CN108336426A - The preparation method and its oxygen vanadium sulfate crystals obtained of a kind of vanadic sulfate - Google Patents
The preparation method and its oxygen vanadium sulfate crystals obtained of a kind of vanadic sulfate Download PDFInfo
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- CN108336426A CN108336426A CN201810121167.1A CN201810121167A CN108336426A CN 108336426 A CN108336426 A CN 108336426A CN 201810121167 A CN201810121167 A CN 201810121167A CN 108336426 A CN108336426 A CN 108336426A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
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Abstract
The invention discloses a kind of preparation method of vanadic sulfate and its oxygen vanadium sulfate crystals obtained, are related to inorganic material separating and purifying technology field.The preparation method of the vanadic sulfate includes the following steps：Tetravalence vanadium solution will be obtained after pentavalent vanadium solution and reducing agent hybrid reaction；After tetravalence vanadium solution is purified, adjustment pH is 78 precipitation tetravalence vanadium hydrates；It is recrystallized with sulfuric acid dissolution tetravalence vanadium hydrate.Method is simple, is easy to industrial operation, what is more important raw material is low without cost for purification, product crystal epigranular.The present invention also provides a kind of oxygen vanadium sulfate crystals, are prepared by above-mentioned preparation method, and crystal purity is high and production is at low cost.
Description
Technical field
The present invention relates to inorganic material separating and purifying technology field, and the preparation method of more particularly to a kind of vanadic sulfate and
Its oxygen vanadium sulfate crystals obtained.
Background technology
Oxygen vanadium sulphate solution is not only the intermediate products of tetravalence V electrolyte and other valence state V electrolytes, also can be used as sulphur
The raw material of sour vanadyl crystal.On domestic market the preparation of oxygen vanadium sulphate solution mainly using vanadic anhydride as raw material,
Dissolving restores to obtain tetravalence V electrolyte in sulfuric acid, such as：Patent CN103420415B, CN102951680B and
CN101805020B；It is re-dissolved in sulfuric acid after vanadic anhydride can also being restored and obtains tetravalence V electrolyte, such as：Patent
CN103401010B。
But purify of high cost there is feedstock purification and product in the preparation process of vanadic sulfate, and yield is low
The problem of.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of vanadic sulfate, it is intended to promote the yield of vanadic sulfate simultaneously
Reduce purifying cost.
Another object of the present invention is to provide a kind of oxygen vanadium sulfate crystals, and preparation method is simple and easy to do, the grain of product
It spends uniform and at low cost.
The present invention solves its technical problem using following technical scheme to realize.
The present invention proposes a kind of preparation method of vanadic sulfate, includes the following steps：
Tetravalence vanadium solution will be obtained after pentavalent vanadium solution and reducing agent hybrid reaction；
After tetravalence vanadium solution is purified, adjustment pH is that tetravalence vanadium hydrate is precipitated in 7-8；
It is recrystallized with sulfuric acid dissolution tetravalence vanadium hydrate.
The present invention also proposes a kind of oxygen vanadium sulfate crystals, is prepared using the preparation method of above-mentioned vanadic sulfate.
The embodiment of the present invention provides a kind of advantageous effect of the preparation method of vanadic sulfate：It is by pentavalent vanadium solution reduction
After tetravalence vanadium solution, tetravalence vanadium solution is purified and tetravalence vanadium hydrate is precipitated by adjusting pH, then carries out weight with sulfuric acid
Crystallization obtains oxygen vanadium sulfate crystals.Method is simple, is easy to industrial operation, what is more important raw material without purification, at
This low, product crystal epigranular.The present invention also provides a kind of oxygen vanadium sulfate crystals, by prepared by above-mentioned preparation method
, crystal purity is high and production is at low cost.
Description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the process flow chart provided by the invention for preparing vanadic sulfate.
Specific implementation mode
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Preparation method to a kind of vanadic sulfate provided in an embodiment of the present invention and its oxygen vanadium sulfate crystals obtained below
It is specifically described.
A kind of preparation method of vanadic sulfate provided in an embodiment of the present invention comprising following steps：
S1, tetravalence vanadium solution will be obtained after pentavalent vanadium solution and reducing agent hybrid reaction.
It should be pointed out that redox reaction occurs at normal temperatures after pentavalent vanadium solution is mixed with reducing agent, obtain
Tetravalence vanadium solution, reaction time 2-5h.The dosage of pentavalent vanadium solution and reducing agent can be according to the proportioning in chemical equation
It is added, and the appropriate excessive vanadium Restore All to ensure five prices of reducing agent is tetravalence vanadium, detailed process is not done excessive superfluous
It states.
Specifically, pentavalent vanadium solution is any one in sodium vanadate solution, vanadic acid potassium solution and pentavalent vanadium sulfuric acid solution
Kind.Pentavalent vanadium in the present invention is not to use vanadic anhydride for raw material, is not related to the processes such as the purifying technique of raw material, and produce
Cost significantly reduces.
Specifically, any one of reducing agent in iron powder, oxalic acid, sodium sulfite, hydrogen sulfide and sulfur dioxide, preferably
For oxalic acid.Oxalic acid is used not generate the waste of pollution environment for reducing agent, and safe operation is reliable, what is more important oxalic acid
Mild condition can react under 70-90 DEG C of temperature condition.
S2, it after purifying tetravalence vanadium solution, adjusts PH and tetravalence vanadium hydrate is precipitated for 7-8.
You need to add is that under weak basic condition, tetravalence vanadium hydrate can be precipitated in tetravalence vanadium solution, and tetravalence vanadium is molten
Crystallization can ensure to obtain the purity of hydrate again after liquid purification.The hydrate starts to be precipitated in pH value 3 or so, is 7 in pH
When amount of precipitation it is maximum, up to 99% or more.
Specifically, during adjustment pH is 7-8 it is adjusted using alkaline solution, it is preferable that alkaline solution is weak
Alkaline solution, it is highly preferred that alkaline solution is ammonium hydroxide.
Specifically, the process of tetravalence vanadium solution purification is by the way of extracting-back extraction or ion exchange.The mistake of ion exchange
Journey is swapped by means of the ion in the ion and weak solution in Solid-state Ion-exchange agent, to reach extraction or removal solution
In certain ions purpose.Inventor has found the purity higher for the product being obtained by extraction by the way of extracting-back extraction.
Specifically, extracting-back extraction process is extracted using phosphoric acid ester extractant, preferably two (2- ethylhexyls)
Phosphate and tributyl phosphate mixed extractant, preferred solvent are kerosene；And compare (O/A) in extraction process is 0.5-2:1,
Extraction time is 2-10min.Inventor has found that carrying out extraction using above-mentioned extractant can ensure to finally obtain the pure of crystal
Degree.
Specifically, a concentration of 0.1-0.5mol/L of di-(2-ethylhexyl)phosphoric acid ester, tributyl phosphate it is a concentration of
0.1-0.3mol/L；Preferably, a concentration of 0.25-0.35mol/L of di-(2-ethylhexyl)phosphoric acid ester, tributyl phosphate it is dense
Degree is 0.15-0.25mol/L.
Further, extracting-back extraction process further includes that the organic phase obtained after the extraction is stripped with sulfuric acid, preferably
Ground, a concentration of 0.5-4mol/L of sulfuric acid, and compare (O/A) in stripping process is 1-10:1；It is highly preferred that in stripping process
Compared to (O/A) be 4-6:1.
Further, as shown in Fig. 1, extracting-back extraction process includes multiple extraction and separation, preferably 3-5 times, and each
Extraction and separation include that extraction and separation and back extraction detach.Back extraction process is to be extracted the extract liquor that extraction and separation obtain again
It takes, to promote the purity of extraction process product, the extract liquor obtained after extraction and separation several times carries out crystallization.
Wherein, first time extraction separation process includes level-one extraction and two level extraction, and two level extraction process is by level-one
The raffinate that extraction process obtains is extracted, and the strip liquor that two level extraction process is obtained returns to the extraction of level-one extraction process
It takes in raw material.
It should be pointed out that the extraction back extraction separating technology provided in the present invention, what is more important easy to operation
The rate of recovery of vanadium is high, is 99% or more, when the high-purity sulphuric acid vanadyl solution concentration of acquisition is 2mol/L, content of impurities is less than
10ppm。
Failure V electrolyte is adjusted through electric discharge, reduction or oxidation it should be pointed out that may be used in other embodiments
The whole purification process for tetravalence vanadium solution.
S3, it is crystallized with sulfuric acid dissolution tetravalence vanadium hydrate.
Specifically, tetravalence vanadium hydrate is carried out that oxygen vanadium sulfate crystals, reaction principle class is obtained by the reaction with sulfuric acid dissolution
Like recrystallization.Preferably, the concentrated sulfuric acid may be used to be dissolved, ensures the granularity of crystallization.
The embodiment of the present invention additionally provides a kind of oxygen vanadium sulfate crystals, using the preparation method preparation of above-mentioned vanadic sulfate
, have the advantages that the purity of product is high and production cost is low etc..
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
The present embodiment provides a kind of preparation methods of vanadic sulfate comprising following steps：
First, the sodium vanadate solution of 0.5mol/L and reducing agent will be added under agitation, the vanadium of five prices is whole
It is reduced to tetravalence vanadium.Wherein, reducing agent is iron powder.Then, using the method for ion exchange by after tetravalence vanadium solution purified solution,
It is adjusted after pH is 7-8 with the ammonium hydroxide of 0.3mol/L and tetravalence vanadium hydrate is precipitated.Finally, with after concentrated sulfuric acid dissolution tetravalence vanadium hydrate
It carries out being recrystallized to give oxygen vanadium sulfate crystals product.
Embodiment 2
The present embodiment provides a kind of preparation methods of vanadic sulfate comprising following steps：
First, the sodium vanadate solution of 0.5mol/L and reducing agent will be added under agitation, the vanadium of five prices is whole
It is reduced to tetravalence vanadium.Wherein, reducing agent is iron powder.
Then, pH is adjusted with the ammonium hydroxide of 0.3mol/L by after tetravalence vanadium solution purified solution using the method for extraction back extraction
For tetravalence vanadium hydrate is precipitated after 7-8；
Wherein, operating method during extracting back extraction is as follows：
By 500mL mixed extractants (containing 0.3mol/L di-(2-ethylhexyl)phosphoric acids and 0.2mol/L tributyl phosphates,
Solvent is kerosene), it is added in tetravalence vanadium solution (500mL), carries out first time extraction and separation, extractant is compared with leachate
(O/A) it is 0.5:1, it vibrates 10 minutes, stands liquid separation and obtain extract liquor (organic phase) and extraction extraction raffinate.
Organic phase is stripped, and is eluted using 1mol/L sulfuric acid, and 100mL is added in the organic phase of 500mL
1.5mol/L sulfuric acid carries out back extraction separation for the first time, and (O/A) is 2 to organic phase compared with water:1, after vibrating 2 minutes, liquid separation is stood,
Remove the strip liquor of layer 100mL.
And extract extraction raffinate carry out two level extraction and separation, that is, extract extraction raffinate 100mL (adding deionized water to 500mL) again with
500mL mixed extractants mixing oscillation 5 minutes, stands liquid separation.100mL is added in the organic phase that two level extraction and separation obtain
It (is 1 compared to O/A that 2mol/L sulfuric acid, which is eluted,:1), oscillation after five minutes, stands liquid separation, and strip liquor 100mL is added to for the first time
In the raw material of extraction and separation.
By the strip liquor 100mL (adding deionized water to 500mL) and 500mL mixed extractants that first time extraction and separation obtain
Mixing carries out second of extraction and separation, and extractant (O/A) compared with leachate is 0.5:1, it vibrates 5 minutes, stands liquid separation.It utilizes
1.5mol/L sulfuric acid is eluted, and the organic of 500mL is added to 100mL 1.5mol/L sulfuric acid, and organic phase is compared with water (O/A)
It is 10:1, oscillation after five minutes, stands liquid separation, removes the strip liquor of layer 100mL.
It will be stripped isolated strip liquor 100mL (adding deionized water to 500mL) and 500mL mixed extractants for the second time
Mixing carries out third time extraction and separation, and extractant (O/A) compared with leachate is 1:1, it vibrates 10 minutes, stands liquid separation.It utilizes
1.5mol/L sulfuric acid is eluted, and the organic of 500mL is added to 100mL 1.5mol/L sulfuric acid, and organic phase is compared with water (O/A)
It is 5:1, oscillation after ten minutes, stands liquid separation, removes the strip liquor of layer 100mL.
Finally, with being crystallized to obtain oxygen vanadium sulfate crystals product after concentrated sulfuric acid dissolution tetravalence vanadium hydrate.
Embodiment 3
It is roughly the same with embodiment 2 the present embodiment provides a kind of preparation method of vanadic sulfate, the difference is that：
Pentavalent vanadium solution is vanadic acid potassium solution, and reducing agent is oxalic acid.
Embodiment 4
It is roughly the same with embodiment 2 the present embodiment provides a kind of preparation method of vanadic sulfate, the difference is that：
Pentavalent vanadium solution is pentavalent vanadium sulfuric acid solution, and reducing agent is sodium sulfite.
Embodiment 5
It is roughly the same with embodiment 2 the present embodiment provides a kind of preparation method of vanadic sulfate, the difference is that：
Pentavalent vanadium solution is sodium vanadate solution, and reducing agent is hydrogen sulfide.
Embodiment 6
It is roughly the same with embodiment 2 the present embodiment provides a kind of preparation method of vanadic sulfate, the difference is that：
Pentavalent vanadium solution is sodium vanadate solution, and reducing agent is sulfur dioxide.
Embodiment 7
It is roughly the same with embodiment 2 the present embodiment provides a kind of preparation method of vanadic sulfate, the difference is that：
Pentavalent vanadium solution is vanadic acid potassium solution, and reducing agent is oxalic acid, and mixed extractant (contains (the 2- second of 0.1mol/L bis-
Base hexyl) phosphoric acid and 0.1mol/L tributyl phosphates, solvent be kerosene).
Embodiment 8
It is roughly the same with embodiment 2 the present embodiment provides a kind of preparation method of vanadic sulfate, the difference is that：
Pentavalent vanadium solution is vanadic acid potassium solution, and reducing agent is oxalic acid, and mixed extractant (contains (the 2- second of 0.5mol/L bis-
Base hexyl) phosphoric acid and 0.5mol/L tributyl phosphates, solvent be kerosene).
Test example 1
The purity that oxygen vanadium sulfate crystals are prepared in embodiment 1-8 is measured using conventional method, be once 98.6%,
99.0%, 99.8%, 99.4,99.5%, 99.4%, 99.6,99.7%.
It can be seen that the purity for the oxygen vanadium sulfate crystals that the preparation method in the present invention obtains is higher, 98.5% with
On, wherein being more suitable for the purification process of reaction system using the method for purification of repeatedly extraction back extraction, finally obtained crystal is uniform,
And purity is all 99% or more.In addition, by embodiment 2-8 it is found that using pentavalent vanadium solution for vanadic acid potassium solution, reducing agent is grass
The purity higher for the oxygen vanadium sulfate crystals that acid obtains, and it is relatively low both as the cost of raw material.
In conclusion a kind of preparation method of vanadic sulfate provided by the invention, is tetravalence vanadium by pentavalent vanadium solution reduction
After solution, tetravalence vanadium solution is purified and tetravalence vanadium hydrate is precipitated by adjusting PH, then with sulfuric acid recrystallize
To oxygen vanadium sulfate crystals.Method is simple, is easy to industrial operation, and what is more important raw material is low without cost for purification, production
Product crystal size is uniform.
The present invention also provides a kind of oxygen vanadium sulfate crystals, are prepared by above-mentioned preparation method, and crystal purity is high
And production is at low cost.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of vanadic sulfate, which is characterized in that include the following steps：
Tetravalence vanadium solution will be obtained after pentavalent vanadium solution and reducing agent hybrid reaction；
After the tetravalence vanadium solution is purified, adjustment pH is that tetravalence vanadium hydrate is precipitated in 7-8；
The tetravalence vanadium hydrate described in sulfuric acid dissolution is recrystallized.
2. the preparation method of vanadic sulfate according to claim 1, which is characterized in that the pentavalent vanadium solution is selected from vanadic acid
Any one in sodium solution, vanadic acid potassium solution and pentavalent vanadium sulfuric acid solution.
3. the preparation method of vanadic sulfate according to claim 1, which is characterized in that the reducing agent is selected from iron powder, grass
Any one in acid, sodium sulfite, hydrogen sulfide and sulfur dioxide, preferably oxalic acid.
4. the preparation method of vanadic sulfate according to claim 1, which is characterized in that by tetravalence vanadium solution purification
Process is by the way of extracting-back extraction or ion exchange.
5. the preparation method of vanadic sulfate according to claim 4, which is characterized in that the extracting-back extraction process is profit
It is extracted with phosphoric acid ester extractant, preferably di-(2-ethylhexyl)phosphoric acid ester and tributyl phosphate mixed extractant, it is excellent
It is kerosene to select solvent；
And compare (O/A) in extraction process is 0.5-2:1, extraction time 2-10min.
6. the preparation method of vanadic sulfate according to claim 5, which is characterized in that the di-(2-ethylhexyl)phosphoric acid
A concentration of 0.1-0.5mol/L of ester, a concentration of 0.1-0.3mol/L of the tributyl phosphate；
Preferably, a concentration of 0.25-0.35mol/L of the di-(2-ethylhexyl)phosphoric acid ester, the tributyl phosphate it is dense
Degree is 0.15-0.25mol/L.
7. the preparation method of vanadic sulfate according to claim 5, which is characterized in that the extracting-back extraction process is also wrapped
The organic phase obtained after the extraction is included to be stripped with sulfuric acid, it is preferable that a concentration of 0.5-4mol/L of the sulfuric acid, and be stripped
Compare (O/A) in the process is 1-10:1；It is highly preferred that compare (O/A) in stripping process is 4-6:1.
8. the preparation method of vanadic sulfate according to claim 4, which is characterized in that the extracting-back extraction process includes
Multiple extraction and separation, preferably 3-5 times, and extraction and separation include that extraction and separation and back extraction detach every time；
And first time extraction separation process includes level-one extraction and two level extraction, the two level extraction process is to extract level-one
The raffinate that process obtains is extracted, and the strip liquor that two level extraction process is obtained returns to the extraction original of level-one extraction process
In material.
9. the preparation method of vanadic sulfate according to claim 1, which is characterized in that adjusting during pH is 7-8 is
It is adjusted using alkaline solution, it is preferable that the alkaline solution is weakly alkaline solution, it is highly preferred that the alkaline solution is
Ammonium hydroxide.
10. a kind of oxygen vanadium sulfate crystals, which is characterized in that using the system of the vanadic sulfate described in any one of claim 1-9
Preparation Method is prepared.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111628202A (en) * | 2020-06-09 | 2020-09-04 | 中国恩菲工程技术有限公司 | VOSO4Preparation method of sulfuric acid solution and VOSO4Electrolyte solution |
| CN112551578A (en) * | 2019-09-25 | 2021-03-26 | 攀钢集团钒钛资源股份有限公司 | Method for preparing vanadyl sulfate solution from sodium vanadate solution in short process |
| CN112551577A (en) * | 2019-09-25 | 2021-03-26 | 攀钢集团钒钛资源股份有限公司 | Preparation method of vanadyl sulfate solution for regeneration of inactivated denitration catalyst |
| CN112551576A (en) * | 2019-09-25 | 2021-03-26 | 攀钢集团钒钛资源股份有限公司 | Preparation method of vanadyl sulfate solution for vanadium electrolyte |
| CN114335645A (en) * | 2021-12-23 | 2022-04-12 | 大连博融新材料有限公司 | Chlorine-vanadium-containing electrolytic liquid crystal, preparation method and application thereof |
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| CN114335645A (en) * | 2021-12-23 | 2022-04-12 | 大连博融新材料有限公司 | Chlorine-vanadium-containing electrolytic liquid crystal, preparation method and application thereof |
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Application publication date: 20180727 |