvent-Impregnated Resins isolation of purified extracting vanadium from stone coal pickling liquor |
| CN105603191A (en) * | 2016-03-10 | 2016-05-25 | 武汉理工大学 | Pretreatment method for deacidification and impurity removal of acid leaching liquid of vanadium extracted from stone coal |
| CN106006735A (en) * | 2016-05-16 | 2016-10-12 | 武汉理工大学 | Method for preparing vanadium trioxide through bone coal vanadium extracting vanadium-rich liquid |
| CN106191439A (en) * | 2016-08-12 | 2016-12-07 | 武汉理工大学 | A kind of method of extracting vanadium from stone coal pickle liquor separating-purifying vanadium |
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