CN106145188A - A kind of method that sodium vanadium extraction liquid prepares V electrolyte high purity vanadic anhydride - Google Patents
A kind of method that sodium vanadium extraction liquid prepares V electrolyte high purity vanadic anhydride Download PDFInfo
- Publication number
- CN106145188A CN106145188A CN201610523348.8A CN201610523348A CN106145188A CN 106145188 A CN106145188 A CN 106145188A CN 201610523348 A CN201610523348 A CN 201610523348A CN 106145188 A CN106145188 A CN 106145188A
- Authority
- CN
- China
- Prior art keywords
- ammonium
- ammonia
- sodium
- vanadium
- extraction liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a kind of method that sodium vanadium extraction liquid prepares V electrolyte high purity vanadic anhydride, described method is: (1) adds ammonium sulfate in sodium vanadium extraction liquid, with sulfuric acid regulation solution pH and stir, is filtrated to get vanadic acid sodium；(2) vanadic acid sodium is placed in the deionized water that temperature is 40～60 DEG C and makes it dissolve, then add in solution containing ammonia and/or ammonium medium, regulate pH to 7～11, then stir, filter and crystallisation by cooling obtains ammonium metavanadate；(3) ammonium metavanadate is dissolved in the deionized water that temperature is 80～100 DEG C, then carries out being filtrated to get filtrate；(4) adding in the filtrate obtained containing ammonia and/or ammonium medium, regulation pH is 7～11, and crystallisation by cooling obtains ammonium metavanadate, the ammonium metavanadate obtained is carried out deamination roasting and prepares vanadic anhydride.The present invention whole course of reaction reaction condition is gentle, easy and simple to handle, and the purity of vanadium pentoxide prepared is high, and the response rate of vanadium is the highest.
Description
Technical field
The invention belongs to field of metallurgy, relate to a kind of method that sodium vanadium extraction liquid prepares vanadic anhydride, particularly relate to
A kind of method that sodium vanadium extraction liquid prepares V electrolyte high purity vanadic anhydride.
Background technology
V electrolyte is a multivalent state, high concentration and the solution system of high stability, is divided into anode electrolyte and negative pole
Electrolyte.Anode electrolyte initial soln typically uses the tetravalent vanadium ion solution being easy to get, and electrolyte liquid typically uses electrification
Learn reduction tetravalence vanadium and obtain trivalent vanadium ion solution, and ensure enough acidity to complete positive and negative electrode reaction, charged after just,
Negative pole can obtain pentavalent vanadium ion solution and divalent vanadium ion solution.All-vanadium flow battery uses the vanadium of different valence state as electrolyte
In active substance, completed the discharge and recharge of battery by reversible electrochemical reaction, convert electrical energy into chemical energy and be stored in vanadium
In electrolyte.Therefore, the scale energy storage of vanadium cell needs substantial amounts of vanadium raw materials to prepare V electrolyte.
V electrolyte is typically prepared with high-purity vanadium oxide for raw material, and the preparation cost of current high-purity vanadium oxide is higher.According to
Data shows, V electrolyte cost structure in vanadium cell system has the biggest with size and the energy storage time of vanadium cell device
Association.In theory, the electrolyte carrier that 1KW electric energy needs the vanadic anhydride of 5.6 kilograms to prepare is stored.Anticipated only wind power system
Year is consumed vanadic anhydride more than 30,000 tons by application vanadium cell energy storage, and market prospect is huge.
CN 103194603A discloses the preparation method of a kind of high-purity sulfuric acid vanadyl solution, and the method is by sodium vanadium extraction
Scavenging solution is directly added into ammonium sulfate, filters, washs and roasting obtains the vanadic anhydride that purity is 99%.
CN 104018011A discloses a kind of method of vanadic anhydride, the extraction of described method and the mode of back extraction
Obtaining the precipitate of vanadium, after washing precipitate, calcining obtains the vanadic anhydride that purity is 99.99%, and the response rate of its vanadium exists
About 76%.
CN 102849795A discloses the preparation method of a kind of high-purity vanadium pentoxide, and described method is by slightly inclined ammonium warp
Alkali is molten, remove impurity, filtration, quenched with oxidation, roguing, the step acquisition purity five oxidations more than 99.9% such as dehydration and deamination
Two vanadium.
But the above-mentioned method preparing vanadic anhydride all exists some problems, as follows:
(1) technique is loaded down with trivial details and vanadium yield is low: use extraction and back extraction to be prepared as the precipitate of vanadium in above-mentioned course of reaction,
Then calcining obtains vanadic anhydride and improves preparation cost；
(2) reaction impurities is high: in above-mentioned course of reaction, directly will add ammonium sulfate preparation in sodium vanadium extraction scavenging solution partially
Ammonium, then roasting obtains vanadium pentoxide, described during not by impurity purification, easily introduce impurity.
Therefore, how to select the process conditions of a kind of short route to prepare high purity vanadic anhydride, and have higher vanadium concurrently
Yield, is a difficult problem facing of existing commercial V electrolyte preparation method.
Summary of the invention
Loaded down with trivial details for technique present in the existing method preparing vanadic anhydride, vanadium yield is low, and reaction impurities is high
Problem, the invention provides a kind of method that sodium vanadium extraction liquid prepares vanadic anhydride.Described method with sodium vanadium extraction liquid is
Raw material, is first added thereto to Sulfovanadic acid and prepares vanadic acid sodium, then it is few to prepare impurity content by addition by several times containing ammonia and/or ammonium medium
Ammonium metavanadate, more finally prepare high purity vanadic anhydride through deamination roasting.Whole course of reaction reaction condition is gentle, operation letter
Just, and the purity of vanadium pentoxide prepared is high, and the response rate of vanadium is the highest.
For reaching this purpose, the present invention by the following technical solutions:
The invention provides a kind of method that sodium vanadium extraction liquid prepares vanadic anhydride, described method includes following step
Rapid:
(1) in sodium vanadium extraction liquid, add ammonium sulfate, with sulfuric acid regulation solution pH and stir, be filtrated to get vanadic acid sodium；
(2) vanadic acid sodium of step (1) gained be placed in the deionized water that temperature is 40～60 DEG C make it dissolve, then to
Solution adds containing ammonia and/or ammonium medium, regulates pH to 7～11, then stir, filter and crystallisation by cooling obtains ammonium metavanadate；
(3) step (2) is obtained ammonium metavanadate to be dissolved in the deionized water that temperature is 80～100 DEG C, then filter
Obtain filtrate；
(4) adding in the filtrate that step (3) obtains containing ammonia and/or ammonium medium, regulation pH is 7～11, and crystallisation by cooling obtains
To ammonium metavanadate, ammonium metavanadate will be obtained and carry out deamination roasting and prepare vanadic anhydride.
Wherein, the temperature of deionized water described in step (2) can be 40 DEG C, 43 DEG C, 45 DEG C, 47 DEG C, 50 DEG C, 53 DEG C, 55
DEG C, 57 DEG C or 60 DEG C etc., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible；Step (2) is adjusted
Joint pH can be 7,8,9,10 or 11 etc., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible；Step
(3) temperature of deionized water described in can be 80 DEG C, 83 DEG C, 85 DEG C, 87 DEG C, 90 DEG C, 93 DEG C, 95 DEG C, 97 DEG C or 100 DEG C etc.,
It is not limited to cited numerical value, listed in the range of other numerical value the most feasible；In step (4), regulation pH can be 7,8,9,10
Or 11 etc., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible.
Following as currently preferred technical scheme, but the restriction of the technical scheme provided not as the present invention, pass through
Techniques below scheme, can preferably reach and realize technical purpose and the beneficial effect of the present invention.
As currently preferred technical scheme, described in step (1) in sodium vanadium extraction liquid the concentration of vanadium ion be 20～
40g/L, such as 20g/L, 23g/L, 25g/L, 27g/L, 30g/L, 33g/L, 35g/L, 37g/L or 40g/L etc., but and not only limit
In cited numerical value, listed in the range of other numerical value the most feasible.
In the application, described sodium vanadium extraction immersion can be the leachate obtained in sodium process for extracting vanadium, specifically, mainly
With sodium carbonate for the thick vanadium slag of roasting additive roasting, then impregnation-calcination product obtains vanadium extraction leachate, described roasting and dipping
All carry out according to method well known in the art.
Preferably, ammonium sulfate described in step (1) is (1～2) with the mass ratio of vanadium ion in sodium vanadium extraction liquid: 1, such as
1:1,1.2:1,1.4:1,1.6:1,1.8:1 or 2:1 etc., it is not limited to cited numerical value, listed in the range of other numbers
It is worth the most feasible.
As currently preferred technical scheme, the concentration >=98wt% of sulphuric acid used in step (1).Sulfur used by the present invention
Acid is the concentrated sulphuric acid that top grade is pure.
Preferably, with sulfur acid for adjusting pH to 8～10 in step (1), such as 8,8.5,9,9.5 or 10 etc., but and not only limit
In cited numerical value, listed in the range of other numerical value the most feasible, more preferably 9.
Preferably, described in step (1), mixing time is 20～60min, such as 20min, 25min, 30min, 35min,
40min, 45min, 50min, 55min or 60min etc., it is not limited to cited numerical value, listed in the range of other numerical value
The most feasible, more preferably 30～35min.
As currently preferred technical scheme, deionization resistivity of water >=18.25M Ω cm used in step (2),
Such as 18.25M Ω cm, 19M Ω cm, 20M Ω cm, 21M Ω cm, 22M Ω cm, 23M Ω cm, 24M Ω cm
Or 25M Ω cm and with first-class, it is not limited to cited numerical value, listed in the range of other numerical value the most feasible.The present invention
Deionized water used by needs to keep certain resistivity, and then ensures the purity of the final vanadic anhydride prepared.
Preferably, described in step (2), the temperature of water is 45～55 DEG C, such as 45 DEG C, 46 DEG C, 47 DEG C, 48 DEG C, 49 DEG C,
50 DEG C, 51 DEG C, 52 DEG C, 53 DEG C, 54 DEG C or 55 DEG C etc., it is not limited to cited numerical value, listed in the range of other numerical value
The most feasible.
As currently preferred technical scheme, contain ammonia described in step (2) and/or ammonium medium is ammonia, liquefied ammonia, ammonia
Or any one or the combination of at least two in ammonium salt, described combination typical case but limiting examples have: ammonia and the group of liquefied ammonia
Close, liquefied ammonia and the combination of the combination of ammonia, ammonia and ammonium salt, the combination of ammonia, liquefied ammonia and ammonia, ammonia, liquefied ammonia, ammonia and ammonium
The combination etc. of salt, it is not limited to cited numerical value, listed in the range of other numerical value the most feasible, more preferably ammonia
Water.
In the present invention, in sodium vanadate solution, add ammonia and/or ammonium medium is to be cemented out by the potassium being wherein mingled with.
Preferably, described ammonium salt is ammonium carbonate and/or ammonium hydrogen carbonate.
Preferably, described in step (2) containing impurity content≤0.1wt%, such as 0.1wt% in ammonia and/or ammonium medium,
0.07wt%, 0.05wt%, 0.03wt% or 0.01wt% etc. and more fractional value, it is not limited to cited numerical value,
In the range of Suo Lie, other numerical value are the most feasible.
Preferably, the addition of ammonia and/or ammonium medium is contained described in step (2) for making solution ph reach 7～11.
As currently preferred technical scheme, described in step (3), the temperature of deionized water is 90～95 DEG C.
Preferably, deionization resistivity of water described in step (3) >=18.25M Ω cm, such as 18.25M Ω cm,
19M Ω cm, 20M Ω cm, 21M Ω cm, 22M Ω cm, 23M Ω cm, 24M Ω cm or 25M Ω cm and more than
Deng, it is not limited to cited numerical value, listed in the range of other numerical value the most feasible.
As currently preferred technical scheme, contain ammonia described in step (4) and/or ammonium medium is ammonia, liquefied ammonia, ammonia
Or any one or the combination of at least two in ammonium salt, described combination typical case but limiting examples have: ammonia and the group of liquefied ammonia
Close, liquefied ammonia and the combination of the combination of ammonia, ammonia and ammonium salt, the combination of ammonia, liquefied ammonia and ammonia, ammonia, liquefied ammonia, ammonia and ammonium
The combination etc. of salt, it is not limited to cited numerical value, listed in the range of other numerical value the most feasible, more preferably ammonia
Gas.
Preferably, step (4) contains the addition of ammonia and/or ammonium medium for making pH value of solution reach 7～11.
Preferably, described ammonium salt is ammonium carbonate and/or ammonium hydrogen carbonate.
Preferably, described in step (4) containing impurity content≤0.1wt%, such as 0.1wt% in ammonia and/or ammonium medium,
0.07wt%, 0.05wt%, 0.03wt% or 0.01wt% etc. and more fractional value, it is not limited to cited numerical value,
In the range of Suo Lie, other numerical value are the most feasible.
As currently preferred technical scheme, described in step (4), the temperature of deamination roasting is 400～500 DEG C, such as
400 DEG C, 410 DEG C, 420 DEG C, 430 DEG C, 440 DEG C, 450 DEG C, 460 DEG C, 470 DEG C, 480 DEG C, 490 DEG C or 500 DEG C etc., but and not only
Be limited to cited numerical value, listed in the range of other numerical value the most feasible, more preferably 460 DEG C.
As currently preferred technical scheme, in step (4), the purity of gained ammonium metavanadate is >=99.9wt%；
Preferably, the purity >=99.9wt% of the vanadic anhydride prepared in step (4).
As currently preferred technical scheme, said method comprising the steps of:
(1) by ammonium sulfate and vanadium ion in sodium vanadium extraction liquid in the sodium vanadium extraction liquid that vanadium ion concentration is 20～40g/L
Mass ratio be (1～2): 1 adds ammonium sulfate, with the sulfuric acid regulation solution pH of concentration >=98wt% and stir 30～35min, mistake
Filter obtains vanadic acid sodium；
(2) vanadic acid sodium of step (1) gained being placed in temperature is 45～55 DEG C, resistivity >=18.25M Ω cm go from
Sub-water makes it dissolve, then add in solution impurity content≤0.1wt% containing ammonia and/or ammonium medium, regulation pH to 7～
11, then stir, filter and crystallisation by cooling obtains ammonium metavanadate；
(3) step (2) obtains ammonium metavanadate being dissolved in temperature is 90～95 DEG C and resistivity >=18.25M Ω cm go
In ionized water, then carry out being filtrated to get filtrate；
(4) add in the filtrate that step (3) obtains impurity content≤0.1wt% containing ammonia and/or ammonium medium, regulate pH
Being 7～11, crystallisation by cooling obtains ammonium metavanadate, the ammonium metavanadate obtained carries out at 400～500 DEG C deamination roasting and prepares five
V 2 O.
Compared with prior art, the method have the advantages that
The present invention, with sodium vanadium extraction liquid as raw material, is first added thereto to Sulfovanadic acid and prepares vanadic acid sodium, then by adding by several times
Prepare, containing ammonia and/or ammonium medium, the ammonium metavanadate that impurity content is few, more finally prepare purity >=99.9wt%'s through deamination roasting
Vanadic anhydride, and the response rate of vanadium is up to more than 95%.Meanwhile, the method for the invention and equipment are simple, reaction condition temperature
With, easy and simple to handle, low cost and be prone to scale and prepare, use the vanadic anhydride of purity >=99.9wt% that the present invention prepares
High-purity sulphuric acid vanadyl electrolyte can be prepared further.
Detailed description of the invention
For the present invention is better described, it is simple to understand technical scheme, below to the present invention the most specifically
Bright.But following embodiment is only the simple example of the present invention, do not represent or limit the scope of the present invention, this
Invention protection domain is as the criterion with claims.
Embodiment 1:
Present embodiments providing a kind of method that sodium vanadium extraction liquid prepares vanadic anhydride, described method is:
(1) measure the sodium vanadium extraction liquid that 1L vanadium concentration is 20g/L, add 22g ammonium sulfate, be subsequently adding concentration >=98wt%
Top grade pure concentrated sulphuric acid regulation pH stir 30min, be filtrated to get vanadic acid sodium；
(2) vanadic acid sodium that step (1) is filtrated to get being placed in temperature is 45 DEG C, the deionization of resistivity 19.25M Ω cm
In water, adding impurity content is the ammonia of 0.05wt% to regulate pH be 7, and stirring makes it dissolve, and then filters crystallisation by cooling and obtains
To ammonium metavanadate；
(3) step (2) obtains ammonium metavanadate being dissolved in temperature is 100 DEG C, the deionized water of resistivity 19.25M Ω cm
In, then carry out being filtrated to get filtrate；
(4) adding impurity content in the filtrate that step (3) obtains is the ammonia of 0.05wt%, and regulation pH is 8, cooling knot
Crystalline substance obtains the ammonium metavanadate that purity is, is 99.95wt%'s by obtain ammonium metavanadate carry out deamination roasting preparing purity in 400 DEG C
Vanadic anhydride, its vanadium recovery is 97%.
In gained vanadic anhydride, each ion concentration is as shown in table 1.
Table 1: each ion concentration table wt% in the vanadic anhydride that embodiment 1 prepares
Embodiment 2:
Present embodiments providing a kind of method that sodium vanadium extraction liquid prepares vanadic anhydride, described method is:
(1) measure the sodium vanadium extraction liquid that 1L vanadium concentration is 22g/L, add 28.6g ammonium sulfate, be subsequently adding concentration >=
The pure concentrated sulphuric acid of top grade of 98wt% regulates pH and stirs 30min, is filtrated to get vanadic acid sodium；
(2) vanadic acid sodium that step (1) is filtrated to get being placed in temperature is 50 DEG C, the deionization of resistivity 21.21M Ω cm
In water, adding ammonia and to regulate pH be 9, in solution, ammonia impurity content is 0.03wt%, and stirring makes it dissolve, and then filters cooling
Crystallization obtains ammonium metavanadate；
(3) step (2) obtains ammonium metavanadate being dissolved in temperature is 95 DEG C, the deionized water of resistivity 21.21M Ω cm
In, then carry out being filtrated to get filtrate；
(4) adding ammonia in the filtrate that step (3) obtains, regulation pH is 7, and crystallisation by cooling obtains the metavanadic acid that purity is
Ammonium, carries out deamination roasting in 490 DEG C and prepares, by obtaining ammonium metavanadate, the vanadic anhydride that purity is 99.94wt%, and its vanadium reclaims
Rate is 95%.
In gained vanadic anhydride, each ion concentration is as shown in table 2.
Table 2: each ion concentration table wt% in the vanadic anhydride that embodiment 2 prepares
Embodiment 3:
Present embodiments providing a kind of method that sodium vanadium extraction liquid prepares vanadic anhydride, described method is:
(1) measure the sodium vanadium extraction liquid that 1L vanadium concentration is 40g/L, add 51g ammonium sulfate, be subsequently adding concentration >=98wt%
Top grade pure concentrated sulphuric acid regulation pH stir 30min, be filtrated to get vanadic acid sodium；
(2) vanadic acid sodium that step (1) is filtrated to get being placed in temperature is 55 DEG C, the deionization of resistivity 18.69M Ω cm
In water, adding impurity content is the ammonium hydrogen carbonate of 0.08wt% to regulate pH be 9.5, and stirring makes it dissolve, and then filters cooling
Crystallization obtains ammonium metavanadate；
(3) step (2) obtains ammonium metavanadate being dissolved in temperature is 90 DEG C, the deionized water of resistivity 18.69M Ω cm
In, then carry out being filtrated to get filtrate；
(4) adding impurity content in the filtrate that step (3) obtains is the ammonium hydrogen carbonate of 0.08wt%, and regulation pH is 11,
Crystallisation by cooling obtains the ammonium metavanadate that purity is, ammonium metavanadate will be obtained carry out deamination roasting prepare purity in 460 DEG C be
The vanadic anhydride of 99.95wt%, its vanadium recovery is 95%.
In gained vanadic anhydride, each ion concentration is as shown in table 3.
Table 3: each ion concentration table wt% in the vanadic anhydride that embodiment 3 prepares
Embodiment 4:
Present embodiments providing a kind of method that sodium vanadium extraction liquid prepares vanadic anhydride, described method is:
(1) measure the sodium vanadium extraction liquid that 1L vanadium concentration is 30g/L, add 32g ammonium sulfate, be subsequently adding concentration >=98wt%
Top grade pure concentrated sulphuric acid regulation pH stir 30min, be filtrated to get vanadic acid sodium；
(2) vanadic acid sodium that step (1) is filtrated to get being placed in temperature is 52 DEG C, the deionization of resistivity 19.52M Ω cm
In water, adding impurity content is the ammonium carbonate of 0.07wt% to regulate pH be 11, and stirring makes it dissolve, and then filters crystallisation by cooling
Obtain ammonium metavanadate；
(3) step (2) obtains ammonium metavanadate being dissolved in temperature is 90 DEG C, the deionized water of resistivity 19.52M Ω cm
In, then carry out being filtrated to get filtrate；
(4) adding impurity content in the filtrate that step (3) obtains is the liquefied ammonia of 0.07wt%, and regulation pH is 10.5, cold
But crystallization obtains the ammonium metavanadate that purity is, ammonium metavanadate will be obtained carry out deamination roasting prepare purity in 440 DEG C be
The vanadic anhydride of 99.96wt%, its vanadium recovery is 96%.
In gained vanadic anhydride, each ion concentration is as shown in table 4.
Table 4: each ion concentration table wt% in the vanadic anhydride that embodiment 4 prepares
Embodiment 5:
Present embodiments providing a kind of method that sodium vanadium extraction liquid prepares vanadic anhydride, described method is:
(1) measure the sodium vanadium extraction liquid that 1L vanadium concentration is 25g/L, add 30.5g ammonium sulfate, be subsequently adding concentration >=
The pure concentrated sulphuric acid of top grade of 98wt% regulates pH and stirs 30min, is filtrated to get vanadic acid sodium；
(2) vanadic acid sodium that step (1) is filtrated to get being placed in temperature is 60 DEG C, the deionization of resistivity 20.02M Ω cm
In water, adding impurity content is the ammonia of 0.05wt% to regulate pH be 7.5, and stirring makes it dissolve, and then filters crystallisation by cooling
Obtain ammonium metavanadate；
(3) step (2) obtains ammonium metavanadate being dissolved in temperature is 85 DEG C, the deionized water of resistivity 20.02M Ω cm
In, then carry out being filtrated to get filtrate；
(4) adding impurity content in the filtrate that step (3) obtains is the liquefied ammonia of 0.05wt%, and regulation pH is 8.5, cooling
Crystallization obtains the ammonium metavanadate that purity is, will obtain ammonium metavanadate carry out deamination roasting preparing purity in 500 DEG C is 99.95wt%
Vanadic anhydride, its vanadium recovery is 96%.
In gained vanadic anhydride, each ion concentration is as shown in table 5.
Table 5: each ion concentration table wt% in the vanadic anhydride that embodiment 5 prepares
Comparative example 1:
This comparative example provides a kind of method that sodium vanadium extraction liquid prepares vanadic anhydride, and described method is except step
(2) outside not adding containing ammonia and/or ammonium medium in solution and in step (4), unclassified stores consumption and preparation method all with enforcement
In example 1 identical, the purity of the final vanadic anhydride prepared is 98.6wt%, and its vanadium recovery is 93wt%.
In gained vanadic anhydride, each ion concentration is as shown in table 6.
Table 6: each ion concentration table wt% in the vanadic anhydride that comparative example 1 prepares
Comparative example 2:
This comparative example provides a kind of method that sodium vanadium extraction liquid prepares vanadic anhydride, and described method is except step
(2) and in step (4) deionization resistivity of water used be 10M Ω cm (＜ 18.25M Ω cm) outward, unclassified stores consumption
The most in the same manner as in Example 1 with preparation method, the purity of the final vanadic anhydride prepared is 98wt%, and its vanadium recovery is
95wt%.
In gained vanadic anhydride, each ion concentration is as shown in table 7.
Table 7: each ion concentration table in the vanadic anhydride that comparative example 2 prepares
The result of integrated embodiment 1-5 and comparative example 1-2 it can be seen that the present invention is with sodium vanadium extraction liquid as raw material, first to
Wherein add Sulfovanadic acid and prepare vanadic acid sodium, then prepare, containing ammonia and/or ammonium medium, the metavanadic acid that impurity content is few by adding by several times
Ammonium, then the vanadic anhydride of purity >=99.9wt% is finally prepared through deamination roasting, and the response rate of vanadium is up to more than 95%.With
Time, the method for the invention and equipment are simple, and reaction condition is gentle, easy and simple to handle, low cost and be prone to scale and prepare, and use
The vanadic anhydride of purity >=99.9wt% that the present invention prepares can prepare high-purity sulphuric acid vanadyl electrolyte further.
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, i.e. do not mean that the present invention have to rely on above-mentioned in detail
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, concrete way choice etc., all falls within the present invention's
Within the scope of protection domain and disclosure.
Claims (10)
1. the method preparing vanadic anhydride with sodium vanadium extraction liquid, it is characterised in that said method comprising the steps of:
(1) in sodium vanadium extraction liquid, add ammonium sulfate, with sulfuric acid regulation solution pH and stir, be filtrated to get vanadic acid sodium；
(2) vanadic acid sodium of step (1) gained is placed in the deionized water that temperature is 40～60 DEG C makes it dissolve, then to solution
Middle addition contains ammonia and/or ammonium medium, regulates pH to 7～11, then stirs, filters and crystallisation by cooling obtains ammonium metavanadate；
(3) step (2) is obtained ammonium metavanadate to be dissolved in the deionized water that temperature is 80～100 DEG C, be then filtrated to get
Filtrate；
(4) adding in the filtrate that step (3) obtains containing ammonia and/or ammonium medium, regulation pH is 7～11, and crystallisation by cooling obtains partially
Ammonium vanadate, carries out deamination roasting by the ammonium metavanadate obtained and prepares vanadic anhydride.
Method the most according to claim 1, it is characterised in that vanadium ion dense in sodium vanadium extraction liquid described in step (1)
Degree is 20～40g/L；
Preferably, ammonium sulfate described in step (1) is (1～2) with the mass ratio of vanadium ion in sodium vanadium extraction liquid: 1.
Method the most according to claim 1 and 2, it is characterised in that the concentration >=98wt% of sulphuric acid used in step (1)；
Preferably, with sulfur acid for adjusting pH to 8～10 in step (1), more preferably 9；
Preferably, described in step (1), mixing time is 20～60min, more preferably 30～35min.
4. according to the method described in any one of claim 1-3, it is characterised in that the resistance of deionized water used in step (2)
Rate >=18.25M Ω cm；
Preferably, described in step (2), the temperature of water is 45～55 DEG C.
5. according to the method described in any one of claim 1-4, it is characterised in that containing ammonia and/or ammonium medium described in step (2)
For any one or the combination of at least two, more preferably ammonia in ammonia, liquefied ammonia, ammonia or ammonium salt；
Preferably, described ammonium salt is ammonium carbonate and/or ammonium hydrogen carbonate；
Preferably, containing impurity content≤0.1wt% in ammonia and/or ammonium medium described in step (2)；
Preferably, the addition containing ammonia and/or ammonium medium described in step (2) makes solution ph reach 7～11.
6. according to the method described in any one of claim 1-5, it is characterised in that the temperature of deionized water described in step (3)
It it is 90～95 DEG C；
Preferably, deionization resistivity of water described in step (3) >=18.25M Ω cm.
7. according to the method described in any one of claim 1-6, it is characterised in that containing ammonia and/or ammonium medium described in step (4)
For any one or the combination of at least two, more preferably ammonia in ammonia, liquefied ammonia, ammonia or ammonium salt；
Preferably, step (4) contains the addition of ammonia and/or ammonium medium for making solution ph reach 7～11；
Preferably, described ammonium salt is ammonium carbonate and/or ammonium hydrogen carbonate；
Preferably, containing impurity content≤0.1wt% in ammonia and/or ammonium medium described in step (4).
8. according to the method described in any one of claim 1-7, it is characterised in that the temperature of deamination roasting described in step (4)
It is 400～500 DEG C, more preferably 460 DEG C.
9. according to the method described in any one of claim 1-8, it is characterised in that the purity of gained ammonium metavanadate in step (4)
For >=99.9wt%；
Preferably, the purity >=99.9wt% of the vanadic anhydride prepared in step (4).
10. according to the method described in any one of claim 1-9, it is characterised in that said method comprising the steps of:
(1) by ammonium sulfate and the matter of vanadium ion in sodium vanadium extraction liquid in the sodium vanadium extraction liquid that vanadium ion concentration is 20～40g/L
Amount is than for (1～2): 1 adds ammonium sulfate, with the sulfuric acid regulation solution pH of concentration >=98wt% and stir 30～35min, filters
To vanadic acid sodium；
(2) vanadic acid sodium of step (1) gained being placed in temperature is 45～55 DEG C, the deionized water of resistivity >=18.25M Ω cm
In make it dissolve, then add in solution impurity content≤0.1wt% containing ammonia and/or ammonium medium, regulate pH to 7～11,
Then stir, filter and crystallisation by cooling obtains ammonium metavanadate；
(3) step (2) obtains ammonium metavanadate being dissolved in temperature is 90～95 DEG C and the deionization of resistivity >=18.25M Ω cm
In water, then carry out being filtrated to get filtrate；
(4) add in the filtrate that step (3) obtains impurity content≤0.1wt% containing ammonia and/or ammonium medium, regulation pH is 7
～11, crystallisation by cooling obtains ammonium metavanadate, will obtain ammonium metavanadate and carry out deamination roasting at 400～500 DEG C and prepare five oxidations
Two vanadium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610523348.8A CN106145188A (en) | 2016-07-05 | 2016-07-05 | A kind of method that sodium vanadium extraction liquid prepares V electrolyte high purity vanadic anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610523348.8A CN106145188A (en) | 2016-07-05 | 2016-07-05 | A kind of method that sodium vanadium extraction liquid prepares V electrolyte high purity vanadic anhydride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106145188A true CN106145188A (en) | 2016-11-23 |
Family
ID=58061756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610523348.8A Pending CN106145188A (en) | 2016-07-05 | 2016-07-05 | A kind of method that sodium vanadium extraction liquid prepares V electrolyte high purity vanadic anhydride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106145188A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106399786A (en) * | 2016-11-25 | 2017-02-15 | 南通汉瑞新材料科技有限公司 | Novel method for preparing vanadium-nitrogen alloy |
| CN107720783A (en) * | 2017-10-23 | 2018-02-23 | 攀钢集团攀枝花钢铁研究院有限公司 | The preparation method of sodium carbonate |
| CN110994061A (en) * | 2019-10-29 | 2020-04-10 | 大连博融新材料有限公司 | Method for recovering vanadium electrolyte |
| CN114436329A (en) * | 2021-12-16 | 2022-05-06 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing high-purity vanadium pentoxide by sodium-vanadium solution two-step method |
| CN114436329B (en) * | 2021-12-16 | 2024-04-30 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing high-purity vanadium pentoxide by sodium vanadium solution two-step method |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10114525A (en) * | 1997-08-29 | 1998-05-06 | Kashima Kita Kyodo Hatsuden Kk | Production of high purity vanadium pentoxide |
| CN101746822A (en) * | 2009-12-30 | 2010-06-23 | 攀钢集团攀枝花钢钒有限公司 | Method for extracting sodium metavanadate from vanadium extraction leaching solution |
| CN102021345A (en) * | 2010-12-30 | 2011-04-20 | 甘肃锦世化工有限责任公司 | Method for recycling vanadium pentoxide and sodium dichromate |
| CN102219257A (en) * | 2011-04-01 | 2011-10-19 | 中国恩菲工程技术有限公司 | Method for preparing vanadium pentoxide |
| CN102220499A (en) * | 2011-04-01 | 2011-10-19 | 中国恩菲工程技术有限公司 | Roasting-leaching method of fine vanadium slags |
| CN102430266A (en) * | 2010-09-29 | 2012-05-02 | 攀钢集团钢铁钒钛股份有限公司 | Method for purifying liquid with vanadium and method for preparing ammonium metavanadate and vanadium oxide |
| CN102477493A (en) * | 2010-11-29 | 2012-05-30 | 攀钢集团钢铁钒钛股份有限公司 | Silicon-removing phosphorus-removing purifying method of sodium-modified vanadium-extraction leachate |
| CN102936049A (en) * | 2012-11-26 | 2013-02-20 | 西南民族大学 | Method for extracting tungsten, titanium and vanadium from waste SCR (selective catalytic reduction) catalyst |
| CN103194603A (en) * | 2013-04-01 | 2013-07-10 | 攀枝花学院 | Preparation method of high-purity vanadium pentoxide |
| CN103420416A (en) * | 2012-05-15 | 2013-12-04 | 攀钢集团攀枝花钢钒有限公司 | Ammonium metavanadate preparation method |
| CN103833078A (en) * | 2014-03-25 | 2014-06-04 | 时国海 | Vanadium precipitation crystallization method for extracting ammonium metavanadate |
| CN104037439A (en) * | 2013-03-05 | 2014-09-10 | 中国人民解放军63971部队 | Combined chemical-electrochemical method for preparing vanadium redox flow battery electrolyte |
| CN104388683A (en) * | 2014-12-08 | 2015-03-04 | 中南大学 | Method for separating and recycling vanadium and chromium from vanadium and chromium-containing material |
| CN104477992A (en) * | 2015-01-07 | 2015-04-01 | 攀钢集团研究院有限公司 | Method for preparing vanadium pentoxide |
| CN104495927A (en) * | 2015-01-07 | 2015-04-08 | 攀钢集团研究院有限公司 | Method for preparing vanadium pentoxide |
| CN104609472A (en) * | 2015-02-17 | 2015-05-13 | 中信锦州金属股份有限公司 | Method for producing vanadium pentoxide from titanium tetrachloride refinement vanadium-removal slurry |
| CN105420520A (en) * | 2015-12-29 | 2016-03-23 | 攀枝花恒弘球团有限公司 | Extraction method for vanadium in vanadium slag |
-
2016
- 2016-07-05 CN CN201610523348.8A patent/CN106145188A/en active Pending
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10114525A (en) * | 1997-08-29 | 1998-05-06 | Kashima Kita Kyodo Hatsuden Kk | Production of high purity vanadium pentoxide |
| CN101746822A (en) * | 2009-12-30 | 2010-06-23 | 攀钢集团攀枝花钢钒有限公司 | Method for extracting sodium metavanadate from vanadium extraction leaching solution |
| CN102430266A (en) * | 2010-09-29 | 2012-05-02 | 攀钢集团钢铁钒钛股份有限公司 | Method for purifying liquid with vanadium and method for preparing ammonium metavanadate and vanadium oxide |
| CN102477493A (en) * | 2010-11-29 | 2012-05-30 | 攀钢集团钢铁钒钛股份有限公司 | Silicon-removing phosphorus-removing purifying method of sodium-modified vanadium-extraction leachate |
| CN102021345A (en) * | 2010-12-30 | 2011-04-20 | 甘肃锦世化工有限责任公司 | Method for recycling vanadium pentoxide and sodium dichromate |
| CN102219257A (en) * | 2011-04-01 | 2011-10-19 | 中国恩菲工程技术有限公司 | Method for preparing vanadium pentoxide |
| CN102220499A (en) * | 2011-04-01 | 2011-10-19 | 中国恩菲工程技术有限公司 | Roasting-leaching method of fine vanadium slags |
| CN103420416A (en) * | 2012-05-15 | 2013-12-04 | 攀钢集团攀枝花钢钒有限公司 | Ammonium metavanadate preparation method |
| CN102936049A (en) * | 2012-11-26 | 2013-02-20 | 西南民族大学 | Method for extracting tungsten, titanium and vanadium from waste SCR (selective catalytic reduction) catalyst |
| CN104037439A (en) * | 2013-03-05 | 2014-09-10 | 中国人民解放军63971部队 | Combined chemical-electrochemical method for preparing vanadium redox flow battery electrolyte |
| CN103194603A (en) * | 2013-04-01 | 2013-07-10 | 攀枝花学院 | Preparation method of high-purity vanadium pentoxide |
| CN103833078A (en) * | 2014-03-25 | 2014-06-04 | 时国海 | Vanadium precipitation crystallization method for extracting ammonium metavanadate |
| CN104388683A (en) * | 2014-12-08 | 2015-03-04 | 中南大学 | Method for separating and recycling vanadium and chromium from vanadium and chromium-containing material |
| CN104477992A (en) * | 2015-01-07 | 2015-04-01 | 攀钢集团研究院有限公司 | Method for preparing vanadium pentoxide |
| CN104495927A (en) * | 2015-01-07 | 2015-04-08 | 攀钢集团研究院有限公司 | Method for preparing vanadium pentoxide |
| CN104609472A (en) * | 2015-02-17 | 2015-05-13 | 中信锦州金属股份有限公司 | Method for producing vanadium pentoxide from titanium tetrachloride refinement vanadium-removal slurry |
| CN105420520A (en) * | 2015-12-29 | 2016-03-23 | 攀枝花恒弘球团有限公司 | Extraction method for vanadium in vanadium slag |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106399786A (en) * | 2016-11-25 | 2017-02-15 | 南通汉瑞新材料科技有限公司 | Novel method for preparing vanadium-nitrogen alloy |
| CN107720783A (en) * | 2017-10-23 | 2018-02-23 | 攀钢集团攀枝花钢铁研究院有限公司 | The preparation method of sodium carbonate |
| CN110994061A (en) * | 2019-10-29 | 2020-04-10 | 大连博融新材料有限公司 | Method for recovering vanadium electrolyte |
| CN114436329A (en) * | 2021-12-16 | 2022-05-06 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing high-purity vanadium pentoxide by sodium-vanadium solution two-step method |
| CN114436329B (en) * | 2021-12-16 | 2024-04-30 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing high-purity vanadium pentoxide by sodium vanadium solution two-step method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108878866B (en) | Method for preparing ternary material precursor and recovering lithium by using ternary cathode material of waste lithium ion battery | |
| CN107994288B (en) | Method for recovering valuable metals in anode material of waste nickel cobalt lithium manganate ternary battery | |
| CN108075203A (en) | A kind of method that valuable metal component recycles in waste and old lithium ion battery material | |
| US20130037416A1 (en) | Method for producing mercury-free alkaline-manganese type electrolyzed manganese dioxide | |
| CN103515642A (en) | Preparation method of vanadium battery electrolyte solution with high purity and high concentration | |
| CN105024072B (en) | A kind of method that lithium ion battery ferric orthophosphate is prepared using iron content raffinate | |
| CN103401010A (en) | Method for preparing electrolytes of all-vanadium flow battery | |
| CN106987719A (en) | A kind of recovery method of CIGS material | |
| CN103505903A (en) | Two-stage extraction preparation method for high-purity vanadyl sulfate solution | |
| CN111471864A (en) | Method for recovering copper, aluminum and iron from waste lithium ion battery leachate | |
| CN104319412A (en) | Method for preparing high-purity and high-concentration vanadium electrolyte | |
| CN106145188A (en) | A kind of method that sodium vanadium extraction liquid prepares V electrolyte high purity vanadic anhydride | |
| CN103904343B (en) | The preparation method of all-vanadium redox flow battery electrolytic solution | |
| CN110395766B (en) | Preparation method of solid vanadyl sulfate | |
| CN103482702B (en) | Method for preparing high-purity vanadium oxide and high-purity electrolyte for vanadium battery | |
| CN105197988A (en) | Ammonia process separation and refinement method of lead sulfate | |
| CN108306071A (en) | A kind of waste lithium ion cell anode material recovery technique | |
| CN104064795A (en) | Preparation method of high-purity vanadyl sulfate electrolyte | |
| CN106450401A (en) | Method for preparing vanadyl sulfate by utilizing waste vanadium electrolyte | |
| CN106684421A (en) | Method for preparing vanadium electrolyte | |
| CN103966438B (en) | A kind of method of vanadium and chromium in electrolytic separation containing vanadium and chromium solution | |
| CN105800688B (en) | A kind of method that solid phase roasting prepares vanadic sulfate | |
| CN105655620B (en) | One kind utilizes V2O5The method for preparing vanadium redox battery negative pole electrolyte | |
| CN109081385B (en) | Method for preparing ternary material by recycling cobalt-manganese waste residues | |
| CN110669940A (en) | Method for preparing vanadium pentoxide by recovering spent vanadium electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 067102 Luanhe Town, Shuangluan District, Chengde, Hebei Applicant after: River steel Limited by Share Ltd Chengde branch Address before: 067000 Luanhe Town, Shuangluan District, Chengde, Hebei Applicant before: Chengde Branch Co., Ltd. of Hebei Iron & Steel Group |
|
| CB02 | Change of applicant information | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161123 |
|
| RJ01 | Rejection of invention patent application after publication |