CN110880606A - A kind of preparation method of high-purity vanadyl sulfate - Google Patents

Abstract

The invention relates to the technical field of flow battery energy storage, and discloses a preparation method of high-purity vanadyl sulfate. Vanadium, until the solution vanadium is 4-valent, use an alkaloid regulator to adjust the pH value of the solution to neutrality, and promote the precipitation of tetravalent vanadium in the solution, the precipitate is reversely dissolved into the sulfuric acid aqueous solution, and an organic precipitant is introduced to make the sulfuric acid oxygen Vanadium accelerates crystallization in the new solution system, and the resulting crystals are of high purity. The preparation method of high-purity vanadyl sulfate uses alkaline vanadium-containing leaching solution and unbalanced 3.5-valent vanadium solution as main raw materials, which facilitates extraction of high-purity vanadyl sulfate from waste, and effectively achieves the effect of waste recycling. The raw materials are more easily obtained, and a more scientific and concise preparation method is facilitated by using an alkaloid regulator and an organic precipitant to process it.

Description

A kind of preparation method of high-purity vanadyl sulfate

technical field

The invention relates to the technical field of liquid flow battery energy storage, in particular to a preparation method of high-purity vanadyl sulfate.

Background technique

The element symbol of vanadium is V, a silver-white metal, belonging to the VB group in the periodic table, atomic number 23, atomic weight 50.9414, body-centered cubic crystal, common valences are +5, +4, +3, +2, the melting point of vanadium Very high, often referred to as refractory metals together with niobium, tantalum, tungsten and molybdenum, it is ductile, hard and non-magnetic, has the ability to resist hydrochloric acid and sulfuric acid, and is more resistant to gas, salt and water than corrosion resistance. Most stainless steels are good, and the metal vanadium in the dense state is relatively stable at room temperature. It does not react with air, water and alkali, and it is also resistant to dilute acids. Vanadium has been discovered twice, the first time was in 1801 by a professor of mineralogy in Mexico City. Jie Liwa found it in a sample of vanadite, which is Pb ₅ (VO ₄ ) ₃ Cl, named because the salt solution of this new element turns bright red when heated "Eriteroni", which means "red", and sent this item to Paris, however, French chemists deduced that it was a contaminated chrome ore, so it was not recognized, and the second discovery was In 1830, when the Swedish chemist Sevstrom was studying the iron ore in the Smalan mining area, he dissolved iron with acid and found vanadium in the residue. Because the color of vanadium compounds is colorful and very beautiful, the ancient Greek The name of a beautiful goddess named Vanadis "Vanadis" in mythology named this new element "Vanadium", and the Chinese named it vanadium according to its transliteration, Sefström, Ville and Berzelius. Others have studied vanadium and confirmed the existence of vanadium, but they have never separated elemental vanadium. Later, in 1830, they wrote that Buddhist temple Telem found it in iron extracted from Swedish iron ore, and affirmed that it was A new element called vanadium, and he was able to show that it was a new element and thus beat a competing chemist from Waller in Simapan (Mexico), who was also working on another A kind of vanadium ore is studied, and traces of vanadium are all over the world. In the earth's crust, the content of vanadium is not much. On average, there is one vanadium atom in 20,000 atoms, which is more than copper, tin, zinc and nickel. In seawater, in marine organisms such as sea urchins, in magnetite, in various bituminous minerals and coal ash, in the Traces of vanadium have been found in the spectral lines of meteorites and the sun. Vanadium is a widely distributed trace element on the earth, its content accounts for about 0.02% of the crust, and it is relatively easy to obtain.

At present, vanadium is an important rare metal and has important applications in catalysts, alloys, batteries and advanced materials. Among them, all-vanadium redox flow batteries, as a new application field of vanadium, are more and more widely used. Compared with traditional batteries, it has the characteristics of fast, large-capacity charge and discharge, low self-discharge rate and simple battery structure. It is an ideal power source for large-scale energy storage of new energy such as wind energy and solar energy. As far as the electrolyte is concerned, the positive electrolyte is composed of a mixed solution of tetravalent and pentavalent vanadium ions and sulfuric acid, and the negative electrolyte is composed of a mixed solution of bivalent and trivalent vanadium ions and sulfuric acid. After the battery is charged, the positive electrode material is pentavalent. Vanadium ion sulfuric acid solution, the negative electrode is divalent vanadium ion sulfuric acid solution, after the battery is discharged, the positive and negative electrodes are tetravalent and trivalent vanadium ion sulfuric acid solution respectively, vanadyl sulfate is the main substance of the electrolyte, and its purity directly affects the performance of the electrolyte , and as a stably existing vanadium substance, it has a prominent role in the fields of medicine, chemical industry and national defense, and it is particularly feasible to extract high-purity vanadyl sulfate from waste, which consumes less energy and is easy to obtain raw materials. It is a promising technology field.

However, in the current production process, it is necessary to use conventional means such as distillation to refine and produce it, which consumes a lot of energy, and the acquisition of raw materials is troublesome, which increases its production cost and reduces its economic benefits. Therefore, a high-purity sulfuric acid is proposed. The preparation method of vanadyl solves the above problems.

SUMMARY OF THE INVENTION

(1) Technical problems solved

Aiming at the deficiencies of the prior art, the present invention provides a preparation method of high-purity vanadyl sulfate, which has the advantages of simple method, easy-to-obtain raw materials, low energy consumption, high purity of the obtained product and higher economic benefits, etc. It needs to use conventional means such as distillation to refine and produce it, which consumes a lot of energy, and the acquisition of raw materials is troublesome, which increases its production cost and reduces its economic benefits.

(2) Technical solutions

In order to realize that the above-mentioned method is simple, the raw materials are easy to obtain, the energy consumption is low, the obtained product has high purity and higher economic benefits, the present invention provides the following technical scheme: a preparation method of high-purity vanadyl sulfate, comprising the following raw materials: Vanadium ore, unbalanced 3.5-valent vanadium solution, alkaloid regulator and organic precipitant.

Another technical problem to be solved by the present invention is to provide a kind of preparation method of high-purity vanadyl sulfate, comprising the following steps:

1) prepare an alkaline vanadium-containing leachate, and obtain an alkaline vanadium-containing leachate by the traditional process of sodium roasting and leaching of vanadium ore;

2) mixed preparation, the alkaline vanadium-containing leaching solution and the unbalanced 3.5-valent vanadium solution are mutually matched, and the trivalent vanadium in the neutralization solution is matched with each other until the solution vanadium is 4-valent;

3) adjust the pH value, use the alkaloid regulator to adjust the pH value of the solution prepared above to neutrality, and promote the precipitation of tetravalent vanadium in the solution;

4) Crystallization, the above-mentioned precipitates are reversely dissolved into an aqueous sulfuric acid solution, and an organic precipitant is introduced to accelerate the crystallization of vanadyl sulfate in the new solution system.

Preferably, the vanadium of the alkaline vanadium-containing leachate in the step 1) exists in the form of +5 valence, the pH value of which is in the range of 8-12, and the vanadium content is 20-45 g/liter.

Preferably, the alkaloid regulator is one or more of atropine, halofugin, theophylline, coumarin, cinchona and berberine, and the compounded organic solvent is chloroform, formamide and acetone. A sort of.

Preferably, the organic precipitant is an alcohol, such as one of ethanol, ethylene glycol and glycerol.

Preferably, after the introduction of the organic precipitating agent in the step 4), the material is kept still in a constant temperature and humidity environment, and vanadyl sulfate crystals are precipitated for a short period of time.

Preferably, the recrystallized crystals are washed with water and filtered to obtain high-purity vanadyl sulfate.

(3) Beneficial effects

Compared with the prior art, the present invention provides a preparation method of high-purity vanadyl sulfate, which has the following beneficial effects:

The preparation method of high-purity vanadyl sulfate uses alkaline vanadium-containing leaching solution and unbalanced 3.5-valent vanadium solution as main raw materials, which facilitates extraction of high-purity vanadyl sulfate from waste, and effectively achieves the effect of waste recycling. It makes its raw materials easier to obtain. By using alkaloid regulators and organic precipitants to process it, it is convenient to adopt a more scientific and concise preparation method, and to abandon the original conventional methods such as distillation, thereby achieving the effect of saving energy. The preparation method is simple and effective, convenient for industrial large-scale production, and can effectively recover most of the vanadium in the waste liquid. At the same time, the method has low loss rate of vanadium and significant economic benefits, so the method is simple, the raw materials are easy to obtain, the The purpose of low energy consumption, high purity of the obtained product and higher economic benefits.

Detailed ways

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. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

A method for preparing high-purity vanadyl sulfate, comprising the following raw materials: vanadium ore, an unbalanced 3.5-valent vanadium solution, an alkaloid regulator and an organic precipitant.

A kind of preparation method of high-purity vanadyl sulfate, is characterized in that, comprises the following steps:

1) prepare an alkaline vanadium-containing leaching solution, obtain an alkaline vanadium-containing leaching solution by the traditional process of sodium roasting and leaching of vanadium ore, and the vanadium of the alkaline vanadium-containing leaching solution exists in the form of +5 valence, and the scope of its pH value is 8 -12, and the vanadium content is 20-45g/liter;

2) mixed preparation, the alkaline vanadium-containing leaching solution and the unbalanced 3.5-valent vanadium solution are mutually matched, and the trivalent vanadium in the neutralization solution is matched with each other until the solution vanadium is 4-valent;

3) adjust pH value, use alkaloid regulator to regulate the solution pH value of above-mentioned preparation to neutrality, and alkaloid regulator is a kind of in atropine, halofugin, theophylline, coumarine, cinchona and berberine Or more than two, the compound organic solvent is one of chloroform, formamide and acetone, and promotes the precipitation of tetravalent vanadium in the solution;

4) crystallization, the above-mentioned precipitate is reversely dissolved in the aqueous sulfuric acid solution, and an organic precipitating agent is introduced, so that vanadyl sulfate accelerates crystallization in the new solution system, and the organic precipitating agent is an alcohol, such as one of ethanol, ethylene glycol and glycerin. After introducing the organic precipitant, the material is kept in a constant temperature and humidity environment for a short time to precipitate vanadyl sulfate crystals, and the recrystallized crystals are washed with water and filtered to obtain high-purity vanadyl sulfate.

Experimental example:

Known vanadium concentration 2.8mol/L 1 liter of failed electrolyte, and vanadium-containing leaching solution 28 g/L 5 liters, mix with each other, stir, add a mixed regulator of atropine, theophylline and acetone, adjust the pH value to 7, let stand , to obtain crude vanadyl sulfate crystals, redissolve them in aqueous sulfuric acid solution, add excess glycerin, and stand for crystallization under constant temperature and humidity environment to obtain 610 grams of vanadyl sulfate crystals, and the recovery rate of vanadium is 89%.

The results of the examples show that the present invention takes the alkaline vanadium-containing leaching solution and the unbalanced 3.5-valent solution as raw materials, and finally obtains high-purity vanadyl sulfate.

The beneficial effects of the invention are as follows: by using the alkaline vanadium-containing leaching solution and the unbalanced 3.5-valent vanadium solution as the main raw materials, it is convenient to extract high-purity vanadyl sulfate from the waste, effectively realize the effect of recycling the waste, and make its raw materials It is easier to obtain, and by using alkaloid regulators and organic precipitants to process it, it is convenient to adopt a more scientific and concise preparation method, and to abandon the original conventional methods such as distillation, thereby realizing the effect of saving energy. The method is simple and effective, convenient for industrial large-scale production, and can effectively recover most of the vanadium in the waste liquid. At the same time, the method has a low loss rate of vanadium and significant economic benefits, so that the method is simple, the raw materials are readily available, and the energy consumption is low. , the purpose of high purity and higher economic benefit of the obtained product solves the need to use conventional means such as distillation to refine and produce it, consumes a lot of energy, and the acquisition of raw materials is more troublesome, which improves its production cost and reduces its cost. question of economic efficiency.

Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, and substitutions can be made in these embodiments without departing from the principle and spirit of the invention and modifications, the scope of the present invention is defined by the appended claims and their equivalents.

Claims (7)

1. a preparation method of high-purity vanadyl sulfate, is characterized in that, comprises following raw material: vanadium ore, unbalanced 3.5-valent vanadium solution, alkaloid regulator and organic precipitating agent. 2. a preparation method of high-purity vanadyl sulfate, is characterized in that, comprises the following steps: 1) prepare an alkaline vanadium-containing leachate, and obtain an alkaline vanadium-containing leachate by the traditional process of sodium roasting and leaching of vanadium ore; 2) mixed preparation, the alkaline vanadium-containing leaching solution and the unbalanced 3.5-valent vanadium solution are mutually matched, and the trivalent vanadium in the neutralization solution is matched with each other until the solution vanadium is 4-valent; 3) adjust the pH value, use the alkaloid regulator to adjust the pH value of the solution prepared above to neutrality, and promote the precipitation of tetravalent vanadium in the solution; 4) Crystallization, the above-mentioned precipitates are reversely dissolved into an aqueous sulfuric acid solution, and an organic precipitant is introduced to accelerate the crystallization of vanadyl sulfate in the new solution system. 3. the preparation method of a kind of high-purity vanadyl sulfate according to claim 1, is characterized in that, the vanadium of the basic vanadium-containing leaching solution in described step 1) exists with +5 valence form, and the scope of its pH value Between 8-12, and the vanadium content is 20-45g/liter. 4. the preparation method of a kind of high-purity vanadyl sulfate according to claim 1, is characterized in that, described alkaloids regulator is in atropine, kaempferol, theophylline, coumadin, cinchona and berberine One or more than two, the compound organic solvent is one of chloroform, formamide and acetone. 5. the preparation method of a kind of high-purity vanadyl sulfate according to claim 1, is characterized in that, described organic precipitating agent is alcohols, such as one of ethanol, ethylene glycol and glycerol. 6. the preparation method of a kind of high-purity vanadyl sulfate according to claim 1, is characterized in that, after described step 4) is introduced into organic precipitation agent, material is still in constant temperature and humidity environment, a little time, Precipitation of vanadyl sulfate crystals. 7. the preparation method of a kind of high-purity vanadyl sulfate according to claim 1 and 7, is characterized in that, described recrystallized crystal obtains high-purity vanadyl sulfate through washing and filtration.