CN106684421B - Method for preparing vanadium electrolyte - Google Patents
Method for preparing vanadium electrolyte Download PDFInfo
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- CN106684421B CN106684421B CN201710024733.2A CN201710024733A CN106684421B CN 106684421 B CN106684421 B CN 106684421B CN 201710024733 A CN201710024733 A CN 201710024733A CN 106684421 B CN106684421 B CN 106684421B
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- 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
Abstract
The invention provides a method for preparing a 3.5-valent vanadium electrolyte, which comprises the following steps: (1) putting vanadium pentoxide into a reaction furnace, adding a reducing substance into the reaction furnace, and carrying out reduction reaction at 500-600 ℃; (2) cooling the reacted materials, washing and filtering for the first time; (3) washing the material after the first washing and filtering with acid liquor for the second time, and then washing and filtering for the third time; (4) and adding the material washed and filtered for the third time into sulfuric acid, and heating until the material is dissolved to obtain the vanadium electrolyte. The method takes high-purity vanadium pentoxide as a raw material, controls reaction conditions, and obtains the high-purity vanadium electrolyte with the valence state of 3.5 by reduction, washing and dissolution, and has the advantages of simple process and equipment, convenient operation, low cost and easy large-scale production.
Description
Technical Field
The invention belongs to the technical field of electrolyte, relates to a method for preparing vanadium electrolyte, and particularly relates to a method for preparing high-purity 3.5-valent vanadium electrolyte with equal capacity of trivalent vanadium and tetravalent vanadium by reducing vanadium pentoxide
Background
The vanadium electrolyte is a solution system with multiple valence states, high concentration and high stability, and is divided into a positive electrolyte and a negative electrolyte. The positive electrolyte is a sulfuric acid solution of V (IV)/V (V), the negative electrolyte is a sulfuric acid solution of V (II)/V (III), a sufficiently high sulfuric acid solution is ensured to complete the positive and negative electrode reactions, and after charging, the positive and negative electrodes can obtain a pentavalent vanadium ion solution and a divalent vanadium ion solution. Therefore, when the 3.5-valent vanadium electrolyte is adopted, the charging and discharging of the all-vanadium redox flow battery can be directly carried out without activation.
Although the existing vanadium electrolyte preparation technology is various, V is mostly used2O5Or V2O3The vanadium electrolyte is prepared by adopting a chemical method, an electrochemical electrolysis method or a combination of the chemical method and the electrochemical electrolysis method as raw materials. However, the vanadium electrolyte generally exists in the form of vanadyl sulfate or other valence vanadium solutions, so that the direct one-step method for obtaining high-purity vanadium electrolyte with the valence of 3.5 and the capacity of tetravalent vanadium and trivalent vanadium and the like is the core problem of the vanadium battery energy storage system.
CN 104638288A discloses an electrochemical preparation method of a 3.5-valent vanadium electrolyte, which uses an electrolysis device to use half volume of a 4-valent vanadium solution as a positive electrode electrolyte and one volume of the 4-valent vanadium solution as a negative electrode electrolyte, and under the action of current supplied by a power supply, controls the electrolysis electric quantity, and reduces the vanadium of the negative electrode electrolyte from 4-valent to 3.5-valent.
CN 1598063A discloses an electrolytic preparation method of an all vanadium ion flow battery electrolyte, which comprises the steps of sequentially adding vanadium trioxide and vanadium pentoxide into a sulfuric acid solution in a ratio of 1:1 to obtain a vanadyl sulfate solution, and then adding additives such as sodium sulfate, an emulsifier OP and the like to carry out electrolysis to obtain a vanadium battery electrolyte in which trivalent vanadium and tetravalent vanadium respectively account for 50% of the total vanadium.
CN 101192674 discloses a preparation method of an electrolyte for an all-vanadium redox flow battery, which comprises the steps of uniformly mixing vanadium trioxide and concentrated sulfuric acid according to a certain proportion, calcining in a tubular electric furnace at 100-300 ℃, and dissolving in dilute sulfuric acid to obtain vanadium battery electrolytes in which trivalent vanadium and tetravalent vanadium respectively account for 50% of the total vanadium.
CN 1719655 discloses an all vanadium ion flow battery electrolyte and a preparation method thereof, which takes qualified vanadium liquid of a vanadium plant as a raw material, uses sulfuric acid to adjust the pH value, then uses liquid sulfur dioxide as a reducing agent to carry out reduction, then uses sodium carbonate to adjust the pH value to obtain vanadium dioxide precipitate, dissolves the precipitate in water, sulfuric acid and ethanol solution, adds an additive, and then carries out electrolysis to obtain vanadium battery electrolyte with trivalent vanadium and quadrivalent vanadium accounting for 50 percent of the total vanadium.
It can be seen that the existing high-purity vanadium electrolyte with 3.5 valence state is generally prepared by an electrolytic method, which requires special equipment and strict sealing conditions, has strict requirements on reaction conditions, and is difficult to apply on a large scale. In the chemical preparation process, additives are generally required to be added or the preparation is not carried out in a single sulfuric acid system, so that the purity of the prepared vanadium electrolyte is difficult to ensure.
Disclosure of Invention
Aiming at the problems that the existing preparation method of the high-purity vanadium electrolyte with the valence state of 3.5 has strict equipment requirement, is difficult to be applied in a large scale, and the purity of the electrolyte is difficult to meet the requirement, the invention provides a method for preparing the vanadium electrolyte with the valence state of 3.5. The method takes high-purity vanadium pentoxide as a raw material, controls reaction conditions, and obtains the high-purity vanadium electrolyte with the valence state of 3.5 by reduction, washing and dissolution, and has the advantages of simple process and equipment, convenient operation, low cost and easy large-scale production.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing a 3.5-valent vanadium electrolyte, which comprises the following steps:
(1) putting vanadium pentoxide into a reaction furnace, adding a reducing substance into the reaction furnace, and carrying out reduction reaction at 500-600 ℃;
(2) cooling the material reacted in the step (1), and washing and filtering for the first time;
(3) washing the material subjected to the first washing and filtering in the step (2) with acid liquor for the second time, and then washing and filtering for the third time;
(4) and (4) adding the material washed and filtered for the third time in the step (3) into sulfuric acid, and heating until the material is dissolved to obtain the vanadium electrolyte.
The temperature of the reduction reaction in step (1) may be 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, or 600 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, the temperature of the reduction reaction is one of the key factors influencing the ratio of vanadium dioxide to vanadium trioxide in the prepared vanadium electrolyte. If the temperature of the reduction reaction is too high, vanadium pentoxide can be melted into tablets; if the reduction reaction temperature is too low, the tetravalent vanadium is too much, and the valence state of the prepared vanadium electrolyte deviates from the target valence state. Therefore, the temperature of the reduction reaction needs to be controlled within a reasonable range.
The term "ppm" as used herein means "mg/L".
The following technical solutions are preferred but not limited to the technical solutions provided by the present invention, and the technical objects and advantages of the present invention can be better achieved and realized by the following technical solutions.
As a preferred embodiment of the present invention, the purity of the vanadium pentoxide in step (1) is not less than 99.5 wt%, for example, 99.5 wt%, 99.6 wt%, 99.7 wt%, 99.8 wt%, or 99.9 wt%, but the purity is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable.
Preferably, the reaction furnace in the step (1) is in a closed state.
Preferably, the reaction furnace in step (1) is an atmosphere furnace.
As a preferred embodiment of the present invention, the reducing substance in step (1) is ammonia gas and/or liquid ammonia, preferably ammonia gas.
Preferably, the content of impurities in the ammonia gas is less than or equal to 0.01 wt%;
preferably, the molar ratio of vanadium pentoxide to reducing substance in step (1) is 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, but not limited to the recited values, and other values not recited within this range of values are equally applicable, preferably 1: 2.5.
In the invention, the dosage of the reducing agent is one of key factors influencing the ratio of vanadium dioxide to vanadium trioxide in the prepared vanadium electrolyte. If the amount of the reducing agent is too large, too much reducing agent remains in the product; if the dosage of the reducing agent is too small, the whole reduction process is insufficient, and vanadium trioxide cannot be obtained.
As a preferable technical scheme of the invention, the reduction temperature in the step (1) is 500-550 ℃.
Preferably, the reduction reaction time in step (1) is 1h to 3h, such as 1h, 1.3h, 1.5h, 1.7h, 2h, 2.3h, 2.5h, 2.7h or 3h, but not limited to the recited values, and other values not recited in the numerical range are also applicable, preferably 1.5h to 2 h.
Preferably, the molar ratio of vanadium dioxide to vanadium trioxide in the material obtained by the reduction reaction in step (1) is (1.05-1.2): 1, for example, 1.05:1, 1.07:1, 1.1:1, 1.13:1, 1.15:1, 1.17:1 or 1.2:1, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferable technical scheme of the invention, the temperature reduction in the step (2) is carried out in an ammonia gas atmosphere.
Preferably, the first washing and the third washing in the step (2) are independently double distilled water.
Preferably, the secondary distilled water has an impurity content of < 20ppm, such as 18ppm, 16ppm, 14ppm, 12ppm, 10ppm, 8ppm, 6ppm or 4ppm and the like and lower, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
As a preferable technical scheme of the invention, the acid solution in the step (3) is sulfuric acid and/or hydrochloric acid.
Preferably, the acid solution of step (3) has a concentration of 1 wt% to 10 wt%, such as 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt%, etc., but not limited to the recited values, and other non-recited values within the range of values are equally applicable, preferably 5 wt% to 8 wt%
As a preferred embodiment of the present invention, the concentration of the sulfuric acid in the step (4) is 25 wt% to 98 wt%, for example, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 98 wt%, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable, preferably 50 wt%.
As a preferable technical scheme of the invention, the vanadium electrolyte in the step (4) is a mixed solution of vanadium dioxide and vanadium trioxide.
Preferably, the vanadium electrolyte in step (4) has an impurity ion content of 10ppm or less, such as 10ppm, 9ppm, 8ppm, 7ppm, 6ppm, 5ppm, 4ppm, 3ppm, 2ppm or 1ppm, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) putting vanadium pentoxide with the purity of more than or equal to 99.5 wt% into a closed atmosphere furnace, introducing ammonia gas with the impurity content of less than or equal to 0.01 wt% into the closed atmosphere furnace, and carrying out reduction reaction for 1.5-2 h at 500-550 ℃ until the volume ratio of vanadium dioxide to vanadium trioxide in a reaction product is (1.05-1.2): 1, wherein the molar ratio of vanadium pentoxide to ammonia gas is 1 (0.6-3);
(2) cooling the materials reacted in the step (1) and carrying out primary washing and filtering by secondary water with the impurity content less than 20 ppm;
(3) carrying out secondary washing on the material subjected to the primary washing and filtering in the step (2) by using sulfuric acid with the concentration of 5-8 wt%, and then carrying out tertiary washing and filtering;
(4) and (4) adding the material washed and filtered for the third time in the step (3) into sulfuric acid, and heating until the material is dissolved to obtain the vanadium electrolyte with impurity ion content less than or equal to 10 ppm.
The vanadium electrolyte prepared by the method for preparing the vanadium electrolyte according to the material using amount and the mixture ratio has the optimal purity.
Compared with the prior art, the invention has the following beneficial effects:
the method takes high-purity vanadium pentoxide as a raw material, controls reaction conditions (namely reaction temperature, dosage of a reducing agent and the like), and obtains the 3.5-valence-state high-purity vanadium electrolyte with impurity ion content less than or equal to 10ppm by reduction, washing and dissolution.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The specific embodiment of the invention provides a method for preparing a 3.5-valent vanadium electrolyte, which comprises the following steps:
(1) putting vanadium pentoxide into a reaction furnace, adding a reducing substance into the reaction furnace, and carrying out reduction reaction at 500-600 ℃;
(2) cooling the material reacted in the step (1), and washing and filtering for the first time;
(3) carrying out secondary washing and filtering on the material subjected to the primary washing and filtering in the step (2) by using sulfuric acid;
(4) and (4) adding the material subjected to the second washing and filtering in the step (3) into sulfuric acid, and heating until the material is dissolved to obtain the vanadium electrolyte.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a preparation method of a 3.5-valent vanadium electrolyte, which comprises the following steps:
(1) placing self-made vanadium pentoxide with the purity of more than or equal to 99.5 wt% in a closed high-temperature energy-saving atmosphere furnace, introducing ammonia gas with the impurity content of less than or equal to 0.01 wt%, wherein the molar ratio of the vanadium pentoxide to the ammonia gas is 1:1.5, and heating to 500 ℃ for reduction for 3 hours;
(2) introducing ammonia gas into the material reacted in the step (1) for cooling, measuring the volume ratio of vanadium dioxide to vanadium trioxide in the reacted material to be 1.05:1 by potentiometric titration, taking out 50g of reactant, washing and filtering by using 1000mL of secondary water with impurity content less than 20ppm for three times;
(3) washing and filtering the material washed and filtered in the step (2) by 1000mL of dilute sulfuric acid with the mass fraction of 1 wt% for three times;
(4) and (4) adding 200mL of secondary water and 42mL of concentrated sulfuric acid into the material subjected to secondary washing and filtering in the step (3), and heating to completely dissolve the material to obtain 1.6mol/L of high-purity vanadium electrolyte with the valence state of 3.5.
The content of each ion in the high-purity vanadium electrolyte was measured, as shown in table 1.
Table 1: ion contents of the high purity vanadium electrolyte in example 1
| Ion(s) | 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 | Not detected out | 2.06 | 0.41 |
Example 2:
the embodiment provides a preparation method of a 3.5-valent vanadium electrolyte, which comprises the following steps:
(1) placing self-made vanadium pentoxide with the purity of more than or equal to 99.5 wt% in a closed high-temperature energy-saving atmosphere furnace, introducing ammonia gas with the impurity content of less than or equal to 0.01 wt%, wherein the molar ratio of the vanadium pentoxide to the ammonia gas is 1:1, and heating to 500 ℃ for reduction for 3 hours;
(2) introducing ammonia gas into the material reacted in the step (1) for cooling, measuring the volume ratio of vanadium dioxide to vanadium trioxide in the reacted material to be 1.1:1 by potentiometric titration, taking out 50g of reactant, washing and filtering by using 1000mL of secondary water with impurity content less than 20ppm for three times;
(3) washing and filtering the material washed and filtered in the step (2) by 1000mL of dilute sulfuric acid with the mass fraction of 10 wt% for three times;
(4) and (4) adding 200mL of secondary water and 50mL of concentrated sulfuric acid into the material subjected to secondary washing and filtering in the step (3), and heating to completely dissolve the material to obtain 1.59mol/L of high-purity vanadium electrolyte with the valence state of 3.5.
The content of each ion in the high-purity vanadium electrolyte was measured as shown in table 2.
Table 2: example 2 ion content of high purity vanadium electrolyte
| Ion(s) | 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 | Not detected out | 1.86 | 0.61 |
Example 3:
the embodiment provides a preparation method of a 3.5-valent vanadium electrolyte, which comprises the following steps:
(1) placing self-made vanadium pentoxide with the purity of more than or equal to 99.5 wt% in a closed high-temperature energy-saving atmosphere furnace, introducing ammonia gas with the impurity content of less than or equal to 0.01 wt%, wherein the molar ratio of the vanadium pentoxide to the ammonia gas is 1:2, and heating to 500 ℃ for reduction for 1 h;
(2) introducing ammonia gas into the material reacted in the step (1) for cooling, measuring the volume ratio of vanadium dioxide to vanadium trioxide in the reacted material to be 1.15:1 by potentiometric titration, taking out 50g of reactant, washing and filtering by using 1000mL of secondary water with impurity content less than 20ppm for three times;
(3) washing and filtering the material washed and filtered in the step (2) by 1000mL of dilute sulfuric acid with the mass fraction of 5 wt% for three times;
(4) and (4) adding 200mL of secondary water and 42mL of concentrated sulfuric acid into the material subjected to secondary washing and filtering in the step (3), and heating to completely dissolve the material to obtain 1.6mol/L of high-purity vanadium electrolyte with the valence state of 3.5.
The content of each ion in the high-purity vanadium electrolyte was measured as shown in table 3.
Table 3: ion contents of high purity vanadium electrolyte in example 3
| Ion(s) | 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 | Not detected out | 2.06 | 0.41 |
Example 4:
the embodiment provides a preparation method of a 3.5-valent vanadium electrolyte, which comprises the following steps:
(1) placing self-made vanadium pentoxide with the purity of more than or equal to 99.5 wt% in a closed high-temperature energy-saving atmosphere furnace, introducing ammonia gas with the impurity content of less than or equal to 0.01 wt%, wherein the molar ratio of the vanadium pentoxide to the ammonia gas is 1:0.8, and heating to 500 ℃ for reduction for 2 hours;
(2) introducing ammonia gas into the material reacted in the step (1) for cooling, measuring the volume ratio of vanadium dioxide to vanadium trioxide in the reacted material to be 1.2:1 by potentiometric titration, taking out 50g of reactant, washing and filtering by using 1000mL of secondary water with impurity content less than 20ppm for three times;
(3) washing and filtering the material washed and filtered in the step (2) by 1000mL of dilute sulfuric acid with the mass fraction of 8 wt% for three times;
(4) and (4) adding 200mL of secondary water and 40mL of concentrated sulfuric acid into the material subjected to secondary washing and filtering in the step (3), and heating to completely dissolve the material to obtain 1.51mol/L of high-purity vanadium electrolyte with the valence state of 3.5.
The content of each ion in the high-purity vanadium electrolyte was measured, as shown in table 4.
Table 4: example 4 ion content of high purity vanadium electrolyte
| Ion(s) | 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 | Not detected out | 1.86 | 0.26 |
Example 5:
the embodiment provides a preparation method of a 3.5-valent vanadium electrolyte, which comprises the following steps:
(1) placing self-made vanadium pentoxide with the purity of more than or equal to 99.5 wt% in a closed high-temperature energy-saving atmosphere furnace, introducing ammonia gas with the impurity content of less than or equal to 0.01 wt%, wherein the molar ratio of the vanadium pentoxide to the ammonia gas is 1:1, and heating to 550 ℃ for reduction for 1.5 h;
(2) introducing ammonia gas into the material reacted in the step (1) for cooling, measuring the volume ratio of vanadium dioxide to vanadium trioxide in the reacted material to be 1.2:1 by potentiometric titration, taking out 50g of reactant, washing and filtering by using 1000mL of secondary water with impurity content less than 20ppm for three times;
(3) washing and filtering the material washed and filtered in the step (2) by 1000mL of dilute sulfuric acid with the mass fraction of 5 wt% for three times;
(4) and (4) adding 200mL of secondary water and 40mL of concentrated sulfuric acid into the material subjected to secondary washing and filtering in the step (3), and heating to completely dissolve the material to obtain 1.63mol/L of high-purity vanadium electrolyte with the valence state of 3.5.
The content of each ion in the high-purity vanadium electrolyte was measured as shown in table 5.
Table 5: ion contents of high purity vanadium electrolyte in example 5
| Ion(s) | 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 | Not detected out | 2.24 | 0.49 |
Example 6:
the embodiment provides a preparation method of a 3.5-valent vanadium electrolyte, which is the same as that in embodiment 1 except that in step (1), the molar ratio of vanadium pentoxide to ammonia gas is 1:0.6, the reduction temperature is 530 ℃, and the use amounts and the preparation process of other materials are the same, so that the 3.5-valent high-purity vanadium electrolyte with the impurity ion content of less than or equal to 10ppm is obtained.
| Ion(s) | 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 | Not detected out | 1.36 | 0.38 |
Example 7:
the embodiment provides a preparation method of a 3.5-valent vanadium electrolyte, which is the same as that in embodiment 1 except that the molar ratio of vanadium pentoxide to ammonia gas in step (1) is 1:3, the reduction temperature is 600 ℃, and the use amounts and preparation processes of other materials are the same as those in embodiment 1, so that the 3.5-valent high-purity vanadium electrolyte with the impurity ion content of less than or equal to 10ppm is obtained.
| Ion(s) | 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 | Not detected out | 2.61 | 0.21 |
Comparative example 1:
the comparative example provides a preparation method of a vanadium electrolyte, except that the molar ratio of vanadium pentoxide to ammonia gas in the step (1) is 1:5 (< 1:3), the use amount and the preparation process of other materials are the same as those in the example 1, the valence of vanadium in the vanadium electrolyte is 30% trivalent state + 70% tetravalent state, the valence state deviates from 3.5 valence state, and a target product cannot be obtained, wherein the content of impurity ions is as follows.
| Ion(s) | 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 | Not detected out | 25.14 | 0.21 |
Comparative example 2:
the comparative example provides a preparation method of a vanadium electrolyte, except that the molar ratio of vanadium pentoxide to ammonia gas in the step (1) is 1:0.1 (> 1:0.6), the use amount and the preparation process of other materials are the same as those in the example 1, the valence of vanadium in the obtained vanadium electrolyte is basically 20% of a tetravalent state and 80% of a pentavalent state, the valence state deviates from 3.5, and a target product cannot be obtained.
Comparative example 3:
the comparative example provides a preparation method of a vanadium electrolyte, except that the reduction temperature in the step (1) is 700 ℃ (more than 600 ℃), the use amount and the preparation process of other materials are the same as those in the example 1, the valence of vanadium in the vanadium electrolyte is quinquevalent, and a target product cannot be obtained.
Comparative example 4:
the comparative example provides a preparation method of a vanadium electrolyte, except that the reduction temperature in the step (1) is 400 ℃ (500 ℃), the dosage and the preparation process of other materials are the same as those in the example 1, the valence of vanadium in the obtained vanadium electrolyte is tetravalent, and a target product cannot be obtained.
It can be seen from the results of examples 1-7 and comparative examples 1-4 that the method of the present invention uses high purity vanadium pentoxide as a raw material, controls the reaction conditions (i.e., reaction temperature, amount of reducing agent, etc.), and obtains a high purity vanadium electrolyte with a valence state of 3.5 having an impurity ion content of less than or equal to 10ppm by reduction, washing and dissolution, and the method has the advantages of simple process and equipment, convenient operation, low cost, and easy mass production.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (14)
1. A method for preparing 3.5-valent vanadium electrolyte with impurity ion content less than or equal to 10ppm is characterized by comprising the following steps:
(1) putting vanadium pentoxide into a reaction furnace, adding a reducing substance into the reaction furnace, and carrying out reduction reaction at 500-600 ℃; the time of the reduction reaction in the step (1) is 1-3 h; the molar ratio of vanadium dioxide to vanadium trioxide in the material obtained by the reduction reaction in the step (1) is (1.05-1.2): 1;
(2) cooling the material reacted in the step (1), and washing and filtering for the first time;
(3) carrying out secondary washing on the material subjected to the primary washing and filtering in the step (2) by using 1-10 wt% of acid liquor, and then carrying out tertiary washing and filtering;
(4) adding the material washed and filtered for the third time in the step (3) into 25-98 wt% of sulfuric acid, and heating until the material is dissolved to obtain vanadium electrolyte;
the reducing substance in the step (1) is ammonia gas;
in the step (1), the molar ratio of the vanadium pentoxide to the reducing substance is 1 (0.6-3).
2. The method according to claim 1, wherein the purity of the vanadium pentoxide in the step (1) is more than or equal to 99.5 wt%.
3. The method according to claim 1, wherein the reaction furnace is in a closed state in the step (1).
4. The method according to claim 1, wherein the reaction furnace in step (1) is an atmosphere furnace.
5. The method of claim 1, wherein the ammonia gas has an impurity content of 0.01 wt.% or less.
6. The method according to claim 1, wherein the molar ratio of vanadium pentoxide to reducing substance in step (1) is 1: 2.5.
7. The method according to claim 1, wherein the reduction temperature in step (1) is 500 ℃ to 550 ℃.
8. The method of claim 1, wherein the temperature reduction in step (2) is performed under an ammonia atmosphere.
9. The method of claim 1, wherein the washing solution used in the first washing in step (2) and the third washing in step (3) is independently double distilled water.
10. The method of claim 9, wherein the secondary distilled water has an impurity level of < 20 ppm.
11. The method according to claim 1, wherein the acid solution in step (3) is sulfuric acid and/or hydrochloric acid.
12. The method according to claim 1, wherein the acid solution in the step (3) has a concentration of 5 wt% to 8 wt%.
13. The method of claim 1, wherein the concentration of the sulfuric acid in step (4) is 50 wt%.
14. Method according to claim 1, characterized in that it comprises the following steps:
(1) putting vanadium pentoxide with the purity of more than or equal to 99.5 wt% into a closed atmosphere furnace, introducing ammonia gas with the impurity content of less than or equal to 0.01 wt% into the closed atmosphere furnace, and carrying out reduction reaction for 1.5-2 h at 500-550 ℃ until the molar ratio of vanadium dioxide to vanadium trioxide in a reaction product is (1.05-1.2): 1, wherein the molar ratio of vanadium pentoxide to ammonia gas is 1 (0.6-3);
(2) cooling the materials reacted in the step (1), and washing and filtering for the first time by using secondary distilled water with the impurity content less than 20 ppm;
(3) carrying out secondary washing on the material subjected to the primary washing and filtering in the step (2) by using sulfuric acid with the concentration of 5-8 wt%, and then carrying out tertiary washing and filtering;
(4) and (4) adding the material washed and filtered for the third time in 25-98 wt% of sulfuric acid, and heating until the material is dissolved to obtain the vanadium electrolyte with impurity ion content less than or equal to 10 ppm.
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| CN110317961A (en) * | 2019-08-07 | 2019-10-11 | 攀钢集团攀枝花钢铁研究院有限公司 | The method for preparing vanadic anhydride containing vanadium solution |
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| CN102074719A (en) * | 2010-12-09 | 2011-05-25 | 攀枝花学院 | Method for preparing electrolyte for all-vanadium redox flow battery |
| 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 |
| CN104124464A (en) * | 2013-04-23 | 2014-10-29 | 中国科学院上海高等研究院 | Preparation method of all-vanadium flow battery electrolyte |
| CN106257725A (en) * | 2016-01-28 | 2016-12-28 | 中国科学院过程工程研究所 | A kind of system and method preparing high activity all-vanadium flow battery specific valence state electrolyte |
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| CN102074719A (en) * | 2010-12-09 | 2011-05-25 | 攀枝花学院 | Method for preparing electrolyte for all-vanadium redox flow battery |
| 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 |
| CN104124464A (en) * | 2013-04-23 | 2014-10-29 | 中国科学院上海高等研究院 | Preparation method of all-vanadium flow battery electrolyte |
| CN106257725A (en) * | 2016-01-28 | 2016-12-28 | 中国科学院过程工程研究所 | A kind of system and method preparing high activity all-vanadium flow battery specific valence state electrolyte |
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