CN109023410A - A method of the separation and Extraction vanadium from containing vanadium solution - Google Patents
A method of the separation and Extraction vanadium from containing vanadium solution Download PDFInfo
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- CN109023410A CN109023410A CN201811029539.4A CN201811029539A CN109023410A CN 109023410 A CN109023410 A CN 109023410A CN 201811029539 A CN201811029539 A CN 201811029539A CN 109023410 A CN109023410 A CN 109023410A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/006—Compounds containing, besides vanadium, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The present invention provides a kind of method of separation and Extraction vanadium from containing vanadium solution, comprising the following steps: step 1, to containing sulfuric acid is added in vanadium solution adjusts sulphur vanadium ratio using electrolytic cell by containing the vanadium electroreduction in vanadium solution to trivalent and obtains the solution of sulfur acid vanadium；The concentrated sulfuric acid is added into the solution of sulfur acid vanadium for step 2, improves sulphur vanadium ratio；After step 3, cooling, it is stirred to react a period of time, filtering obtains vanadic sulfate V2(SO4)3`(x)H2SO4.nH2O and impure crystalline mother solution, wherein 1 >=x >=0.The method energy depth separation of present invention separation and Extraction vanadium from containing vanadium solution obtains vanadic sulfate crystal, this method is simple and easy, and separation costs are cheap containing the vanadium and impurity in vanadium solution.
Description
Technical field
The present invention relates to hydrometallurgical technology more particularly to a kind of methods of the separation and Extraction vanadium from containing vanadium solution.
Background technique
Currently, the method for extracting vfanadium compound from containing vanadium solution is more, comprising: the red vanadium precipitation method, the ammonium salt precipitation method, iron
Salt precipitation method and calcium salt precipitation method.Wherein the effect of the Separation of vanadium and molybdenum of the red vanadium precipitation method, the ammonium salt precipitation method is bad, the separation of vanadium potassium
There is also some problems for effect.Molysite deposition method and calcium salt precipitation method are more suitable for low concentration vanadium solution, such as vanadium-containing water (vanadium
Content is less than or equal to 20g/L more) processing, and obtained product purity is poor, keeps its application limited.
All-vanadium redox flow battery electrolyte is a kind of sulfate liquor rich in mixed valence vanadium, and the traditional method of vanadium extraction is first
First precipitating obtains ammonium vanadate, obtains barium oxide by calcining, obtains electrolyte solution through acid dissolution, or by electrolysis, is passed through
The process crossed is longer, and production operation is responsible for, higher cost, and generates a large amount of ammoniated wastewater, and processing cost is high, in environmental protection
In the case that supervision is increasingly severe, cost is higher and higher.A kind of urgently good separating effect, the low vanadium extraction containing vanadium solution of separation costs
Method.
Summary of the invention
It is an object of the present invention to separate effect for the different degrees of presence containing the method for extracting vfanadium compound in vanadium solution
The problem that fruit is poor, separation costs are high, a kind of method for proposing separation and Extraction vanadium from containing vanadium solution, the separation of this method energy depth contain
Vanadium and impurity in vanadium solution obtain vanadic sulfate crystal, and this method is simple and easy, and separation costs are cheap.
To achieve the above object, the technical solution adopted by the present invention is that: a kind of side of the separation and Extraction vanadium from containing vanadium solution
Method, comprising the following steps:
Step 1, to containing sulfuric acid is added in vanadium solution, adjust sulphur vanadium ratio, will be electrolysed containing the vanadium in vanadium solution using electrolytic cell
Trivalent is reverted to, the solution of sulfur acid vanadium is obtained；
The concentrated sulfuric acid is added into the solution of sulfur acid vanadium for step 2, improves sulphur vanadium ratio；
After step 3, cooling, it is stirred to react a period of time, filtering obtains vanadic sulfate V2(SO4)3`(x)H2SO4.nH2O and contain
The crystalline mother solution of impurity, wherein 1 >=x >=0.
Further, it is prepared by being dissolved in water containing vanadium raw materials containing vanadium solution in step 1.It is described containing vanadium raw materials include but
It is not limited to containing V2O5Petroleum burnning ash, industrial ammonium metavanadate, industry V2O5, industrial ammonium poly-vanadate, v-bearing steel slag, one in vanadium slag
Kind is a variety of.The V2O5Petroleum burnning ash water is dissolved in after sodium roasting, be prepared containing vanadium solution (sodium vanadate solution).
The industry ammonium metavanadate adding sodium hydroxide and water are dissolved into containing vanadium solution.The industry V2O5Adding sodium hydroxide and water are dissolved into
Containing vanadium solution.
It further, is 0.1-5mol/L, preferably 1-3mol/L containing vanadium ion concentration in vanadium solution in step 1.
Further, the ratio between amount of substance of sulphur and vanadium is S:V >=1.5, preferably 5 >=S:V >=1.5 in step 1.
Further, electrolytic parameter is current density 50-150A/m in step 12, 0-50 DEG C, it is electrolysed 2-10h, preferably
Current density 70-100A/m2, 10-50 DEG C, it is electrolysed 4-6h, preferred current density 80A/m2, room temperature, electrolysis 5h.
Further, the sulfuric acid concentration in step 1 is 50-92.5%wt.
Further, the concentrated sulfuric acid concentration in step 2 is 92.5-99.8%wt.
Further, the range of the ratio between amount of substance of the sulphur in step 2 and vanadium be 10 >=S:V > 1.5, preferably 6 >=
S:V > 3.
Further, the cooling temperature in step 3 is 0-60 DEG C, preferably 10-30 DEG C.
Further, the reaction time in step 3 is 0.1-48h, preferably 4-12h.
The method of present invention separation and Extraction vanadium from containing vanadium solution, by dissolving, crystallize, realize containing vanadium in vanadium solution with
The separation of impurity, and vanadic sulfate solid is obtained, which dissolves through water, can get all-vanadium redox flow battery electrolyte.This
The method of invention separation and Extraction vanadium from containing vanadium solution has the advantage that compared with prior art
1) present invention will be reduced into trivalent containing the vanadium in vanadium solution, form sulfuric acid vanadium solution, then pass through by electroreduction
Sulfuric acid, which is added, promotes vanadic sulfate supersaturated, and crystalline deposit obtains crystal in the form of sulfuric acid, vanadic sulfate double salt, realizes vanadium and solution
And the separation of impurity；
2) present invention can depth separation containing the vanadium and impurity in vanadium solution, obtain vanadic sulfate crystal, the process avoid using
Ammonium salt also reduces production cost while reducing the discharge and energy consumption of the three wastes；
3) the vanadic sulfate crystal purity that the present invention is prepared is high, can be directly used in the system of all-vanadium redox flow battery electrolyte
It is standby；
4) present invention method of separation and Extraction vanadium from containing vanadium solution is simple and easy, and separation costs are cheap, can be generally applicable
In containing V2O5Petroleum burnning ash, industrial ammonium metavanadate, industry V2O5, industrial ammonium poly-vanadate, v-bearing steel slag, vanadium slag etc. contain vanadium raw materials
The recycling of middle vanadium.
Detailed description of the invention
Fig. 1 is the XRD diagram piece of 1 gained vanadic sulfate crystal of embodiment；
Fig. 2 is the scanning electron microscope (SEM) photograph (1000 times) of 1 gained vanadic sulfate crystal of embodiment.
Specific embodiment
The present invention is further described with reference to embodiments:
Embodiment 1
This implementation discloses a kind of method of separation and Extraction vanadium from containing vanadium solution, to separate the vanadium in industrial ammonium metavanadate
For (the industry ammonium metavanadate: molybdenum content 1.2%wt, with V2O5Meter concentration is 73.5%wt).Specifically from containing in vanadium solution
The method of separation and Extraction vanadium the following steps are included:
Step 1, industrial ammonium metavanadate adding sodium hydroxide and water are dissolved into containing vanadium solution, and sodium hydroxide is added by ammonium metavanadate
All dissolutions, it is described to contain in vanadium solution with V2O5Meter concentration is 188g/L, takes volume 1L's to contain vanadium solution；
Step 2, at room temperature is stirred evenly to above-mentioned containing 92.5%wt sulfuric acid 240ml is added in vanadium solution；
Step 3 contains vanadium solution as in electrolytic cell for what step 2 obtained, and using electrolytic cell electroreduction, electrolytic condition is such as
Under:
Anolyte is 5%wt aqueous sulfuric acid, electrode area 100cm2, electric current 1A, room temperature, constant-current electrolysis, acquisition sulfur-bearing
The solution of sour vanadium, with V2O5Meter concentration is 151g/L；
Step 4, obtained to step 3 electrolysis containing the 150ml concentrated sulfuric acid (99.8%wt) is added in vanadium solution, stir evenly,
2g vanadic sulfate crystal is added as crystal seed, is cooled to room temperature, stirs 36h, filtering obtains vanadic sulfate crystal V2(SO4)3`(x)
H2SO4.nH2O and crystalline mother solution.
If Fig. 1 and the visible obtained material of table 1 are vanadic sulfate, the impurity content of product is lower, meets all-vanadium flow battery electricity
The requirement for solving liquid, can be calculated x=0.069, n=9.8 by table 1.Fig. 2 is the scanning electron microscope of the present embodiment vanadic sulfate crystal
Figure.
The detection of content of element result (unit %wt) of 1 embodiment of table, 1 gained vanadic sulfate crystal
| V | 17.80% |
| SO4 2 | 52.47% |
| K | 0.0009% |
| Na | 0.0005% |
| Fe | 0.0009% |
| Al | 0.0007% |
| Mo | 0.0004% |
| Cr | 0.0003% |
| Mn | 0.0000% |
| Ca | 0.0011% |
| W | 0.0003% |
| Mg | 0.0004% |
Embodiment 2
This implementation discloses a kind of method of separation and Extraction vanadium from containing vanadium solution, to separate in petroleum burnning ash for vanadium,
The following steps are included:
Step 1, with V2O5The petroleum burnning ash for counting 50%wt, by sodium roasting, with V2O5The content of meter becomes 35%wt,
It is dissolved in water, obtains sodium vanadate solution, with V2O5Meter concentration is 281g/L, takes volume 1L's to contain vanadium solution；
Step 2, at room temperature is stirred evenly to above-mentioned containing 92.5%wt sulfuric acid 525ml is added in vanadium solution；
Step 3 contains vanadium solution as in electrolytic cell for what step 2 obtained, and using electrolytic cell electroreduction, electrolytic condition is such as
Under:
Anolyte is 5%wt aqueous sulfuric acid, electrode area 100cm2, electric current 1A, room temperature, constant-current electrolysis, acquisition sulfur-bearing
The solution of sour vanadium, concentration are；
Step 4, obtained to step 3 electrolysis containing the 200ml concentrated sulfuric acid (99.8%wt) is added in vanadium solution, stir evenly,
2g vanadic sulfate crystal is added as crystal seed, is cooled to room temperature, for 24 hours, filtering obtains vanadic sulfate crystal V for stirring2(SO4)3`(x)
H2SO4.nH2O and crystalline mother solution.
If the visible obtained material vanadic sulfate impurity content of table 2 is lower, meet the requirement of all-vanadium redox flow battery electrolyte.By table
2 can be calculated x=1, n=11.
The detection of content of element result (unit %wt) of 2. embodiment of table, 2 gained vanadic sulfate crystal
Embodiment 3
This implementation discloses a kind of method of separation and Extraction vanadium from containing vanadium solution, to separate industrial V2O5(contain potassium 2.1%
Wt, with V2O5Count content 98.3%wt) in for vanadium, comprising the following steps:
Step 1, to industrial V2O5Adding sodium hydroxide solid and water are dissolved into solution, contain V2O5Concentration is 450g/L, takes volume
1L's contains vanadium solution；
Step 2, at room temperature is stirred evenly to above-mentioned containing 92.5%wt sulfuric acid 565ml is added in vanadium solution；
Step 3 contains vanadium solution as in electrolytic cell for what step 2 obtained, and using electrolytic cell electroreduction, electrolytic condition is such as
Under:
Anolyte is 5%wt aqueous sulfuric acid, electrode area 100cm2, electric current 1A, room temperature, constant-current electrolysis, acquisition sulfur-bearing
The solution of sour vanadium, V2O5Meter concentration is 314g/L；
Step 4, obtained to step 3 electrolysis containing the 175ml concentrated sulfuric acid (99.8%wt) is added in vanadium solution, stir evenly,
2g vanadic sulfate crystal is added as crystal seed, is cooled to room temperature, stirs 36h, filtering obtains vanadic sulfate crystal V2(SO4)3`(x)
H2SO4.nH2O and crystalline mother solution.
Obtained material vanadic sulfate impurity content as seen in Table 3 is lower, meets the requirement of all-vanadium redox flow battery electrolyte, can be with
X=0.394, n=10.5 is calculated.
The detection of content of element result (unit %wt) of 3. embodiment of table, 3 gained vanadic sulfate crystal
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of method of the separation and Extraction vanadium from containing vanadium solution, which comprises the following steps:
Step 1, to containing sulfuric acid is added in vanadium solution, adjust sulphur vanadium ratio, will be containing the vanadium electroreduction in vanadium solution using electrolytic cell
To trivalent, the solution of sulfur acid vanadium is obtained；
The concentrated sulfuric acid is added into the solution of sulfur acid vanadium for step 2, improves sulphur vanadium ratio；
After step 3, cooling, it is stirred to react a period of time, filtering obtains vanadic sulfate V2(SO4)3`(x)H2SO4.nH2O and impure
Crystalline mother solution, wherein 1 >=x >=0.
2. according to claim 1 from containing vanadium solution separation and Extraction vanadium method, which is characterized in that it is described to be containing vanadium raw materials
Containing V2O5Petroleum burnning ash, industrial ammonium metavanadate, industry V2O5, industrial ammonium poly-vanadate, v-bearing steel slag, one of vanadium slag or more
Kind.
3. according to claim 1 from containing vanadium solution separation and Extraction vanadium method, which is characterized in that in step 1 containing vanadium it is molten
Liquid concentration is 0.1-5mol/L.
4. according to claim 1 from containing vanadium solution separation and Extraction vanadium method, which is characterized in that sulphur and vanadium in step 1
The ratio between the amount of substance be S:V >=1.5.
5. according to claim 1 from containing vanadium solution separation and Extraction vanadium method, which is characterized in that in step 1 be electrolysed ginseng
Number is current density 50-150A/m2, 0-50 DEG C, it is electrolysed 2-10h.
6. according to claim 1 from containing vanadium solution separation and Extraction vanadium method, which is characterized in that the sulfuric acid in step 1
Concentration is 50-92.5%wt.
7. according to claim 1 from containing vanadium solution separation and Extraction vanadium method, which is characterized in that the dense sulphur in step 2
Acid concentration is 92.5-99.8%wt.
8. according to claim 1 from containing vanadium solution separation and Extraction vanadium method, which is characterized in that sulphur in step 2 and
The range of the ratio between the amount of substance of vanadium is 10 >=S:V >=1.5.
9. according to claim 1 from containing vanadium solution separation and Extraction vanadium method, which is characterized in that the cooling in step 3
Temperature is 0-60 DEG C.
10. according to claim 1 from containing vanadium solution separation and Extraction vanadium method, which is characterized in that the reaction in step 3
Time is 0.1-48h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101126124A (en) * | 2007-07-06 | 2008-02-20 | 北京普能世纪科技有限公司 | Method for preparing high-purity electrolyte for vanadium battery from stone-like coal |
| CN106350680A (en) * | 2016-08-31 | 2017-01-25 | 大连博融新材料股份有限公司 | Method for extracting valuable metals from petroleum ash through sodium salt roasting |
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2018
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101126124A (en) * | 2007-07-06 | 2008-02-20 | 北京普能世纪科技有限公司 | Method for preparing high-purity electrolyte for vanadium battery from stone-like coal |
| CN106350680A (en) * | 2016-08-31 | 2017-01-25 | 大连博融新材料股份有限公司 | Method for extracting valuable metals from petroleum ash through sodium salt roasting |
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| 刘然 等: "五氧化二钒电解制备全钒液流电池V3+电解液", 《高效化学工程学报》 * |
| 向小绢 等: "V2(SO4)3的制备及其在固体钒电池中的应用", 《广州化学》 * |
| 赵秦生 等: "《钒冶金（第1版）》", 30 November 2015, 中南大学出版社 * |
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Address after: No.20, Yingchun street, Huayuankou Economic Zone, Dalian, Liaoning, 116450 Patentee after: Dalian Rongke Energy Storage Group Co.,Ltd. Address before: No.20, Yingchun street, Huayuankou Economic Zone, Dalian, Liaoning, 116450 Patentee before: DALIAN BOLONG NEW MATERIALS Co.,Ltd. |
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