CN110880606A - Preparation method of high-purity vanadyl sulfate - Google Patents
Preparation method of high-purity vanadyl sulfate Download PDFInfo
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- CN110880606A CN110880606A CN201911060998.3A CN201911060998A CN110880606A CN 110880606 A CN110880606 A CN 110880606A CN 201911060998 A CN201911060998 A CN 201911060998A CN 110880606 A CN110880606 A CN 110880606A
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- vanadium
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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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
Abstract
The invention relates to the technical field of energy storage of flow batteries, and discloses a preparation method of high-purity vanadyl sulfate, which specifically comprises the steps of taking alkaline vanadium-containing leachate and unbalanced 3.5-valent solution as raw materials, mutually matching and neutralizing trivalent vanadium in the solution until the vanadium in the solution is in a valence state of 4, adjusting the pH value of the solution to be neutral by using an alkaloid regulator, promoting separation of tetravalent vanadium in the solution, reversely dissolving the precipitate into a sulfuric acid aqueous solution, and introducing an organic precipitator to accelerate crystallization of vanadyl sulfate in a new solution system, so that the obtained crystal has high purity. According to the preparation method of the high-purity vanadyl sulfate, the alkaline vanadium-containing leachate and the unbalanced 3.5-valent vanadium solution are used as main raw materials, so that the high-purity vanadyl sulfate can be conveniently extracted from waste materials, the effect of recycling waste materials is effectively realized, the raw materials are easier to obtain, and the preparation method is more scientific and concise by processing the waste materials by adopting an alkaloid regulator and an organic precipitator.
Description
Technical Field
The invention relates to the technical field of energy storage of flow batteries, in particular to a preparation method of high-purity vanadyl sulfate.
Background
Vanadium, having the elemental symbol V, is a silver-white metal belonging to group VB of the periodic table, atomic number 23, atomic weight 50.9414, body-centered cubic crystals, having the usual valence of +5, +4, +3, +2, has a very high melting point, is often associated with niobium, tantalum, tungsten and molybdenum and is called refractory metal, is ductile, hard and non-magnetic, has resistance to hydrochloric acid and sulfuric acid, and has better resistance to gas, salt and water than most stainless steels, is more stable in the dense state at room temperature, is not affected by air, water and alkali, and is resistant to dilute acid, and is found twice in succession, the first being found in 1801 by professor javanica in mineral science in mexico city, he found it in a sub-vanadate sample, which is Pb5(VO4)3Cl, which is named "Aliettron", because the salt solution of this new element shows a bright red color when heated, and this article is sent to Paris, however, it was not acknowledged by French chemists that it is a contaminated chromium ore, and the second finding was that in 1830, Swedish chemists, Sefstrom, studied the iron ore in the Maran area, dissolved the iron with acid, found vanadium in the residue, and because the vanadium compound is very beautiful in its variegated and colourful color, it was just in the ancient Greek mythThe new element, named "Vanadium" by its translation, was named "vanadia" by the name of "Vanadis", chinese was named Vanadium by its translation, and both serpentin, veller and beidelius studied Vanadium, confirming the presence of Vanadium, but they did not always separate it, and later, in 1830, written forsteri wood found it in iron extracted from the swedish iron ore, and certainly this was a new element, named Vanadium, which he could prove to be a new element and therefore defeat a chemist who competed with him, from sn maho (mexico), who also studied another Vanadium ore, the trail of Vanadium being distributed throughout the world, in the earth crust, the content of Vanadium was not less, on average in two million atoms, one Vanadium atom, more than the contents of copper, tin, zinc and nickel, but too scattered Vanadium, there are almost no deposits in large amounts, and the trace of vanadium is found in sea water, in marine organisms such as sea urchins, in magnetite, in various bituminous minerals and coal ashes, in meteorites falling on the earth and in the spectral line of the sun. Vanadium is a trace element widely distributed on the earth, and the content of vanadium accounts for about 0.02 percent of the earth crust, and the vanadium is relatively easy to obtain.
At present, vanadium is an important rare metal, and has important applications in the aspects of catalysts, alloys, batteries, advanced materials and the like, wherein, the vanadium redox flow battery is used as a new application field of vanadium, and is more and more widely applied, compared with the traditional storage battery, the vanadium redox flow battery has the characteristics of rapid, large-capacity charge and discharge, low self-discharge rate, simple battery structure and the like, and is an ideal power supply form for meeting the large-scale energy storage of novel energy sources such as wind energy, solar energy and the like, as the electrolyte of the battery active substance, the positive electrolyte consists of a mixed solution of tetravalent and pentavalent vanadium ions and sulfuric acid, the negative electrolyte consists of a mixed solution of divalent and trivalent vanadium ions and sulfuric acid, after the battery is charged, the positive substance is a pentavalent vanadium ion sulfuric acid solution, the negative electrode is a divalent vanadium ion sulfuric acid solution, after the battery is discharged, the positive electrode and negative electrodes are respectively a tetravalent and trivalent vanadium ion sulfuric, the vanadyl sulfate is used as a main substance of the electrolyte, the purity of the vanadyl sulfate directly influences the performance of the electrolyte, and the vanadyl sulfate is used as a stable vanadium substance and has outstanding effects in the fields of medicine, chemical industry, national defense and the like.
However, in the production process, conventional means such as distillation and the like are required to be utilized to refine the vanadyl sulfate, so that a large amount of energy is consumed, the raw materials are troublesome to obtain, the production cost is improved, and the economic benefit is reduced.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the preparation method of the high-purity vanadyl sulfate, which has the advantages of simple method, easily obtained raw materials, low energy consumption, high purity of the obtained product, higher economic benefit and the like, and solves the problems that the conventional means such as distillation and the like are required to be utilized to refine the vanadyl sulfate, a large amount of energy is consumed, the raw materials are relatively troublesome to obtain, the production cost is improved, and the economic benefit is reduced.
(II) technical scheme
In order to realize the purposes of simple method, easily obtained raw materials, low energy consumption, high purity of the obtained product and higher economic benefit, the invention provides the following technical scheme: a preparation method of high-purity vanadyl sulfate comprises the following raw materials: vanadium ore, unbalanced 3.5-valent vanadium solution, alkaloid regulator and organic precipitant.
The invention aims to solve another technical problem of providing a preparation method of high-purity vanadyl sulfate, which comprises the following steps:
1) preparing alkaline vanadium-containing leaching liquid, and obtaining the alkaline vanadium-containing leaching liquid by the traditional process of sodium roasting and leaching vanadium ores;
2) mixing and preparing, namely performing mutual matching on the alkaline vanadium-containing leaching solution and the unbalanced vanadium solution with the valence of 3.5, and performing mutual matching to neutralize trivalent vanadium in the solution until the vanadium in the solution is in the valence of 4;
3) adjusting the pH value, adjusting the pH value of the prepared solution to be neutral by using an alkaloid regulator, and promoting the precipitation of tetravalent vanadium in the solution;
4) and (3) crystallizing, namely reversely dissolving the precipitate into a sulfuric acid aqueous solution, and introducing an organic precipitator to accelerate crystallization of vanadyl sulfate in a new solution system.
Preferably, the alkaline vanadium-containing leachate in step 1) has vanadium in the form of +5, a pH value ranging from 8 to 12, and a vanadium content ranging from 20 to 45 g/l.
Preferably, the alkaloid regulator is one or more of atropine, dichroine, theophylline, guline, cinchona and berberine, and the compound organic solvent is one of chloroform, formamide and acetone.
Preferably, the organic precipitant is an alcohol, such as one of ethanol, ethylene glycol and glycerol.
Preferably, after the organic precipitant is introduced in the step 4), the material is kept still in a constant temperature and humidity environment for a little time to separate out vanadyl sulfate crystals.
Preferably, the recrystallized crystal is washed with water and filtered to obtain high-purity vanadyl sulfate.
(III) advantageous effects
Compared with the prior art, the invention provides a preparation method of high-purity vanadyl sulfate, which has the following beneficial effects:
according to the preparation method of high-purity vanadyl sulfate, alkaline vanadium-containing leachate and unbalanced 3.5-valent vanadium solution are used as main raw materials, so that high-purity vanadyl sulfate can be conveniently extracted from waste materials, the effect of recycling waste materials is effectively realized, the raw materials are easier to obtain, the waste materials are processed by adopting an alkaloid regulator and an organic precipitator, a more scientific and concise preparation method is convenient to adopt, the conventional means such as original distillation and the like are abandoned, and therefore, the effect of saving energy is realized.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A preparation method of high-purity vanadyl sulfate comprises the following raw materials: vanadium ore, unbalanced 3.5-valent vanadium solution, alkaloid regulator and organic precipitant.
The preparation method of the high-purity vanadyl sulfate is characterized by comprising the following steps of:
1) preparing an alkaline vanadium-containing leaching solution, and obtaining the alkaline vanadium-containing leaching solution by a traditional process of sodium roasting and leaching vanadium ores, wherein vanadium in the alkaline vanadium-containing leaching solution exists in a +5 valence form, the pH value range of the alkaline vanadium-containing leaching solution is between 8 and 12, and the vanadium content is 20 to 45 g/L;
2) mixing and preparing, namely performing mutual matching on the alkaline vanadium-containing leaching solution and the unbalanced vanadium solution with the valence of 3.5, and performing mutual matching to neutralize trivalent vanadium in the solution until the vanadium in the solution is in the valence of 4;
3) adjusting the pH value, and adjusting the pH value of the prepared solution to be neutral by using an alkaloid regulator, wherein the alkaloid regulator is one or more of atropine, dichroine, theophylline, gulconiine, cinchona and berberine, and the compound organic solvent is one of chloroform, formamide and acetone, and promotes tetravalent vanadium in the solution to be separated out;
4) and (2) crystallizing, namely reversely dissolving the precipitate into a sulfuric acid aqueous solution, introducing an organic precipitator to accelerate crystallization of vanadyl sulfate in a new solution system, wherein the organic precipitator is an alcohol substance, such as one of ethanol, glycol and glycerol, standing the material in a constant-temperature and constant-humidity environment after introducing the organic precipitator, separating vanadyl sulfate crystals for a little time, and washing and filtering the recrystallized crystals to obtain high-purity vanadyl sulfate.
Experimental example:
knowing that the concentration of vanadium is 2.8mol/L, the failure electrolyte is 1L, the leaching solution containing vanadium is 28 g/L and 5L, mixing, stirring, adding a mixed regulator of atropine, theophylline and acetone, regulating the pH value to be 7, standing to obtain coarse vanadyl sulfate crystals, dissolving the coarse vanadyl sulfate crystals in a sulfuric acid aqueous solution, adding excessive glycerol, standing and crystallizing in a constant-temperature and constant-humidity environment to obtain 610 g of vanadyl sulfate crystals, wherein the recovery rate of vanadium is 89%.
The results of the examples show that the invention uses alkaline vanadium-containing leaching solution and unbalanced 3.5-valent solution as raw materials to finally obtain high-purity vanadyl sulfate.
The invention has the beneficial effects that: by using alkaline vanadium-containing leachate and unbalanced 3.5-valent vanadium solution as main raw materials, high-purity vanadyl sulfate is conveniently extracted from waste, the effect of recycling waste is effectively realized, the raw materials are easier to obtain, the waste is processed by using an alkaloid regulator and an organic precipitator, a more scientific and concise preparation method is convenient to adopt, and the original conventional means such as distillation and the like are abandoned, so that the effect of saving energy is realized, the preparation method is simple and effective, is convenient for industrial large-scale production, can effectively recover most of vanadium in waste liquid, and has low vanadium loss rate and obvious economic benefit, so that the aims of simple method, easy obtainment of raw materials, low energy consumption, high purity of obtained products and higher economic benefit are fulfilled, the problem that the conventional means such as distillation and the like are required to be used for refining production is solved, consumes a large amount of energy, has troublesome acquisition of raw materials, improves the production cost and reduces the economic benefit.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. The preparation method of the high-purity vanadyl sulfate is characterized by comprising the following raw materials: vanadium ore, unbalanced 3.5-valent vanadium solution, alkaloid regulator and organic precipitant.
2. The preparation method of the high-purity vanadyl sulfate is characterized by comprising the following steps of:
1) preparing alkaline vanadium-containing leaching liquid, and obtaining the alkaline vanadium-containing leaching liquid by the traditional process of sodium roasting and leaching vanadium ores;
2) mixing and preparing, namely performing mutual matching on the alkaline vanadium-containing leaching solution and the unbalanced vanadium solution with the valence of 3.5, and performing mutual matching to neutralize trivalent vanadium in the solution until the vanadium in the solution is in the valence of 4;
3) adjusting the pH value, adjusting the pH value of the prepared solution to be neutral by using an alkaloid regulator, and promoting the precipitation of tetravalent vanadium in the solution;
4) and (3) crystallizing, namely reversely dissolving the precipitate into a sulfuric acid aqueous solution, and introducing an organic precipitator to accelerate crystallization of vanadyl sulfate in a new solution system.
3. The method for preparing high-purity vanadyl sulfate according to claim 1, wherein the alkaline vanadium-containing leachate obtained in step 1) contains vanadium in +5 form, has a pH value in the range of 8-12, and contains vanadium in an amount of 20-45 g/L.
4. The preparation method of high-purity vanadyl sulfate according to claim 1, wherein the alkaloid regulator is one or more of atropine, dichroine, theophylline, guline, cinchona and berberine, and the compound organic solvent is one of chloroform, formamide and acetone.
5. The method for preparing high-purity vanadyl sulfate according to claim 1, wherein the organic precipitant is an alcohol such as one of ethanol, ethylene glycol and glycerol.
6. The method for preparing high-purity vanadyl sulfate according to claim 1, wherein after the organic precipitant is introduced in the step 4), the material is kept still in a constant temperature and humidity environment for a little time to separate out vanadyl sulfate crystals.
7. The method for preparing high-purity vanadyl sulfate according to claim 1 or 7, wherein the recrystallized crystals are washed with water and filtered to obtain high-purity vanadyl sulfate.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010028977A1 (en) * | 1995-05-03 | 2001-10-11 | Michael Kazacos | High energy density vanadium electrolyte solutions, methods of preparation thereof and all-vanadium redox cells and batteries containing high energy vanadium electrolyte solutions |
| WO2005014484A1 (en) * | 2003-08-11 | 2005-02-17 | Nippon Oil Corporation | Method for producing aqueous tetravalent vanadyl sulfate solution |
| CN106395898A (en) * | 2016-08-30 | 2017-02-15 | 沈阳东源环境科技有限公司 | Method for preparing nano copper vanadate from berberine copper-containing waste liquor |
| CN106745246A (en) * | 2016-11-11 | 2017-05-31 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method for preparing vanadic sulfate |
| CN108358777A (en) * | 2018-04-18 | 2018-08-03 | 武汉科技大学 | A kind of preparation method based on three three potassium ferric oxalates of hydration containing vanadium solution |
| CN109360997A (en) * | 2018-10-30 | 2019-02-19 | 成都先进金属材料产业技术研究院有限公司 | The regeneration method of sulfuric acid system failure V electrolyte |
-
2019
- 2019-11-01 CN CN201911060998.3A patent/CN110880606A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010028977A1 (en) * | 1995-05-03 | 2001-10-11 | Michael Kazacos | High energy density vanadium electrolyte solutions, methods of preparation thereof and all-vanadium redox cells and batteries containing high energy vanadium electrolyte solutions |
| WO2005014484A1 (en) * | 2003-08-11 | 2005-02-17 | Nippon Oil Corporation | Method for producing aqueous tetravalent vanadyl sulfate solution |
| CN106395898A (en) * | 2016-08-30 | 2017-02-15 | 沈阳东源环境科技有限公司 | Method for preparing nano copper vanadate from berberine copper-containing waste liquor |
| CN106745246A (en) * | 2016-11-11 | 2017-05-31 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method for preparing vanadic sulfate |
| CN108358777A (en) * | 2018-04-18 | 2018-08-03 | 武汉科技大学 | A kind of preparation method based on three three potassium ferric oxalates of hydration containing vanadium solution |
| CN109360997A (en) * | 2018-10-30 | 2019-02-19 | 成都先进金属材料产业技术研究院有限公司 | The regeneration method of sulfuric acid system failure V electrolyte |
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Application publication date: 20200313 |