CN115621515A - Method for preparing vanadium electrolyte for all-vanadium redox flow battery from vanadium-containing raw material in short process and vanadium electrolyte - Google Patents
Method for preparing vanadium electrolyte for all-vanadium redox flow battery from vanadium-containing raw material in short process and vanadium electrolyte Download PDFInfo
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Abstract
The application provides a method for preparing vanadium electrolyte for an all-vanadium redox flow battery from vanadium-containing raw materials in a short process and the vanadium electrolyte, and relates to the technical field of vanadium batteries. The method comprises the following steps: mixing the vanadium-containing raw material and a sodium roasting agent for sodium roasting, and then selectively leaching to obtain vanadium-containing leaching solution; carrying out primary impurity removal on the vanadium-containing leaching solution by using magnesium salt and/or aluminum salt, and carrying out solid-liquid separation to obtain filtrate and primary purification slag; adjusting the pH of the filtrate to remove impurities and heavy metals for the second time, and performing solid-liquid separation to obtain vanadium-containing purified liquid and secondary filter residues; mixing the vanadium-containing purification solution with ammonium salt, and carrying out vanadium precipitation reaction to obtain ammonium metavanadate; calcining ammonium metavanadate to obtain a high-purity vanadium-containing oxide pure product or a calcined product of a plurality of oxides; and mixing the calcined product, pure water and concentrated sulfuric acid, and carrying out solid-liquid separation after dissolution reaction to obtain the vanadium electrolyte for the all-vanadium redox flow battery. The method provided by the application has the advantages of short process flow, low operation cost and adjustable electrolyte valence state.
Description
Technical Field
The application relates to the field of vanadium batteries, in particular to a method for preparing vanadium electrolyte for an all-vanadium redox flow battery from vanadium-containing raw materials in a short process and the vanadium electrolyte.
Background
With the development and application of renewable energy, large-scale high-efficiency energy storage technology becomes a hotspot for research and development in the energy field. The all-vanadium liquid flow energy storage system has the advantages of no pollution, long service life, high energy efficiency, simple maintenance and the like, and has huge application prospects in the fields of solar energy, wind energy storage and grid connection, power grid peak regulation, remote power supply systems, uninterruptible power supplies and the like.
The vanadium electrolyte is one of the most important components in the all-vanadium redox flow battery as a carrier of an active substance, the performance-concentration of the electrolyte directly influences the performance-energy density of the battery, and how to obtain the high-performance vanadium electrolyte becomes a hot spot of competitive research of researchers in various countries. The preparation method of the vanadium electrolyte generally comprises a chemical synthesis method, an electrolytic method and the like. All the raw materials are high-purity vanadium pentoxide, and Ammonium Metavanadate (AMV) is required to be firstly subjected to're-dissolution-purification-vanadium precipitation-calcination' for preparing the high-purity vanadium pentoxide. The subsequent chemical synthesis method and the electrolytic method both need chemical reduction dissolution or electrolytic reduction dissolution, and have complex process flow and high production cost. In order to shorten the process flow and reduce the operation cost, researches are made on preparing the vanadium electrolyte by adopting an extraction process and a short flow aiming at the vanadium-containing leachate, but the vanadium electrolyte still relates to the reduction and oxidation processes, and the prepared electrolyte has high organic matter content and low vanadium concentration and has great influence on the performance of the vanadium flow battery.
At present, the production process flow of the vanadium electrolyte is complex, the production cost is high, and a technology for preparing qualified vanadium electrolyte from vanadium-containing raw materials in a short flow needs to be researched and developed urgently.
Disclosure of Invention
The application aims to provide a method for preparing vanadium electrolyte for an all-vanadium redox flow battery from vanadium-containing raw materials in a short process and the vanadium electrolyte, so as to solve the problems.
In order to achieve the purpose, the following technical scheme is adopted in the application:
a method for preparing vanadium electrolyte for an all-vanadium redox flow battery from vanadium-containing raw materials in a short process comprises the following steps:
mixing a vanadium-containing raw material and a sodium-modified roasting agent for sodium-modified roasting, and then selectively leaching to obtain a vanadium-containing leaching solution;
carrying out first impurity removal on the vanadium-containing leachate by using magnesium salt and/or aluminum salt, and carrying out solid-liquid separation to obtain filtrate and first purification slag; adjusting the pH of the filtrate to remove impurities and heavy metals for the second time, and performing solid-liquid separation to obtain vanadium-containing purified liquid and secondary filter residues;
mixing the vanadium-containing purified solution with ammonium salt, and carrying out a vanadium precipitation reaction to obtain ammonium metavanadate; calcining the ammonium metavanadate to obtain a high-purity vanadium-containing oxide pure product or a calcined product of a plurality of oxides;
mixing the raw materials including the calcined product, pure water and concentrated sulfuric acid, and carrying out solid-liquid separation after dissolution reaction to obtain the vanadium electrolyte for the all-vanadium redox flow battery.
Preferably, the sodium roasting agent comprises one or more of sodium carbonate, sodium sulfate, sodium chloride and sodium hydroxide;
the temperature of the sodium treatment roasting is 700-900 ℃, and the time is 1-4h;
preferably, the temperature of the selective leaching is 60-90 ℃; the selective leaching is carried out by using water or an alkali solution, and the liquid-solid ratio is (2-5) mL:1g, and the pH value of the system is 7-10.
Preferably, the magnesium salt comprises magnesium chloride and/or magnesium sulfate, and the aluminum salt comprises aluminum chloride and aluminum sulfate;
the dosage of the magnesium salt and/or the aluminum salt is 1.2 times of the theoretical dosage;
the temperature of the first impurity removal is 60-90 ℃, and the time is 0.5-2h.
Preferably, during the second impurity removal, the pH value of the system is adjusted to 10-10.5, the temperature is 60-90 ℃, and the time is 0.5-2h.
Preferably, the ammonium salt comprises one or more of ammonium chloride, ammonium sulfate, ammonium carbonate and ammonium nitrate;
the pH value of the vanadium precipitation reaction system is 8.5-10, the reaction temperature is 10-40 ℃, and the reaction time is 0.5-2h.
Preferably, after the vanadium precipitation reaction is finished, washing the product to remove potassium and sodium.
Preferably, the calcination is carried out in an oxidizing atmosphere or a reducing atmosphere;
the oxidizing atmosphere comprises air or oxygen;
the reducing atmosphere comprises one or more of hydrogen, carbon monoxide and ammonia;
the calcining temperature is 500-1000 ℃, and the calcining time is 1-3h.
Preferably, the molar ratio of V in the concentrated sulfuric acid and the calcined product is (2.2-2.8): 1;
the temperature of the dissolution reaction is 90-130 ℃, and the time is 1-3h.
Preferably, the calcined product comprises one or more of high purity vanadium pentoxide, vanadium dioxide and vanadium trioxide.
The application also provides a vanadium electrolyte prepared by the method for preparing the vanadium electrolyte for the all-vanadium redox flow battery from the vanadium-containing raw material in a short process.
Compared with the prior art, the beneficial effect of this application includes:
the method for preparing the vanadium electrolyte for the all-vanadium redox flow battery from the vanadium-containing raw material in a short process adjusts the existing process route of ' roasting and leaching the vanadium-containing raw material, purifying, preparing AMV, redissolving and purifying the AMV, preparing a high-purity AMV product, calcining the AMV, preparing high-purity vanadium pentoxide, reducing and roasting, dissolving and preparing the vanadium electrolyte ' into ' the vanadium-containing raw material, performing sodium salt roasting, selectively leaching, deeply purifying (first and second impurities), precipitating vanadium reaction, preparing the high-purity AMV product, roasting the AMV, dissolving the vanadium electrolyteThe vanadium electrolyte is decomposed, the procedures of 'AMV redissolution purification' and 'AMV calcination' are omitted, the process flow is shortened, and a large amount of sodium hydroxide and ammonium salt are avoided in the 'AMV redissolution purification' link. AMV reduction calcination process utilizes NH carried in AMV 3 As a reducing agent, the consumption of reducing gas is obviously reduced, and the method can realize that the ratio of different vanadium oxides is accurately controlled through roasting atmosphere and time so as to further obtain vanadium electrolytes with different valence states. In the dissolving reaction, vanadium trioxide is used as a catalyst to promote the dissolution of vanadium pentoxide and vanadium dioxide, so that the dissolving reaction rate is increased, and the production efficiency is improved. The method simplifies the process flow, obviously reduces the production cost and can produce vanadium electrolytes with different valence states.
The vanadium electrolyte provided by the application has the advantages of low organic matter content, high vanadium concentration and adjustable vanadium valence, and the vanadium battery prepared by using the vanadium electrolyte has excellent performance.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required in the embodiments will be briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
Fig. 1 is a schematic flow diagram of a method for preparing a vanadium electrolyte for an all-vanadium redox flow battery from a vanadium-containing raw material in a short process according to an embodiment.
Detailed Description
The terms as used herein:
"by 8230; \ 8230; preparation" is synonymous with "comprising". As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of 823070, 8230composition" excludes any unspecified elements, steps or components. If used in a claim, this phrase shall render the claim closed except for the materials described except for those materials normally associated therewith. When the phrase "consisting of 8230' \8230"; composition "appears in a clause of the subject matter of the claims and not immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4," "1 to 3," "1 to 2 and 4 to 5," "1 to 3 and 5," and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent an arbitrary unit mass, for example, 1g or 2.689 g. If the parts by mass of the component A are a parts and the parts by mass of the component B are B parts, the mass ratio of the component A to the component B is expressed as a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
A method for preparing vanadium electrolyte for an all-vanadium redox flow battery from vanadium-containing raw materials in a short process comprises the following steps:
mixing the vanadium-containing raw material and a sodium roasting agent for sodium roasting, and then selectively leaching to obtain vanadium-containing leaching solution;
carrying out primary impurity removal on the vanadium-containing leaching solution by using magnesium salt and/or aluminum salt, and carrying out solid-liquid separation to obtain filtrate and primary purification slag; adjusting the pH value of the filtrate to remove impurities and heavy metals for the second time, and performing solid-liquid separation to obtain vanadium-containing purified liquid and secondary filter residue;
mixing the vanadium-containing purified solution with ammonium salt, and carrying out a vanadium precipitation reaction to obtain ammonium metavanadate; calcining the ammonium metavanadate to obtain a high-purity vanadium-containing oxide pure product or a calcined product of a plurality of oxides;
mixing the raw materials including the calcined product, pure water and concentrated sulfuric acid, and carrying out solid-liquid separation after dissolution reaction to obtain the vanadium electrolyte for the all-vanadium redox flow battery.
In an alternative embodiment, the sodium roasting agent comprises one or more of sodium carbonate, sodium sulfate, sodium chloride, and sodium hydroxide;
in an alternative embodiment, the sodium roasting temperature is 700-900 ℃ and the time is 1-4h.
Optionally, the temperature of the sodium treatment roasting may be any value between 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ or 700-900 ℃, and the time may be any value between 1h, 2h, 3h, 4h or 1-4h.
In a preferred embodiment, the temperature of the sodium roasting is 850 ℃ and the time is 2h, and the sodium roasting agent is sodium carbonate.
In an alternative embodiment, the temperature of the selective leaching is 60-90 ℃; the selective leaching is carried out by using water or an alkali solution, and the liquid-solid ratio is (2-5) mL:1g, and the pH value of the system is 7-10.
Optionally, the temperature of the selective leaching may be any value between 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 60-90 ℃; the selective leaching is carried out using water or an alkali solution, and the liquid-solid ratio may be 2mL:1g, 3mL:1g, 4mL:1g, 5mL:1g or (2-5) mL:1g, the system pH may be 7, 8, 9, 10 or any value between 7 and 10.
In a preferred embodiment, the selective leaching is carried out using water at a temperature of 60 ℃ and a liquid-to-solid ratio of 2.5mL:1g, the pH of the system was 8.5.
In an alternative embodiment, the magnesium salt comprises magnesium chloride and/or magnesium sulfate and the aluminum salt comprises aluminum chloride and aluminum sulfate; magnesium chloride is preferred.
In an alternative embodiment, the amount of the magnesium salt and/or the aluminum salt is 1.2 times the theoretical amount;
in an alternative embodiment, the first removal of impurities is carried out at a temperature of 60 to 90 ℃ for a time of 0.5 to 2 hours.
In an optional embodiment, during the second impurity removal, the pH of the system is adjusted to 10-10.5, the temperature is 60-90 ℃, and the time is 0.5-2h.
Optionally, the temperature of the first impurity removal may be any value between 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 60-90 ℃, and the time may be any value between 0.5h, 1h, 1.5h, 2h or 0.5-2h. During the second impurity removal, the pH value of the adjusting system can be any value between 10, 10.1, 10.2, 10.3, 10.4, 10.5 or 10-10.5, the temperature can be any value between 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 60-90 ℃, and the time can be any value between 0.5h, 1h, 1.5h, 2h or 0.5-2h.
In an alternative embodiment, the ammonium salt comprises one or more of ammonium chloride, ammonium sulfate, ammonium carbonate, and ammonium nitrate; ammonium chloride is preferred, in an amount of 1.5 times the theoretical amount.
In an alternative embodiment, the pH value of the system for the vanadium precipitation reaction is 8.5-10, the reaction temperature is 10-40 ℃, and the reaction time is 0.5-2h.
Optionally, the pH of the system of the vanadium precipitation reaction may be any value between 8.5, 9, 9.5, 10 or 8.5 and 10, the reaction temperature may be any value between 10 ℃, 20 ℃, 30 ℃, 40 ℃ or 10 and 40 ℃, and the time may be any value between 0.5h, 1h, 1.5h, 2h or 0.5 and 2h.
In an alternative embodiment, the product is washed to remove potassium and sodium after the vanadium precipitation reaction is finished.
In an alternative embodiment, the calcination is carried out in an oxidizing atmosphere or a reducing atmosphere;
in an alternative embodiment, the oxidizing atmosphere comprises air or oxygen;
in an alternative embodiment, the reducing atmosphere comprises one or more of hydrogen, carbon monoxide and ammonia; hydrogen is preferred.
In an alternative embodiment, the calcination is carried out at a temperature of 500 to 1000 ℃ for a time of 1 to 3 hours.
Optionally, the calcination temperature may be 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃ or any value between 500 ℃ and 1000 ℃, and the calcination time may be 1h, 2h, 3h or any value between 1h and 3h.
In an alternative embodiment, the molar ratio of V in the concentrated sulfuric acid and the calcined product is (2.2-2.8): 1; preferably 2.5:1.
alternatively, the molar ratio of the concentrated sulfuric acid to V in the calcined product may be 2.2: 1. 2.3: 1. 2.4: 1. 2.5:1. 2.6: 1. 2.7: 1. 2.8:1 or (2.2-2.8): 1, or any value between.
In an alternative embodiment, the dissolution reaction is carried out at a temperature of 90 to 130 ℃ for a time of 1 to 3 hours.
Optionally, the temperature of the dissolution reaction may be any value between 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃ or 90-130 ℃, and the time may be any value between 1h, 2h, 3h or 1-3h.
In an alternative embodiment, the calcined product comprises one or more of vanadium pentoxide, vanadium dioxide, and vanadium trioxide. Preferably V 2 O 5 :V 2 O 3 The molar ratio is 1 2 :V 2 O 3 The molar ratio is 1.
The proportion of different vanadium oxides is accurately controlled, and vanadium electrolytes with different valence states are further obtained to meet the requirements.
The application also provides a vanadium electrolyte prepared by the method for preparing the vanadium electrolyte for the all-vanadium redox flow battery from the vanadium-containing raw material in a short process.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Example 1
As shown in fig. 1, this embodiment provides a method for preparing a vanadium electrolyte for an all-vanadium redox flow battery from a vanadium-containing raw material in a short process, including the following steps:
the vanadium-containing waste catalyst is used as a raw material, the mass content of vanadium is 9.31%, and main impurity elements comprise aluminum, silicon, phosphorus, iron, calcium and the like.
1) Taking vanadium-containing waste catalyst, adding 22wt% of sodium carbonate for sodium salt roasting, wherein the roasting temperature is 800 ℃, and the roasting time is 2 hours; selectively leaching the roasted sand to obtain vanadium-containing leachate, controlling the leaching temperature to be 70 ℃, and controlling the liquid-solid ratio to be 2.5mL:1g, pH 9 and vanadium leaching rate of 93.52 percent;
2) And (4) removing impurities of the vanadium-containing leaching solution twice. Removing impurities for the first time, adopting aluminum chloride with the addition of 10g/L, controlling the reaction temperature at 90 ℃, reacting for 1h, and filtering for the first time after the reaction is finished to obtain filtrate and purified slag for the first time; and (3) secondary impurity removal, continuously adjusting the pH value of the filtrate to 10, removing heavy metals (iron, nickel, calcium and the like), controlling the reaction temperature to be 90 ℃, reacting for 0.5h, and performing secondary filtration after the reaction is finished to obtain vanadium-containing purified liquid and secondary purified slag, wherein the impurity removal rate is more than 98%.
3) And (2) performing ammonium salt vanadium precipitation on the vanadium-containing purification solution, adjusting the pH to 9, controlling the reaction temperature to be 20 ℃, controlling the reaction time to be 1h, and after the reaction is finished, performing centrifugal washing on the product by using pure water to remove K and Na, wherein the washing water consumption is 3mL and 1g, so that high-purity ammonium metavanadate is obtained, and the purity reaches 99.6%.
4) Calcining high-purity ammonium metavanadate with H 2 Controlling the reducing atmosphere (flow rate of 100 mL/min) as a reducing gas, and calciningThe temperature is 600 ℃, the calcining time is 1.5h, and vanadium dioxide is obtained: the vanadium trioxide is a vanadium-containing oxide of 1.
5) Taking vanadium dioxide: vanadium trioxide is 1:1, controlling the reaction temperature to be 110 ℃, reacting for 2 hours, filtering after the reaction is finished to obtain vanadium-containing electrolyte, wherein the vanadium concentration of the electrolyte is 1.72mol/L, the sulfate radical concentration is 4.35mol/L, and the vanadium comprehensive valence state is 3.49, so that the requirement of the vanadium flow battery on the 3.5-valent electrolyte is met.
Example 2
The embodiment provides a method for preparing a vanadium electrolyte for an all-vanadium redox flow battery from a vanadium-containing raw material in a short process, which comprises the following steps:
the method takes petroleum coke containing vanadium as a raw material, the content of vanadium is 4.52wt%, and main impurity elements comprise nickel, aluminum, silicon, phosphorus, iron, calcium and the like.
1) Taking vanadium-containing waste catalyst, adding 10 wt% of sodium carbonate to carry out sodium salt roasting, wherein the roasting temperature is 900 ℃, and the roasting time is 2h; selectively alkaline leaching the roasted sand to obtain vanadium-containing leaching solution, controlling the leaching temperature to be 80 ℃, and controlling the liquid-solid ratio to be 5mL:1g, pH 10 and vanadium leaching rate of 91.44%;
2) And (4) removing impurities twice aiming at the vanadium-containing leaching solution. Removing impurities for the first time, adopting magnesium chloride with the addition of 10g/L, controlling the reaction temperature at 90 ℃, reacting for 1h, and filtering for the first time after the reaction is finished to obtain filtrate and purified slag for the first time; and (3) removing impurities for the second time, taking the filtrate, continuously adjusting the pH value to 10.5, removing heavy metals (iron, nickel, calcium and the like), controlling the reaction temperature to be 90 ℃, reacting for 1h, performing secondary filtration after the reaction is finished to obtain vanadium-containing purified liquid and secondary purified slag, wherein the impurity removal rate is more than 98%.
3) And (2) performing ammonium salt vanadium precipitation on the vanadium-containing purification solution, adjusting the pH to 8.5, controlling the reaction temperature to be 20 ℃, and controlling the reaction time to be 0.5h, after the reaction is finished, performing centrifugal washing on the product by using pure water to remove K and Na, wherein the washing water consumption is 4mL and 1g, so that high-purity ammonium metavanadate is obtained, and the purity reaches 99.8%.
4) Calcining the high-purity ammonium metavanadate, namely introducing air to perform oxidizing roasting at 580 ℃ for 2 hours to obtain the high-purity vanadium pentoxide.
Then calcining the high-purity ammonium metavanadate, introducing hydrogen and ensuring H 2 And (4) excessive, wherein the calcining temperature is 620 ℃, and the calcining time is 3 hours, so that the high-purity vanadium trioxide is obtained.
5) Mixing vanadium pentoxide and vanadium trioxide according to a molar ratio of 1: the method comprises the following steps of 1, controlling the reaction temperature to be 120 ℃, controlling the reaction time to be 2.5h, filtering after the reaction is finished to obtain vanadium-containing electrolyte, wherein the vanadium concentration of the electrolyte is 1.75mol/L, the sulfate radical concentration is 4.51mol/L, and the vanadium comprehensive valence state is 3.52, so that the requirement of the vanadium flow battery on the vanadium electrolyte with the valence of 3.5 is met.
Example 3
The embodiment provides a method for preparing vanadium electrolyte for an all-vanadium redox flow battery from vanadium-containing raw materials in a short process, which comprises the following steps:
the waste vanadium-containing catalyst is used as raw material, the vanadium content is 9.31wt%, and the main impurity elements include aluminum, silicon, phosphorus, iron, calcium and the like.
1) Taking vanadium-containing waste catalyst, adding 22wt% of sodium carbonate, and performing sodium salt roasting at 800 ℃ for 2h; selectively leaching the calcine to obtain vanadium-containing leaching solution, controlling the leaching temperature to be 70 ℃, the liquid-solid ratio to be 2.5 and the pH to be 9, and controlling the leaching rate of vanadium to reach 93.52 percent;
2) And (4) removing impurities of the vanadium-containing leaching solution twice. Removing impurities for the first time, adopting aluminum chloride with the addition of 10g/L, controlling the reaction temperature at 90 ℃, reacting for 1h, and filtering for the first time after the reaction is finished to obtain filtrate and purified slag for the first time; and (3) secondary impurity removal, continuously adjusting the pH value of the filtrate to 10, removing heavy metals (iron, nickel, calcium and the like), controlling the reaction temperature to be 90 ℃, reacting for 0.5h, and performing secondary filtration after the reaction is finished to obtain vanadium-containing purified liquid and secondary purified slag, wherein the impurity removal rate is more than 98%.
3) And (2) performing ammonium salt vanadium precipitation on the vanadium-containing purification solution, adjusting the pH to 9, controlling the reaction temperature to be 20 ℃, controlling the reaction time to be 1h, and after the reaction is finished, performing centrifugal washing on the product by using pure water to remove K and Na, wherein the washing water consumption is 3mL and 1g, so that high-purity ammonium metavanadate is obtained, and the purity reaches 99.6%.
4) Calcining high-purity ammonium metavanadate with H 2 And controlling the reducing atmosphere (the flow rate is 200 mL/min) as reducing gas, wherein the calcining temperature is 620 ℃, and the calcining time is 2.5h, so as to obtain the vanadium-containing oxide with 100% of vanadium trioxide.
5) Taking vanadium-containing oxide, adding pure water and concentrated sulfuric acid, wherein the molar ratio of the concentrated sulfuric acid to V is 2.5:1, controlling the reaction temperature at 130 ℃, reacting for 2h, filtering after the reaction is finished to obtain vanadium-containing electrolyte, wherein the vanadium concentration of the electrolyte is 1.75mol/L, the sulfate radical concentration is 4.25mol/L, and the vanadium comprehensive valence state is 3.01, so that the requirement of the vanadium flow battery on the vanadium-containing electrolyte with the valence of 3 is met.
Comparative example 1
The petroleum coke containing vanadium is used as a raw material, the vanadium content is 4.52wt%, and the main impurity elements comprise nickel, aluminum, silicon, phosphorus, iron, calcium and the like.
1) Taking vanadium-containing waste catalyst, adding 10 wt% of sodium carbonate to carry out sodium salt roasting, wherein the roasting temperature is 900 ℃, and the roasting time is 2h; selectively alkaline leaching the roasted sand to obtain vanadium-containing leaching solution, controlling the leaching temperature to be 80 ℃, and controlling the liquid-solid ratio to be 5mL:1g, pH 10 and vanadium leaching rate of 91.44%;
2) And (4) removing impurities of the vanadium-containing leaching solution twice. Removing impurities for the first time, namely adopting magnesium chloride, controlling the addition amount of the magnesium chloride to be 5g/L, controlling the reaction temperature to be 90 ℃, reacting for 1h, and filtering for the first time after the reaction is finished to obtain filtrate and purified slag for the first time; and (3) secondary impurity removal, continuously adjusting the pH value of the filtrate to 9, removing heavy metals (iron, nickel, calcium and the like), controlling the reaction temperature to be 90 ℃, reacting for 1h, performing secondary filtration after the reaction is finished to obtain vanadium-containing purified liquid and secondary purified slag, wherein the impurity removal rate is more than 98%.
3) And (2) performing ammonium salt vanadium precipitation on the vanadium-containing purification solution, adjusting the pH to 8.5, controlling the reaction temperature to be 20 ℃, and controlling the reaction time to be 0.5h, after the reaction is finished, performing centrifugal washing on the product by using pure water to remove K and Na, wherein the washing water consumption is 4mL and 1g, so that high-purity ammonium metavanadate is obtained, and the purity reaches 99.8%.
4) Calcining the high-purity ammonium metavanadate, namely introducing air to perform oxidizing roasting at 580 ℃ for 2 hours to obtain the high-purity vanadium pentoxide.
Then calcining the high-purity ammonium metavanadate, introducing hydrogen and ensuring H 2 And (4) excessive calcining temperature is 620 ℃, and calcining time is 3h, so that high-purity vanadium trioxide is obtained.
5) Mixing vanadium pentoxide and vanadium trioxide according to a ratio of 1: controlling the reaction temperature to be 120 ℃, controlling the reaction time to be 2.5h, filtering after the reaction is finished to obtain vanadium-containing electrolyte, wherein the vanadium concentration of the electrolyte is 1.74mol/L, the sulfate radical concentration is 4.25mol/L, the vanadium comprehensive valence state is 3.48, but the content of silicon and iron impurity elements is respectively 68 and 89ppm, and the requirement of the vanadium flow battery vanadium electrolyte on the impurity content is not met.
Comparative example 2
The comparative example provides a method for preparing vanadium electrolyte for an all-vanadium redox flow battery from vanadium-containing raw materials in a short process, which comprises the following steps:
the waste catalyst containing vanadium is used as raw material, the vanadium content is 9.31wt%, and the main impurity elements include aluminum, silicon, phosphorus, iron, calcium and the like.
1) Taking vanadium-containing waste catalyst, adding 22wt% of sodium carbonate for sodium salt roasting, wherein the roasting temperature is 800 ℃, and the roasting time is 2 hours; selectively leaching the calcine to obtain vanadium-containing leaching solution, controlling the leaching temperature to be 70 ℃, the liquid-solid ratio to be 2.5 and the pH to be 9, and controlling the leaching rate of vanadium to reach 93.52 percent;
2) And (4) removing impurities of the vanadium-containing leaching solution twice. Removing impurities for the first time, adopting aluminum chloride with the addition of 10g/L, controlling the reaction temperature at 90 ℃, reacting for 1h, and filtering for the first time after the reaction is finished to obtain filtrate and purified slag for the first time; and (3) removing impurities for the second time, taking the filtrate, continuously adjusting the pH value to 10, removing heavy metals (iron, nickel, calcium and the like), controlling the reaction temperature to be 90 ℃, reacting for 0.5h, performing secondary filtration after the reaction is finished to obtain vanadium-containing purified liquid and secondary purified slag, wherein the impurity removal rate is more than 98%.
3) And (2) precipitating vanadium by using ammonium salt aiming at the vanadium-containing purification solution, adjusting the pH to be 9, controlling the reaction temperature to be 20 ℃, controlling the reaction time to be 1h, and after the reaction is finished, carrying out centrifugal washing on the product by using pure water to remove K and Na, wherein the washing water consumption is 3mL and 1g, so that high-purity ammonium metavanadate is obtained, and the purity reaches 99.6%.
4) Calcining high-purity ammonium metavanadate with H 2 And controlling the reducing atmosphere as reducing gas, wherein the calcining temperature is 620 ℃, and the calcining time is 2.5h, thus obtaining the vanadium-containing oxide with 100 percent of vanadium trioxide.
5) Taking vanadium-containing oxide, adding pure water and concentrated sulfuric acid, wherein the molar ratio of the concentrated sulfuric acid to V is 2.8:1, controlling the reaction temperature to be 80 ℃, reacting for 2 hours, filtering to obtain vanadium-containing electrolyte after the reaction is finished, wherein the vanadium concentration of the electrolyte is 1.25mol/L, the sulfate radical concentration is 3.65mol/L, the vanadium comprehensive valence state is 3.78, the dissolving slag amount of vanadium-containing oxide is large, the dissolving rate is only 76.55%, the dissolving effects of vanadium and sulfate radical are poor, and the requirements of the vanadium electrolyte on the vanadium concentration and the sulfate radical concentration cannot be met.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, and not to limit the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. A method for preparing vanadium electrolyte for an all-vanadium redox flow battery from vanadium-containing raw materials in a short process is characterized by comprising the following steps:
mixing a vanadium-containing raw material and a sodium-modified roasting agent for sodium-modified roasting, and then selectively leaching to obtain a vanadium-containing leaching solution;
carrying out primary impurity removal on the vanadium-containing leaching solution by using magnesium salt and/or aluminum salt, and carrying out solid-liquid separation to obtain filtrate and primary purification slag; adjusting the pH of the filtrate to remove impurities and heavy metals for the second time, and performing solid-liquid separation to obtain vanadium-containing purified liquid and secondary filter residues;
mixing the vanadium-containing purified liquid with ammonium salt, and carrying out vanadium precipitation reaction to obtain ammonium metavanadate; calcining the ammonium metavanadate to obtain a high-purity vanadium-containing oxide pure product or a calcined product of a plurality of oxides;
mixing the raw materials including the calcined product, pure water and concentrated sulfuric acid, and carrying out solid-liquid separation after dissolution reaction to obtain the vanadium electrolyte for the all-vanadium redox flow battery.
2. The method of claim 1, wherein the sodium roasting agent comprises one or more of sodium carbonate, sodium sulfate, sodium chloride, and sodium hydroxide;
the temperature of the sodium treatment roasting is 700-900 ℃, and the time is 1-4h;
the temperature of the selective leaching is 60-90 ℃; the selective leaching is carried out by using water or an alkali solution, and the liquid-solid ratio is (2-5) mL:1g, and the pH value of the system is 7-10.
3. The method of claim 1, wherein the magnesium salt comprises magnesium chloride and/or magnesium sulfate, and the aluminum salt comprises aluminum chloride and aluminum sulfate;
the dosage of the magnesium salt and/or the aluminum salt is 1.2 times of the theoretical dosage;
the temperature of the first impurity removal is 60-90 ℃, and the time is 0.5-2h.
4. The method according to claim 1, wherein during the second impurity removal, the pH value of the system is adjusted to 10-10.5, the temperature is 60-90 ℃, and the time is 0.5-2h.
5. The method of claim 1, wherein the ammonium salt comprises one or more of ammonium chloride, ammonium sulfate, ammonium carbonate, and ammonium nitrate;
the pH value of the system for vanadium precipitation reaction is 8.5-10, the reaction temperature is 10-40 ℃, and the reaction time is 0.5-2h.
6. The method according to claim 5, wherein the product is washed to remove potassium and sodium after the vanadium precipitation reaction is finished.
7. The method according to claim 1, characterized in that the calcination is carried out in an oxidizing atmosphere or a reducing atmosphere;
the oxidizing atmosphere comprises air or oxygen;
the reducing atmosphere comprises one or more of hydrogen, carbon monoxide and ammonia;
the calcining temperature is 500-1000 ℃, and the calcining time is 1-3h.
8. The process according to claim 1, characterized in that the molar ratio of the concentrated sulfuric acid to V in the calcined product is (2.2-2.8): 1;
the temperature of the dissolution reaction is 90-130 ℃, and the time is 1-3h.
9. The process of any one of claims 1-8, wherein the calcined product comprises one or more of high purity vanadium pentoxide, vanadium dioxide, and vanadium trioxide.
10. The vanadium electrolyte is characterized by being prepared by the method for preparing the vanadium electrolyte for the all-vanadium redox flow battery from the vanadium-containing raw material in a short process according to any one of claims 1 to 9.
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| CN101339993A (en) * | 2007-07-05 | 2009-01-07 | 三星Sdi株式会社 | Cathode active material for non-aqueous electrolyte rechargeable battery and manufacturing method thereof |
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| CN101339993A (en) * | 2007-07-05 | 2009-01-07 | 三星Sdi株式会社 | Cathode active material for non-aqueous electrolyte rechargeable battery and manufacturing method thereof |
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