CN106684421A - Method for preparing vanadium electrolyte - Google Patents
Method for preparing vanadium electrolyte Download PDFInfo
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- CN106684421A CN106684421A CN201710024733.2A CN201710024733A CN106684421A CN 106684421 A CN106684421 A CN 106684421A CN 201710024733 A CN201710024733 A CN 201710024733A CN 106684421 A CN106684421 A CN 106684421A
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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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Abstract
The invention provides a method for preparing 3.5-valence vanadium electrolyte. The method includes the following steps: (1) vanadium pentoxide is put into a reactor, and is added with a reducing substance to carry out reduction reaction under 500 DEG C to 600 DEG C; (2) after reaction, the material is cooled, and is washed and filtered for the first time; (3) after being washed and filtered for the first time, the material is washed with acid liquor for the second time, and is then washed and filtered for the third time; (4) after being washed and filtered for the third time, the material is added into sulfuric acid and heated until the material is dissolved, and thereby the vanadium electrolyte is obtained. With high-purity vanadium pentoxide as material, the method disclosed by the invention controls reaction conditions, the 3.5-valence state high-purity vanadium electrolyte can be obtained by reduction, washing and dissolution, the process and equipment are simple, operation is convenient, the cost is low, and mass production is easy.
Description
Technical field
The invention belongs to technical field of electrolyte, is related to a kind of method for preparing V electrolyte, more particularly to one kind is by five
The method that V 2 O reduction prepares high-purity 3.5 valency V electrolytes of capacity such as trivalent vanadium and tetravalence vanadium
Background technology
V electrolyte is the solution system of multivalent state, high concentration and a high stability, point positive and negative electrode electrolyte.Positive pole
The sulfuric acid solution of electrolyte V (IV)/V (V), electrolyte liquid is the sulfuric acid solution of V (II)/V (III), and is ensured sufficiently high
To complete positive and negative electrode reaction in sulfuric acid solution, charged rear positive and negative electrode can obtain pentavalent vanadium ion solution and divalent vanadium ion is molten
Liquid.When therefore, using 3.5 valency V electrolyte, the discharge and recharge of all-vanadium flow battery can be carried out directly without the need for activation.
The technology of preparing of existing V electrolyte is although varied, but mostly with V2O5Or V2O3For raw material, using chemistry
Method, electrochemical electrolysis method or both are combined and prepare V electrolyte.But V electrolyte is typically with vanadium oxysulfate or other valence states
Vanadic acid solution form is present, therefore, direct one-step method obtains the high purity vanadium electrolysis of 3.5 valence states of capacity such as tetravalence vanadium and trivalent vanadium
Liquid is the key problem of vanadium energy storage system.
CN 104638288A disclose a kind of electrochemical preparation method of 3.5 valency V electrolyte, and it utilizes electrolysis unit to incite somebody to action
4 valency vanadium solutions of moiety volume as anode electrolyte, using 4 valency vanadium solutions of a volume as electrolyte liquid, in power supply
Under the function of current for providing, electrolysis electricity is controlled, the vanadium of electrolyte liquid is restored to into 3.5 valencys by 4 valencys.
CN 1598063A disclose a kind of electrolytic preparation method of full vanadium ion fluid cell electrolyte, and methods described exists
1:Vanadium sesquioxide is sequentially added in 1 sulfuric acid solution and vanadic anhydride obtains oxygen vanadium sulphate solution, be subsequently adding sodium sulfate,
The additives such as polyoxyethylene nonylphenol ether are carried out being electrolysed and obtain trivalent vanadium and tetravalence vanadium respectively accounts for the electrolyte of vanadium redox battery of total vanadium 50%.
CN 101192674 discloses a kind of preparation method of all-vanadium redox flow battery electrolytic solution, and it is by three oxygen
Change two vanadium to mix by a certain percentage in electric tube furnace after 100 DEG C~300 DEG C calcinings with concentrated sulphuric acid, in being dissolved in dilute sulfuric acid,
Obtain trivalent vanadium and tetravalence vanadium respectively accounts for the electrolyte of vanadium redox battery of total vanadium 50%.
CN 1719655 discloses a kind of full vanadium ion fluid cell electrolyte and preparation method thereof, and it is with the qualified vanadium of vanadium factory
Liquid is raw material, with being reduced by reducing agent of liquid sulfur dioxide after sulfur acid for adjusting pH value, then adjusts pH value with sodium carbonate
Vanadium dioxide precipitation is obtained, precipitation is dissolved in water, sulphuric acid, ethanol solution, add additive, then electrolysis obtains trivalent vanadium and four
Valency vanadium respectively accounts for the electrolyte of vanadium redox battery of total vanadium 50%.
As can be seen that high-purity V electrolyte of existing 3.5 valence state is typically prepared by electrolytic method, this needs special setting
Standby and strict air-proof condition, requires reaction condition strict, it is difficult to large-scale application.And chemical method is general during preparing
Need to add additive or the not preparation in single sulfuric acid system, it is difficult to ensure the purity of obtained V electrolyte.
The content of the invention
Equipment requirements present in preparation method for high-purity V electrolyte of existing 3.5 valence state are strict, be difficult to big rule
Mould application and electrolyte purity are difficult to the problems such as reaching requirement, the invention provides a kind of side for preparing 3.5 valency V electrolytes
Method.The method of the invention controls reaction condition with high purity vanadic anhydride as raw material, by reduction, washing and dissolving
High-purity V electrolyte of 3.5 valence states is obtained, technique and equipment are simple, easy to operate, low cost, it is easy to large-scale production.
It is that, up to this purpose, the present invention is employed the following technical solutions：
The invention provides a kind of method for preparing 3.5 valency V electrolytes, the method comprising the steps of：
(1) vanadic anhydride is placed in reacting furnace, adds reducing substances to carry out reduction reaction at 500 DEG C~600 DEG C；
(2) step (1) reacting rear material is lowered the temperature and carries out first time washing and filtration；
(3) material after step (2) being washed and filtered Jing first time carries out second washing with acid solution, then carries out the 3rd
Secondary washing and filtration；
(4) material by step (3) Jing after third time is washed and filtered is added in sulphuric acid and is heated to material dissolution, obtains vanadium
Electrolyte.
Wherein, the temperature of reduction reaction described in step (1) can for 500 DEG C, 510 DEG C, 520 DEG C, 530 DEG C, 540 DEG C, 550
DEG C, 560 DEG C, 570 DEG C, 580 DEG C, 590 DEG C or 600 DEG C etc., it is not limited to cited numerical value, in the numerical range other
Unrequited numerical value is equally applicable.
In the present invention, the temperature of the reduction reaction is to affect vanadium dioxide and Vanadium sesquioxide in obtained V electrolyte
One of key factor of ratio.If reduction reaction temperature is too high, vanadic anhydride can be made to melt piece agent；If reduction reaction temperature
It is too low, tetravalence vanadium can be made excessive, the valence state for making obtained V electrolyte deviates target valence state.Therefore need to be by the temperature control of reduction reaction
System is in the reasonable scope.
Heretofore described " ppm " is referred to " mg/L ".
It is following as currently preferred technical scheme, but not as the present invention provide technical scheme restriction, pass through
Technical scheme below, can preferably reach and realize the technical purpose and beneficial effect of the present invention.
As currently preferred technical scheme, the purity >=99.5wt% of step (1) vanadic anhydride, for example
99.5wt%, 99.6wt%, 99.7wt%, 99.8wt% or 99.9wt% etc., it is not limited to cited numerical value, the number
Other unrequited numerical value are equally applicable in the range of value.
Preferably, reacting furnace described in step (1) is air-tight state.
Preferably, reacting furnace described in step (1) is atmosphere furnace.
Used as currently preferred technical scheme, reducing substances described in step (1) are ammonia and/or liquefied ammonia, preferably
Ammonia.
Preferably, impurity content≤0.01wt% in the ammonia；
Preferably, vanadic anhydride described in step (1) and the mol ratio of reducing substances are 1:(0.6~3), such as 1:
0.6、1:0.8、1:1、1:1.2、1:1.4、1:1.6、1:1.8、1:2、1:2.2、1:2.4、1:2.6、1:2.8 or 1:3 etc., but and
It is not limited only to other unrequited numerical value in cited numerical value, the numerical range equally applicable, preferably 1:2.5.
In the present invention, the consumption of reducing agent is to affect vanadium dioxide and Vanadium sesquioxide ratio in obtained V electrolyte
One of key factor.If the consumption of reducing agent is excessive, can make to remain excessive reducing agent in product；If the consumption mistake of reducing agent
It is few, whole reduction process can be made insufficient, cannot get Vanadium sesquioxide.
Used as currently preferred technical scheme, reduction temperature described in step (1) is 500 DEG C~550 DEG C.
Preferably, the time of step (1) reduction reaction be 1h~3h, such as 1h, 1.3h, 1.5h, 1.7h, 2h,
2.3h, 2.5h, 2.7h or 3h etc., it is not limited to other unrequited numerical value are same in cited numerical value, the numerical range
Sample is suitable for, preferably 1.5h~2h.
Preferably, vanadium dioxide and the mol ratio of Vanadium sesquioxide are (1.05 in the material that step (1) reduction reaction is obtained
~1.2):1, such as 1.05:1、1.07:1、1.1:1、1.13:1、1.15:1、1.17:1 or 1.2:1 etc., it is not limited to institute
Other unrequited numerical value are equally applicable in the numerical value enumerated, the numerical range.
Used as currently preferred technical scheme, step (2) cooling is carried out under ammonia atmosphere.
Preferably, it is independently redistilled water used by step (2) the first time washing and third time washing.
Preferably, impurity content ＜ 20ppm in the redistilled water, such as 18ppm, 16ppm, 14ppm, 12ppm,
10ppm, 8ppm, 6ppm or 4ppm etc. and lower loading, it is not limited to cited numerical value, in the numerical range other
Unrequited numerical value is equally applicable.
Used as currently preferred technical scheme, step (3) acid solution is sulphuric acid and/or hydrochloric acid.
Preferably, the concentration of step (3) acid solution be 1wt%~10wt%, such as 1wt%, 2wt%, 3wt%,
4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt% etc., it is not limited to cited numerical value, the numerical value
In the range of other unrequited numerical value it is equally applicable, preferably 5wt%~8wt%
Used as currently preferred technical scheme, the concentration of step (4) sulphuric acid is 25wt%~98wt%, for example
25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%,
80wt%, 85wt%, 90wt% or 98wt% etc., it is not limited to other are not arranged in cited numerical value, the numerical range
The numerical value of act is equally applicable, preferably 50wt%.
Used as currently preferred technical scheme, step (4) V electrolyte is vanadium dioxide and Vanadium sesquioxide
Mixed solution.
Preferably, in step (4) V electrolyte impurity ion content≤10ppm, such as 10ppm, 9ppm,
8ppm, 7ppm, 6ppm, 5ppm, 4ppm, 3ppm, 2ppm or 1ppm etc., it is not limited to cited numerical value, the numerical value model
Other unrequited numerical value are equally applicable in enclosing.
As currently preferred technical scheme, the method comprising the steps of：
(1) purity >=99.5wt% vanadic anhydrides are placed in closed atmosphere stove, are passed through impurity content≤0.01wt%
Ammonia reduction reaction 1.5h~2h is carried out at 500 DEG C~550 DEG C to vanadium dioxide in product and Vanadium sesquioxide
Capacity Ratio is (1.05~1.2):1, wherein vanadic anhydride and the mol ratio of ammonia are 1:(0.6~3)；
(2) by step (1) reacting rear material lower the temperature and carried out with the secondary water of impurity content ＜ 20ppm washing for the first time and
Filter；
(3) material after step (2) being washed and filtered Jing first time is carried out with the sulphuric acid that concentration is 5wt%~8wt%
Wash, then carry out third time washing and filtration for second；
(4) material by step (3) Jing after third time is washed and filtered is added in sulphuric acid and is heated to material dissolution, obtains miscellaneous
Matter ion concentration≤V electrolyte of 10ppm.
V electrolyte purity obtained in the method that V electrolyte is prepared with above-mentioned material amounts and proportioning of the invention is optimum.
Compared with prior art, the invention has the advantages that：
The method of the invention controls reaction condition (i.e. reaction temperature and reduction with high purity vanadic anhydride as raw material
Agent consumption etc.), by reduction, washing and dissolving be obtained impurity ion content≤the high purity vanadium electricity of 3.5 valence states of 10ppm
Liquid is solved, technique and equipment are simple, easy to operate, low cost, it is easy to large-scale production.
Specific embodiment
For the present invention is better described, technical scheme is readily appreciated, below to the present invention further specifically
It is bright.But following embodiments is only the simple example of the present invention, the scope of the present invention is not represented or limits, this
Invention protection domain is defined by claims.
Specific embodiment of the invention part provide a kind of method for preparing 3.5 valency V electrolytes, methods described include with
Lower step：
(1) vanadic anhydride is placed in reacting furnace, adds reducing substances to carry out reduction reaction at 500 DEG C~600 DEG C；
(2) step (1) reacting rear material is lowered the temperature and carries out first time washing and filtration；
(3) material after step (2) being washed and filtered Jing first time carries out second washing and filtration with sulphuric acid；
(4) material by step (3) Jing after second is washed and filtered is added in sulphuric acid and is heated to material dissolution, obtains vanadium
Electrolyte.
It is below present invention typical case but non-limiting example：
Embodiment 1：
A kind of preparation method of 3.5 valency V electrolyte is present embodiments provided, be the method comprising the steps of：
(1) vanadic anhydride of homemade purity >=99.5wt% is placed in closed high-temperature energy-conservation atmosphere furnace, is passed through
Impurity content≤0.01wt% ammonias, vanadic anhydride is 1 with the mol ratio of ammonia:1.5, it is warming up to 500 DEG C of reduction 3h；
(2) ammonia cooling will be passed through in step (1) reacting rear material, Jing constant-current titrations measure titanium dioxide in reacting rear material
Vanadium is 1.05 with the Capacity Ratio of Vanadium sesquioxide:1,50g reactants are taken out, with the secondary water of 1000mL impurity content ＜ 20ppm
Washed in three times and filtered；
(3) it is that 1wt% dilute sulfuric acids enter in three times with 1000mL mass fractions by the scrubbed material with after filtration of step (2)
Row washing and filtration；
(4) material by step (3) Jing after second is washed and filtered adds 200mL secondary waters and the heating of 42mL concentrated sulphuric acids
It is all dissolved, obtain high-purity V electrolyte of 3.5 valence states of 1.6mol/L.
Each ion concentration in high-purity V electrolyte is determined, as shown in table 1.
Table 1：Each ion concentration in high-purity V electrolyte in embodiment 1
| Ion | Al | Ca | Cr | Fe | K | Mg | Mn | Na | P_ | Si | Ti |
| Unit ppm | 6.21 | 4.25 | 1.05 | 7.23 | 2.14 | 0.37 | 0.29 | 6.58 | Do not detect | 2.06 | 0.41 |
Embodiment 2：
A kind of preparation method of 3.5 valency V electrolyte is present embodiments provided, be the method comprising the steps of：
(1) vanadic anhydride of homemade purity >=99.5wt% is placed in closed high-temperature energy-conservation atmosphere furnace, is passed through
Impurity content≤0.01wt% ammonias, vanadic anhydride is 1 with the mol ratio of ammonia:1, it is warming up to 500 DEG C of reduction 3h；
(2) ammonia cooling will be passed through in step (1) reacting rear material, Jing constant-current titrations measure titanium dioxide in reacting rear material
Vanadium is 1.1 with the Capacity Ratio of Vanadium sesquioxide:1,50g reactants are taken out, with the secondary moisture of 1000mL impurity content ＜ 20ppm
Washed and filtered for three times；
(3) by step (2) it is scrubbed and filter after material with 1000mL mass fractions be 10wt% dilute sulfuric acids in three times
Washed and filtered；
(4) material by step (3) Jing after second is washed and filtered adds 200mL secondary waters and the heating of 50mL concentrated sulphuric acids
It is all dissolved, obtain high-purity V electrolyte of 3.5 valence states of 1.59mol/L.
Each ion concentration in high-purity V electrolyte is determined, as shown in table 2.
Table 2：Each ion concentration in high-purity V electrolyte in embodiment 2
| Ion | Al | Ca | Cr | Fe | K | Mg | Mn | Na | P_ | Si | Ti |
| Unit ppm | 5.87 | 4.31 | 1.12 | 6.87 | 2.31 | 0.41 | 0.16 | 5.92 | Do not detect | 1.86 | 0.61 |
Embodiment 3：
A kind of preparation method of 3.5 valency V electrolyte is present embodiments provided, be the method comprising the steps of：
(1) vanadic anhydride of homemade purity >=99.5wt% is placed in closed high-temperature energy-conservation atmosphere furnace, is passed through
Impurity content≤0.01wt% ammonias, vanadic anhydride is 1 with the mol ratio of ammonia:2, it is warming up to 500 DEG C of reduction 1h；
(2) ammonia cooling will be passed through in step (1) reacting rear material, Jing constant-current titrations measure titanium dioxide in reacting rear material
Vanadium is 1.15 with the Capacity Ratio of Vanadium sesquioxide:1,50g reactants are taken out, with the secondary water of 1000mL impurity content ＜ 20ppm
Washed in three times and filtered；
(3) it is that 5wt% dilute sulfuric acids enter in three times with 1000mL mass fractions by the scrubbed material with after filtration of step (2)
Row washing and filtration；
(4) material by step (3) Jing after second is washed and filtered adds 200mL secondary waters and the heating of 42mL concentrated sulphuric acids
It is all dissolved, obtain high-purity V electrolyte of 3.5 valence states of 1.6mol/L.
Each ion concentration in high-purity V electrolyte is determined, as shown in table 3.
Table 3：Each ion concentration in high-purity V electrolyte in embodiment 3
| Ion | Al | Ca | Cr | Fe | K | Mg | Mn | Na | P_ | Si | Ti |
| Unit ppm | 6.21 | 4.25 | 1.05 | 7.23 | 2.14 | 0.37 | 0.29 | 6.58 | Do not detect | 2.06 | 0.41 |
Embodiment 4：
A kind of preparation method of 3.5 valency V electrolyte is present embodiments provided, be the method comprising the steps of：
(1) vanadic anhydride of homemade purity >=99.5wt% is placed in closed high-temperature energy-conservation atmosphere furnace, is passed through
Impurity content≤0.01wt% ammonias, vanadic anhydride is 1 with the mol ratio of ammonia:0.8, it is warming up to 500 DEG C of reductase 12 h；
(2) ammonia cooling will be passed through in step (1) reacting rear material, Jing constant-current titrations measure titanium dioxide in reacting rear material
Vanadium is 1.2 with the Capacity Ratio of Vanadium sesquioxide:1,50g reactants are taken out, with the secondary moisture of 1000mL impurity content ＜ 20ppm
Washed and filtered for three times；
(3) it is that 8wt% dilute sulfuric acids enter in three times with 1000mL mass fractions by the scrubbed material with after filtration of step (2)
Row washing and filtration；
(4) material by step (3) Jing after second is washed and filtered adds 200mL secondary waters and the heating of 40mL concentrated sulphuric acids
It is all dissolved, obtain high-purity V electrolyte of 3.5 valence states of 1.51mol/L.
Each ion concentration in high-purity V electrolyte is determined, as shown in table 4.
Table 4：Each ion concentration in high-purity V electrolyte in embodiment 4
| Ion | Al | Ca | Cr | Fe | K | Mg | Mn | Na | P_ | Si | Ti |
| Unit ppm | 5.62 | 3.97 | 0.98 | 6.89 | 2.01 | 0.29 | 0.13 | 6.02 | Do not detect | 1.86 | 0.26 |
Embodiment 5：
A kind of preparation method of 3.5 valency V electrolyte is present embodiments provided, be the method comprising the steps of：
(1) vanadic anhydride of homemade purity >=99.5wt% is placed in closed high-temperature energy-conservation atmosphere furnace, is passed through
Impurity content≤0.01wt% ammonias, vanadic anhydride is 1 with the mol ratio of ammonia:1, it is warming up to 550 DEG C of reduction 1.5h；
(2) ammonia cooling will be passed through in step (1) reacting rear material, Jing constant-current titrations measure titanium dioxide in reacting rear material
Vanadium is 1.2 with the Capacity Ratio of Vanadium sesquioxide:1,50g reactants are taken out, with the secondary moisture of 1000mL impurity content ＜ 20ppm
Washed and filtered for three times；
(3) it is that 5wt% dilute sulfuric acids enter in three times with 1000mL mass fractions by the scrubbed material with after filtration of step (2)
Row washing and filtration；
(4) material by step (3) Jing after second is washed and filtered adds 200mL secondary waters and the heating of 40mL concentrated sulphuric acids
It is all dissolved, obtain high-purity V electrolyte of 3.5 valence states of 1.63mol/L.
Each ion concentration in high-purity V electrolyte is determined, as shown in table 5.
Table 5：Each ion concentration in high-purity V electrolyte in embodiment 5
| Ion | Al | Ca | Cr | Fe | K | Mg | Mn | Na | P_ | Si | Ti |
| Unit ppm | 6.56 | 4.13 | 1.21 | 7.56 | 2.08 | 0.35 | 0.32 | 6.41 | Do not detect | 2.24 | 0.49 |
Embodiment 6：
A kind of preparation method of 3.5 valency V electrolyte is present embodiments provided, methods described is except five oxidations in step (1)
Two vanadium are 1 with the mol ratio of ammonia:0.6, reduction temperature is 530 DEG C outer, unclassified stores consumption and preparation process with embodiment 1
In it is identical, obtain impurity ion content≤high-purity V electrolyte of 3.5 valence states of 10ppm.
| Ion | Al | Ca | Cr | Fe | K | Mg | Mn | Na | P_ | Si | Ti |
| Unit ppm | 5.83 | 3.61 | 1.02 | 6.95 | 2.12 | 0.42 | 0.12 | 5.43 | Do not detect | 1.36 | 0.38 |
Embodiment 7：
A kind of preparation method of 3.5 valency V electrolyte is present embodiments provided, methods described is except five oxidations in step (1)
Two vanadium are 1 with the mol ratio of ammonia:3, reduction temperature is 600 DEG C outer, unclassified stores consumption and preparation process with embodiment 1 in
It is identical, obtain impurity ion content≤high-purity V electrolyte of 3.5 valence states of 10ppm.
| Ion | Al | Ca | Cr | Fe | K | Mg | Mn | Na | P_ | Si | Ti |
| Unit ppm | 6.23 | 4.23 | 1.09 | 7.32 | 2.35 | 0.32 | 0.23 | 6.12 | Do not detect | 2.61 | 0.21 |
Comparative example 1：
This comparative example provides a kind of preparation method of V electrolyte, and methods described is except vanadic anhydride in step (1)
It is 1 with the mol ratio of ammonia:5 (＜ 1:3) outward, unclassified stores consumption is in the same manner as in Example 1 with preparation process, obtains vanadium electricity
The price of vanadium is the valence state of 30% 3 valence state+70% four in solution liquid, and its valence state deviates 3.5 valencys, it is impossible to target product is obtained, wherein miscellaneous
Matter ion concentration is as follows.
| Ion | Al | Ca | Cr | Fe | K | Mg | Mn | Na | P_ | Si | Ti |
| Unit ppm | 6.56 | 4.23 | 1.09 | 7.45 | 2.35 | 0.32 | 0.61 | 6.12 | Do not detect | 25.14 | 0.21 |
Comparative example 2：
This comparative example provides a kind of preparation method of V electrolyte, and methods described is except vanadic anhydride in step (1)
It is 1 with the mol ratio of ammonia:0.1 (＞ 1:0.6) outward, unclassified stores consumption is in the same manner as in Example 1 with preparation process, obtains
The price of vanadium is the essentially valence state of 20% 4 valence state+80% five in V electrolyte, and its valence state deviates 3.5 valencys, it is impossible to obtain target
Product.
Comparative example 3：
This comparative example provide a kind of preparation method of V electrolyte, methods described except in step (1) reduction temperature be
700 DEG C (600 DEG C of ＞) outward, unclassified stores consumption is in the same manner as in Example 1 with preparation process, obtains the valency of vanadium in V electrolyte
Position is five valence states, it is impossible to obtain target product.
Comparative example 4：
This comparative example provide a kind of preparation method of V electrolyte, methods described except in step (1) reduction temperature be
400 DEG C (500 DEG C of ＜) outward, unclassified stores consumption is in the same manner as in Example 1 with preparation process, obtains the valency of vanadium in V electrolyte
Position is four valence states, it is impossible to obtain target product.
The result of integrated embodiment 1-7 and comparative example 1-4 can be seen that the method for the invention with high purity vanadic anhydride
For raw material, control reaction condition (i.e. reaction temperature and reducing agent consumption etc.), it is obtained by reduction, washing and dissolving miscellaneous
Matter ion concentration≤high-purity V electrolyte of 3.5 valence states of 10ppm, technique and equipment it is simple, easy to operate, low cost, easily
In large-scale production.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff it will be clearly understood that any improvement in the present invention, the equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (9)
1. a kind of method for preparing 3.5 valency V electrolytes, it is characterised in that the method comprising the steps of：
(1) vanadic anhydride is placed in reacting furnace, adds reducing substances to carry out reduction reaction at 500 DEG C~600 DEG C；
(2) step (1) reacting rear material is lowered the temperature and carries out first time washing and filtration；
(3) material after step (2) being washed and filtered Jing first time carries out second washing with acid solution, then carries out washing for the third time
Wash and filter；
(4) material by step (3) Jing after third time is washed and filtered is added in sulphuric acid and is heated to material dissolution, obtains vanadium electrolysis
Liquid.
2. method according to claim 1, it is characterised in that the purity of step (1) vanadic anhydride >=
99.5wt%；
Preferably, reacting furnace described in step (1) is air-tight state；
Preferably, reacting furnace described in step (1) is atmosphere furnace.
3. method according to claim 1 and 2, it is characterised in that reducing substances described in step (1) be ammonia and/or
Liquefied ammonia, preferably ammonia；
Preferably, impurity content≤0.01wt% in the ammonia；
Preferably, vanadic anhydride described in step (1) and the mol ratio of reducing substances are 1:(0.6~3), preferably 1:2.5.
4. the method according to any one of claim 1-3, it is characterised in that reduction temperature described in step (1) is 500 DEG C
~550 DEG C；
Preferably, the time of step (1) reduction reaction is 1h~3h, preferably 1.5h~2h；
Preferably, in the material that step (1) reduction reaction is obtained the mol ratio of vanadium dioxide and Vanadium sesquioxide for (1.05~
1.2):1。
5. the method according to any one of claim 1-4, it is characterised in that step (2) cooling is in ammonia atmosphere
Under carry out；
Preferably, it is independently redistilled water that step (2) the first time washing and third time wash cleaning mixture used；
Preferably, impurity content ＜ 20ppm in the redistilled water.
6. the method according to any one of claim 1-5, it is characterised in that step (3) acid solution is sulphuric acid and/or salt
Acid；
Preferably, the concentration of step (3) acid solution is 1wt%~10wt%, preferably 5wt%~8wt%.
7. the method according to any one of claim 1-6, it is characterised in that the concentration of step (4) sulphuric acid is
25wt%~98wt%, preferably 50wt%.
8. the method according to any one of claim 1-7, it is characterised in that step (4) V electrolyte is titanium dioxide
The mixed solution of vanadium and Vanadium sesquioxide；
Preferably, in step (4) V electrolyte impurity ion content≤10ppm.
9. the method according to any one of claim 1-8, it is characterised in that the method comprising the steps of：
(1) purity >=99.5wt% vanadic anhydrides are placed in closed atmosphere stove, are passed through the ammonia of impurity content≤0.01wt%
Gas carries out reduction reaction 1.5h~2h to vanadium dioxide in product and the capacity of Vanadium sesquioxide at 500 DEG C~550 DEG C
Than for (1.05~1.2):1, wherein vanadic anhydride and the mol ratio of ammonia are 1:(0.6~3)；
(2) step (1) reacting rear material is lowered the temperature and carries out with the secondary water of impurity content ＜ 20ppm first time and washed and mistake
Filter；
(3) material after step (2) being washed and filtered Jing first time carries out second with the sulphuric acid that concentration is 5wt%~8wt%
Secondary washing, then carry out third time washing and filtration；
(4) by step (3) Jing third time wash and filter after material add sulphuric acid in be heated to material dissolution, obtain impurity from
Sub- content≤V electrolyte of 10ppm.
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| CN110838592A (en) * | 2018-08-16 | 2020-02-25 | 江苏泛宇能源有限公司 | Preparation method of flow battery electrolyte |
| CN114361549A (en) * | 2022-01-20 | 2022-04-15 | 北京普能世纪科技有限公司 | Method for preparing vanadium electrolyte for all-vanadium redox flow battery |
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