CN103014377B - Vanadium liquid purification method - Google Patents

Abstract

The invention provides a method for purifying vanadium liquid. The vanadium liquid contains vanadate ions, silicate ions, aluminum ions and calcium ions. Contacting, so that the silicate ions in the vanadium liquid and the impurity remover A form a precipitate, and the aluminum ions and calcium ions in the vanadium liquid form a precipitate with the impurity remover B. According to the method for purifying vanadium liquid provided by the present invention, it is possible to make PO ₄ ^3- <0.005g/L, SiO ₄ ^2- <0.005g/L, Ca ²⁺ <0.005g/L, Al ³ in the purified vanadium liquid ⁺ <0.01g/L, and has the advantages of simple and easy-to-use process, loose composition requirements of vanadium liquid, low equipment requirements, convenient operation, low cost, and good social and economic benefits.

Description

A kind of purification method of vanadium liquid

technical field

The invention relates to a method for purifying vanadium liquid.

Background technique

Vanadium products with lower calcium, aluminum, silicon and phosphorus content are vanadium products with higher added value. It is used in different industries and has different technical requirements. It can usually be used in metallurgy, chemical industry, medicine, energy, environmental protection, aerospace and other industries, and has an irreplaceable role.

In the process of leaching and extracting vanadium from vanadium-containing clinker, some impurities are also leached into the solution together with vanadium. The vanadium-containing leach solution usually contains impurity ions such as iron, manganese, chromium, silicon, phosphorus, aluminum, calcium, etc., which affect the precipitation. The quality of vanadium and products, these impurity ions are under the adjustment of the pH value of the leaching solution, most of the impurity ions undergo hydrolysis reaction and precipitate into the sedimentation residue, but phosphorus, silicon, calcium and aluminum still form soluble compounds after hydrolysis and remain in the leaching solution , Seriously affect Shen vanadium and product quality, must be removed. Therefore, special purification treatment is required. Conventional removal methods usually include solvent extraction or ion exchange, but the removal effect is not ideal. Therefore, how to remove impurities phosphorus, silicon, calcium and aluminum from vanadium-containing clinker leachate to meet the product Quality requirements are of great significance.

The impurity phosphorus in the vanadium-containing clinker leachate mainly exists in the form of phosphate ions. In the domestic industry, calcium chloride aqueous solution is often used to generate calcium phosphate from phosphate ions, and at the same time destroy the colloid, so that the suspended solids coagulate and settle, thereby removing phosphate ions in the vanadium-containing clinker leachate, but this method has the effect of removing phosphate ions. The pH value range is narrow, and the pH control is difficult; Germany uses gypsum milk as a phosphorus removal agent, but there is a problem of large dosage; there are also ammonium magnesium phosphate precipitation methods, so that the phosphate ion is replaced by magnesium phosphate or ammonium phosphate The magnesium form precipitates from solution, and this method requires a long (up to 48 hours) standing process, which reduces production efficiency.

Impurity silicon in vanadium-containing clinker leaching solution mainly exists in the form of orthosilicate ion, which has colloidal properties. Generally, the inorganic salt electrolyte coagulant is added to form a precipitate to remove it. The coagulant includes aluminum sulfate, alum, magnesium chloride and calcium chloride.

The Chinese invention patent application of CN 101182036A discloses a process for preparing high-purity vanadium pentoxide. The process uses hydrochloric acid to adjust the pH value of the analysis solution to 8-9, adopts aluminum sulfate as a purifying agent, stirs and reacts for 40-50 hours, and stands still for 48 ~72 hours; separate the solid-liquid mixture after standing, adjust the pH value of the filtrate to 8-9 with hydrochloric acid, and add ammonium chloride to react for 3-4 days under the condition of stirring at room temperature; the obtained ammonium metavanadate after standing Centrifugal dehydration of the crystal, and centrifugal washing with distilled water at the same time; after dehydration, ammonium metavanadate is burned in an electric calciner at 500-550°C for 6-8 hours, and high-purity vanadium pentoxide is obtained after cooling, and the purity of the obtained product is more than 99.5%. . This process is only limited to the purification of vanadium liquid after roasting flow and ion exchange of vanadium ore, and does not involve vanadium liquid components such as leaching vanadium liquid from vanadium slag clinker, direct leaching vanadium liquid from vanadium ore, and vanadium liquid obtained by dissolving crude vanadium products. More complex vanadium liquid purification; and the adjustment of pH value is limited to hydrochloric acid, the purification pH value is limited to 8-9, and the purification agent is only aluminum sulfate; the reaction time is long and the process is complicated.

The Chinese invention patent application of CN 101724756A discloses a method for removing phosphorus and silicon from a vanadium-containing clinker leaching solution. The method performs the following steps on the vanadium-containing clinker leaching solution obtained after leaching the vanadium-containing clinker: taking the vanadium-containing clinker leaching solution The temperature is set within the temperature range from 60°C to boiling: adjust the pH value of the vanadium-containing clinker leaching solution; use acid and alkali to adjust the pH value of the vanadium-containing clinker leaching solution according to the type of purifying agent to be added; add purifying agent, add The amount of scavenger is determined according to the amount of phosphorus and silicon detected in the vanadium-containing clinker leachate and the reaction formula between phosphorus and silicon in the vanadium-containing clinker leachate and the scavenger; the obtained vanadium-containing clinker leachate is cooled and filtering to obtain a low-phosphorus and low-silicon vanadium liquid. However, this method is limited to the removal of impurities from the vanadium solution of the vanadium-containing clinker leaching solution, which has certain limitations, and can only remove phosphate ions and silicate ions at the same time, but cannot remove other calcium ions and aluminum ions.

It can be seen that the traditional vanadium liquid purification and impurity removal has certain limitations. It is limited to the purification and removal of vanadium liquid after vanadium ore roasting flow, ion exchange or vanadium slag clinker leaching vanadium liquid. Directly leaching vanadium liquid from vanadium ore, leaching vanadium liquid by blowing vanadium and vanadium slag in molten iron, vanadium liquid extracted from stone coal, and vanadium liquid obtained by dissolving crude vanadium products, etc. limited. Therefore, it is very necessary to develop a purification method suitable for a wider and more complex composition of vanadium liquid.

Contents of the invention

The object of the present invention is to overcome the limitations of the purification and impurity removal of vanadium liquid in the prior art, and provide a vanadium liquid purification method involving a wide range of vanadium liquid and capable of simultaneously removing various ionic impurities.

Aiming at the deficiencies in the prior art, the inventors of the present invention have carried out a large amount of research, and found that adding in the vanadium liquid can form precipitates with silicate ions or can promote silicate ions to form precipitates or colloids without forming with vanadate ions. The substance of precipitation or colloid is used as impurity remover A and can generate precipitation with aluminum ion and calcium ion or can promote aluminum ion and calcium ion to generate precipitation or colloid and does not generate precipitation or colloid with vanadate ion as impurity remover B, It can simultaneously remove phosphate ions, silicate ions, calcium ions and aluminum ions in the vanadium liquid, and the content of free phosphate ions, silicate ions, calcium ions and aluminum ions in the purified vanadium liquid is controlled at a low level under the content.

The invention provides a method for purifying vanadium liquid. The vanadium liquid contains vanadate ions, silicate ions, aluminum ions and calcium ions. The method comprises contacting the vanadium liquid with impurity remover A and impurity remover B, and The product obtained after contacting is subjected to solid-liquid separation; wherein, the impurity remover A is a substance that can generate precipitates with silicate ions or can promote the formation of precipitates or colloids with silicate ions and does not generate precipitates or colloids with vanadate ions, so The impurity remover B is a substance that can form precipitates with aluminum ions and calcium ions or can promote the formation of precipitates or colloids with aluminum ions and calcium ions without forming precipitates or colloids with vanadate ions.

The vanadium liquid purification method provided by the method of the present invention can simultaneously remove various metal ions such as phosphate ions, silicate ions, calcium ions and aluminum ions in the vanadium liquid, and the phosphate ions and silicate ions in the purified vanadium liquid , calcium ion and aluminum ion content: PO ₄ ^3- <0.005g/L, SiO ₄ ^2- <0.005g/L, Ca ²⁺ <0.005g/L, Al ³⁺ <0.01g/L; with simple process Easy to use, loose vanadium liquid composition requirements, low equipment requirements, convenient operation, low cost, and good social and economic benefits.

Detailed ways

The invention provides a method for purifying vanadium liquid. The vanadium liquid contains vanadate ions, silicate ions, aluminum ions and calcium ions. The method comprises contacting the vanadium liquid with impurity remover A and impurity remover B, and The product obtained after contacting is subjected to solid-liquid separation; wherein, the impurity remover A is a substance that can generate precipitates with silicate ions or can promote the formation of precipitates or colloids with silicate ions and does not generate precipitates or colloids with vanadate ions, so The impurity remover B is a substance that can form precipitates with aluminum ions and calcium ions or can promote the formation of precipitates or colloids between aluminum ions and calcium ions without forming precipitates or colloids with vanadate ions.

According to the present invention, the mode of contacting the vanadium liquid with the impurity remover A and the impurity remover B can be that the vanadium liquid, the impurity remover A and the impurity remover B are simultaneously added into the reactor for contacting; The liquid and the impurity remover A are added to the reactor, and the impurity remover B is directly added to the reactor for contact without filtering; it is also possible to add the vanadium liquid and the impurity remover B into the reactor first, and then directly Add impurity remover A to the reactor for contacting; it is also possible to add vanadium liquid to the reactor first, and then add impurity remover A and impurity remover B to the reactor successively or simultaneously; it is also possible to first add impurity remover A and impurity remover B into the reactor, and then add vanadium liquid into the reactor. In the present invention, the vanadium liquid, the impurity remover A and the impurity remover B are preferably added to the reactor at the same time or the vanadium liquid is added to the reactor first, and then the impurity remover A and the impurity remover B are added to the reactor simultaneously or successively, And the time interval between adding impurity remover A and impurity remover B is less than 5 minutes. The precipitate formed by filtration under the above-mentioned preferred conditions is easier to separate. The time interval between the addition of the impurity remover A and the impurity remover B refers to the period from the completion of one addition to the start of the other addition.

According to the present invention, the composition requirements of the vanadium liquid are relatively loose, and can be a vanadium liquid containing vanadate ions, preferably an alkaline or neutral vanadium liquid containing vanadate ions, and more preferably obtained by leaching and filtering vanadium-containing clinker One of vanadium liquid, vanadium liquid obtained by direct leaching and filtration of vanadium ore, vanadium liquid obtained by dissolving crude vanadium products, vanadium liquid leached from molten iron blowing vanadium and vanadium slag, and vanadium liquid extracted from stone coal.

According to the present invention, the impurity remover A is a substance that can generate precipitates with free silicate ions in the vanadium liquid or can promote the formation of precipitates or colloids of silicate ions. Preferably, the impurity remover A is aluminum salts, iron salts, The mixture of any two in magnesium salt and ammonium salt, more preferably described aluminum salt can be aluminum sulfate, aluminum chloride and aluminum nitrate, more preferably described aluminum salt is preferably aluminum sulfate; More preferably described iron salt can be Ferric sulfate, ferric chloride and ferric nitrate, more preferably the iron salt is preferably ferric sulfate; more preferably the magnesium salt can be magnesium sulfate, magnesium chloride and magnesium nitrate, more preferably the magnesium salt is preferably magnesium sulfate More preferably, the ammonium salt can be ammonium sulfate, ammonium chloride, ammonium nitrate, and more preferably, the ammonium salt is preferably ammonium sulfate.

According to the present invention, the amount of the impurity remover A is such that the concentration of free silicate ions in the obtained vanadium liquid after contacting is less than 0.005 g/liter. The amount of silicate ions detected was determined with the Reaction Equation for the Impurity Removal Agent A. The consumption of described impurity remover A is determined by following formula (1):

W1＝k1×(2C ₀ ×V)/m (1)

Wherein, W represents the molar number of impurity remover A in terms of metal cations reacted with silicate ions, _C represents the molar concentration of silicate ions in the vanadium liquid, and the unit is mole/liter, and V represents the volume of the vanadium liquid, in units is the liter, m represents the valence state of the metal cation reacting with the silicate ion in the impurity remover A, k1=0.9-1.1.

According to the present invention, the vanadium liquid also contains phosphate ions, and the impurity remover A can generate precipitates with silicate ions and phosphate ions or can promote the formation of precipitates or colloids with silicate ions and phosphate ions and does not interact with vanadium Acid radical ions generate precipitates or colloidal substances, and the amount of the impurity remover A also makes the free phosphate ion concentration in the obtained vanadium liquid after contacting less than 0.005 g/liter. Specifically, the amount of the impurity remover A is as follows: The above formula (2) determines:

W2＝k2×{(2C ₀ ×V)/m+(3C ₁ ×V)/m} (2)

Wherein, W represents the molar number of impurity removal agent A based on _metal cations reacted with silicate ions and phosphate ions, C represents the molar concentration of silicate ions in the vanadium liquid, and the unit is mol/liter, and C represents _vanadium The molar concentration of the phosphate ion in the liquid, the unit is mole/liter, V represents the volume of the vanadium liquid, the unit is liter, m represents the valence state of the metal cation reacted with the silicate ion and the phosphate ion in the impurity remover A, k2 = 0.9-1.1.

According to the present invention, the impurity remover B is a substance that can react with aluminum ions and calcium ions to form precipitates or can promote aluminum ions and calcium ions to form precipitates or colloids. Preferably, the impurity remover B is carbonate, oxalic acid One of salt and acetate, more preferably carbonate. The carbonate may be one of sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, more preferably sodium carbonate.

According to the present invention, the amount of the impurity remover B makes the concentration of free aluminum ions less than 0.01 g/liter and calcium ion concentration less than 0.005 g/liter in the obtained vanadium liquid after contacting, specifically, adding the impurity remover B The amount is determined by the amount of calcium ions and aluminum ions detected in the vanadium liquid and the reaction formula of the impurity remover B. The consumption of described impurity remover B is determined by following formula (3):

W3＝k3×(3C ₂ ×V)/n+(2C ₃ ×V)/n (3)

Wherein, W3 represents the molar number of impurity remover B based on the anion that reacts with aluminum ions and calcium ions to form a precipitate, C ₂ represents the molar concentration of aluminum ions in the vanadium liquid, and the unit is mole/liter, and C ₃ represents the molar concentration in the vanadium liquid The molar concentration of calcium ions, the unit is mol/liter, V represents the volume of the vanadium liquid, the unit is liters, n represents the valence state of anions reacting with aluminum ions and calcium ions in the impurity remover B, k3=0.9-1.1.

According to the present invention, the vanadium liquid is contacted with impurity remover A and impurity remover B simultaneously, and the product obtained after contact is subjected to solid-liquid separation; the conditions of the contact are such that the concentration of free silicate ions in the vanadium liquid is Less than 0.005g/L, the concentration of free phosphate ions in the vanadium solution is less than 0.005g/L, the concentration of free aluminum ions in the vanadium solution is less than 0.01g/L and the concentration of calcium ions is less than 0.005g/L.

According to the present invention, the contacting conditions include a temperature ranging from 60° C. to the boiling temperature of the vanadium liquid, a time of 0.5-1.5 hours, preferably 1 hour, and a pH of 8-11.

According to the present invention, the solid-liquid separation can be carried out by methods known in the art, and solid-liquid separation can be carried out by using a solid-liquid separator, a sieve, or a Buchner funnel. In the present invention, the solid-liquid separation is preferably carried out by suction filtration using a Buchner funnel.

According to a specific embodiment of the present invention, the purification method of described vanadium liquid comprises the following steps:

(1) process vanadium-containing raw materials, and filter to obtain vanadium liquid containing vanadate ions;

(2) The vanadium liquid is contacted with the impurity remover A and the impurity remover B; the contact condition is: the temperature is that the vanadium liquid is heated to 60° C. to the boiling temperature of the vanadium liquid, according to the impurity remover A and the impurity remover B The type and amount of the vanadium solution are adjusted to pH=8-11 with acid or alkali, reacted for 0.5-1.5 hours, cooled to normal temperature, and filtered to obtain filtrate.

The method of the present invention can be applicable to various vanadium-containing solutions containing vanadate, phosphate, silicate, aluminum ions and calcium ions. Preferably, the total vanadium content in the vanadium solution is 5-80g/L, and the phosphate The ion content is 0.035-0.055g/L, the silicate ion content is 1.18-1.25g/L, the aluminum ion content is 0.03-0.05g/L, and the calcium ion content is 0.115-0.129g/L.

The vanadium solution meeting the above conditions can be, for example, vanadium solution obtained by leaching and filtering vanadium-containing clinker, vanadium solution obtained by direct leaching and filtering of vanadium ore, vanadium solution obtained by dissolving crude vanadium products, vanadium solution leached from molten iron vanadium vanadium slag and One or more types of vanadium extraction solution from stone coal.

According to the present invention, various treatments can be performed on the vanadium-containing raw materials to obtain the above-mentioned vanadium liquid. The vanadium-containing raw material can be processed according to methods known to those skilled in the art, preferably, the vanadium-containing raw material is treated as an alkaline or neutral vanadium solution containing vanadate ions, specifically, the vanadium-containing For vanadium ore, vanadium ore can be directly leached and filtered to obtain vanadium liquid; similarly, for molten iron blowing vanadium vanadium slag, it can be obtained by directly leaching and filtering molten iron vanadium vanadium slag Vanadium liquid; for stone coal, it is also possible to directly leach and filter the stone coal to obtain vanadium liquid; if it is a crude vanadium product, the crude vanadium product can be dissolved to obtain vanadium liquid.

According to the present invention, according to the type and amount of the impurity remover to be added, an acid or alkali is selected to adjust the pH=8-11 of the vanadium liquid. The acid or alkali is not particularly limited, and can be known to those skilled in the art Some acids or bases, for example, the acid can be hydrochloric acid, nitric acid and sulfuric acid, preferably hydrochloric acid; the base can be sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, preferably sodium hydroxide.

The present invention will be further described below in conjunction with embodiment.

The vanadium liquid used in embodiments 1-4 is the ordinary vanadium liquid A obtained by leaching and filtering vanadium-containing clinker, the vanadium liquid used in embodiment 5 is the vanadium liquid B obtained by direct leaching and filtering vanadium ore, and the vanadium liquid used in embodiment 6 is crude vanadium product The vanadium liquid C of dissolving gained, the vanadium liquid used in embodiment 7 is molten iron blowing vanadium vanadium slag leaching vanadium liquid D, the vanadium liquid used in embodiment 8 is stone coal vanadium vanadium liquid E; The main chemical composition of embodiment 1-8 is as table 1, the unit is g·L ^-1 .

Table 1

TV PO ₄ ^3- Mg ²⁺ Na ⁺ SiO ₄ ^2- TFe TCr Mn Al ³⁺ Ca ²⁺ pH A 33.86 0.052 0.002 28.04 1.19 0.010 1.51 0.001 0.05 0.122 10.45 B 8.56 0.045 0.004 7.56 1.18 0.02 0.85 0.002 0.04 0.118 10.35 C 45.89 0.048 0.003 33.5 1.20 0.01 0.05 0.001 0.03 0.125 10.85 D 27.56 0.055 0.001 29.18 1.25 0.010 1.05 0.003 0.048 0.129 10.55 E 75.21 0.035 0.002 23.5 1.22 0.01 0.04 0.001 0.05 0.115 10.22

Example 1

This embodiment is used to illustrate the vanadium liquid purification method provided by the present invention.

Add 300mL common vanadium solution A obtained by leaching and filtering the vanadium-containing clinker in Table 1 into a 500mL clean beaker, stir, heat to the boiling temperature of the vanadium solution, and add 12g impurity remover A and impurity remover B (4g aluminum sulfate Al ₂ (SO ₄ ) ₃ ·18H ₂ O, 6g of magnesium sulfate (MgSO ₄ ·7H ₂ O and 2g of sodium carbonate), adjust the pH of the vanadium solution to 8, react for 0.5h, cool to room temperature, and filter to obtain PO ₄ ^3- =0.003g/L, SiO ₄ ^2- =0.003g/L, Ca ²⁺ =0.002g/L, Al ³⁺ =0.008g/L vanadium solution.

Comparative example 1

A method for removing phosphorus and silicon from a vanadium-containing clinker leaching solution disclosed in CN 101724756A is used to purify the vanadium solution. Specific steps are as follows:

Add 1000ml of ordinary vanadium liquid A obtained by leaching and filtering the vanadium-containing clinker in 2000ml clean beaker in Table 1, heat to boiling, adjust the pH value of the vanadium liquid to 8.5, then add 5g of anhydrous magnesium chloride and anhydrous aluminum sulfate to fully stir, and react Fully react for 1 hour, cool to room temperature, and filter to obtain vanadium liquid with PO ₄ ^3- =0.006g/L, SiO ₄ ^2- =0.0084g/L, Ca ²⁺ =0.122g/L, Al ³⁺ =0.05g/L .

Comparative example 2

The common vanadium liquid A in Table 1 is purified according to the method in Example 1, the difference is that the impurity remover A is not added to the vanadium liquid, but is directly added to the vanadium liquid after being heated to the boiling temperature of the vanadium liquid 1g impurity remover B (sodium carbonate), adjust the pH of the filtrate to 8, react for 0.5h, cool to room temperature, and filter to obtain PO ₄ ³ =0.052g/L, SiO ₄ ^2- =1.19g/L, Ca ²⁺ =0.002g/L, Al ³⁺ =0.008g/L vanadium solution.

Example 2

This embodiment is used to illustrate the vanadium liquid purification method provided by the present invention.

Add 300mL common vanadium solution A obtained by leaching and filtering the vanadium-containing clinker in Table 1 into a 500mL clean beaker, stir, heat to the boiling temperature of the vanadium solution, and add 12g impurity remover A and impurity remover B (4g aluminum sulfate Al ₂ (SO ₄ ) ₃ .18H ₂ O, 6g of iron sulfate Fe ₂ (SO ₄ ) ₃ .9H ₂ O and 2g of sodium carbonate), adjust with acid or alkali to make the vanadium liquid pH=8, react for 1h, cool to At room temperature, filter to obtain vanadium liquid with PO ₄ ^3-- =0.002g/L, SiO ₄ ^2- =0.004g/L, Ca ²⁺ =0.003g/L, Al ³⁺ =0.009g/L.

Example 3

This embodiment is used to illustrate the vanadium liquid purification method provided by the present invention.

In a 500mL clean beaker, add 300mL common vanadium solution A obtained by leaching and filtering the vanadium-containing clinker in Table 1, stir, and heat to the boiling temperature of the vanadium solution, and simultaneously add 12g impurity remover A and impurity remover B (4g iron sulfate ₂ (SO ₄ ) ₃ .9H ₂ O, 6g of magnesium sulfate (MgSO ₄ .7H ₂ O and 2g of sodium carbonate), adjust with acid or alkali to make the pH of the vanadium liquid=10, react for 1.5h, cool to room temperature, filter, A vanadium solution of PO ₄ ^3- =0.004g/L, SiO ₄ ^2- =0.004g/L, Ca ²⁺ =0.002g/L, Al ³⁺ =0.009g/L was obtained.

Example 4

This embodiment is used to illustrate the vanadium liquid purification method provided by the present invention.

Add 300mL common vanadium solution A obtained by leaching and filtering the vanadium-containing clinker in Table 1 into a 500mL clean beaker, stir, heat to the boiling temperature of the vanadium solution, and add 12g impurity remover A and impurity remover B (4g aluminum sulfate Al ₂ (SO ₄ ) ₃ 18H ₂ O, 6g of ammonium sulfate (NH ₄ ) ₂ SO ₄ and 2g of sodium bicarbonate), adjust with acid or alkali to make the pH of the vanadium liquid = 9, react for 1h, cool to room temperature, filter , to obtain PO ₄ ^3- =0.002g/L, SiO ₄ ^2- =0.003g/L, Ca ²⁺ =0.004g/L, Al ³⁺ =0.008g/L vanadium solution.

Example 5

This embodiment is used to illustrate the vanadium liquid purification method provided by the present invention.

In the 500mL clean beaker, add 300mL vanadium ore direct leaching and filtering gained vanadium liquid B in Table 1, stir, be heated to the boiling temperature of vanadium liquid, add 12g impurity remover A and impurity remover B simultaneously (4g aluminum sulfate Al ₂ ( SO ₄ ) ₃ ·18H ₂ O, 6g of magnesium sulfate (MgSO ₄ ·7H ₂ O and 2g of sodium carbonate), adjust with acid or alkali to make the pH of the vanadium liquid = 8, react for 0.5h, cool to room temperature, filter to obtain PO ₄ ^3- =0.003g/L, SiO ₄ ^2- =0.004g/L, Ca ²⁺ =0.004g/L, Al ³⁺ =0.009g/L vanadium solution.

Example 6

This embodiment is used to illustrate the vanadium liquid purification method provided by the present invention.

In the 500mL clean beaker, add the vanadium liquid C obtained by dissolving the crude vanadium product in 300mL table 1, stir, be heated to the boiling temperature of the vanadium liquid, add 12g impurity remover A and impurity remover B simultaneously (4g aluminum sulfate Al ₂ (SO ₄ ) 3.18H ₂ O, 6g of magnesium sulfate (MgSO ₄ .7H ₂ O and 2g of sodium carbonate) _, adjust with acid or alkali to make the pH of the vanadium liquid = 8, react for 0.5h, cool to room temperature, filter to obtain PO ₄ ^3- =0.003g/L, SiO ₄ ^2- =0.002g/L, Ca ²⁺ =0.002g/L, Al ³⁺ =0.009g/L vanadium solution.

Example 7

This embodiment is used to illustrate the vanadium liquid purification method provided by the present invention.

Add 300mL of molten iron blowing vanadium vanadium slag leaching vanadium liquid D in 500mL clean beaker in Table 1, stir, be heated to the boiling temperature of vanadium liquid, add 12g impurity remover A and impurity remover B simultaneously (4g aluminum sulfate Al ₂ (SO ₄ ) 3.18H ₂ O, 6g of magnesium sulfate (MgSO ₄ .7H ₂ O and 2g of sodium carbonate) _, adjust with acid or alkali to make the pH of the vanadium liquid = 8, react for 0.5h, cool to room temperature, filter to obtain PO ₄ ^3- =0.004g/L, SiO ₄ ^2- =0.002g/L, Ca ²⁺ =0.003g/L, Al ³⁺ =0.008g/L vanadium solution.

Example 8

This embodiment is used to illustrate the vanadium liquid purification method provided by the present invention.

Add 300mL of vanadium extraction solution E from stone coal in Table 1 to a 500mL clean beaker, stir, and heat to the boiling temperature of the vanadium solution, and simultaneously add 12g of impurity remover A and impurity remover B (4g of aluminum sulfate Al ₂ (SO ₄ ) ₃ 18H ₂ O, 6g of magnesium sulfate MgSO ₄ 7H ₂ O and 2g of sodium carbonate), adjusted with acid or alkali to make the pH of the vanadium solution = 8, reacted for 0.5h, cooled to room temperature, filtered to obtain PO ₄ ^3- = 0.002g/L, SiO ₄ ^2- =0.002g/L, Ca ²⁺ =0.004g/L, Al ³⁺ =0.009g/L vanadium solution.

Example 9

This embodiment is used to illustrate the vanadium liquid purification method provided by the present invention.

According to the method of Example 8, vanadium extracting liquid E from stone coal is purified, the difference is that 10g impurity remover A (4g aluminum sulfate Al ₂ (SO ₄ ) ₃ 18H ₂ O and 6g of magnesium sulfate MgSO ₄ 7H ₂ O) was replaced by 10 g of magnesium sulfate MgSO ₄ ·7H ₂ O, resulting in PO ₄ ^3- = 0.004 g/L, SiO ₄ ^2- = 0.004 g/L, Ca ²⁺ = 0.004 g/L, Al ³⁺ = 0.009g/L vanadium solution.

Claims (11)

1. a purification method of vanadium liquid, this vanadium liquid contains vanadate ion, silicate ion, aluminum ion and calcium ion, and the method comprises that vanadium liquid is contacted with impurity remover A and impurity remover B, and will contact The resulting product is subjected to solid-liquid separation; wherein, the impurity remover A is a material that can generate precipitates with silicate ions or can promote the formation of precipitates or colloids with silicate ions and does not generate precipitates or colloids with vanadate ions. Dopant B is a substance that can generate precipitates with aluminum ions and calcium ions or can promote the formation of precipitates or colloids between aluminum ions and calcium ions and does not generate precipitates or colloids with vanadate ions; Wherein, the impurity remover A is a mixture of any two of aluminum salts, iron salts, magnesium salts and ammonium salts; the impurity remover B is sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate one or more; Wherein, the vanadium liquid is one or more of vanadium liquid obtained by direct leaching and filtration of vanadium ore, vanadium liquid obtained by dissolving crude vanadium products, vanadium liquid leached from molten iron vanadium vanadium slag, and vanadium liquid extracted from stone coal. 2. The method according to claim 1, wherein, the consumption of the impurity remover A makes the free silicate ion concentration in the obtained vanadium liquid after contacting less than 0.005 g/liter. 3. The method according to claim 1 or 2, wherein the consumption of the impurity remover A is determined by the following formula (1): W1＝k1×(2C ₀ ×V)/m (1) Wherein, W represents the molar number of impurity removal agent A in terms of metal cations reacted with silicate ions, _C represents the molar concentration of silicate ions in the vanadium liquid, and the unit is mole/liter, and V represents the volume of the vanadium liquid, in units is liters, m represents the valence state of metal cations reacting with silicate ions in the impurity remover A, k1=0.9-1.1. 4. method according to claim 1, wherein, described vanadium liquid also contains phosphate ion, and described impurity removal agent A can generate precipitation with silicate ion and phosphate ion or can promote silicate ion and phosphate ion Ions form precipitates or colloids and do not form precipitates or colloids with vanadate ions. The amount of the impurity remover A also makes the concentration of free phosphate ions in the vanadium liquid obtained after contacting less than 0.005 g/L. 5. method according to claim 4, wherein, the consumption of described impurity remover A is determined by following formula (2): W2＝k2×{(2C ₀ ×V)/m+(3C ₁ ×V)/m} (2) Wherein, W represents the molar number of impurity removal agent A based on _metal cations reacted with silicate ions and phosphate ions, C represents the molar concentration of silicate ions in the vanadium liquid, and the unit is mol/liter, and C represents _vanadium The molar concentration of the phosphate ion in the liquid, the unit is mole/liter, V represents the volume of the vanadium liquid, the unit is liter, m represents the valence state of the metal cation reacted with the silicate ion and the phosphate ion in the impurity remover A, k2 = 0.9-1.1. 6. The method according to claim 1, wherein the aluminum salt is aluminum sulfate, the iron salt is iron sulfate, the magnesium salt is magnesium sulfate, and the ammonium salt is ammonium sulfate. 7. The method according to claim 1, 2 or 4, wherein the contacting conditions include a temperature of 60° C. to the boiling temperature of vanadium liquid, a time of 0.5-1.5 hours, and a pH of 8-11. 8. method according to claim 1, wherein, the consumption of described impurity removal agent B makes the free aluminum ion concentration in the gained vanadium liquid after contacting less than 0.01 gram/liter and the free calcium ion concentration in the vanadium liquid less than 0.005 gram /Lift. 9. The method according to claim 1 or 8, wherein the consumption of the impurity remover B is determined by the following formula (3): W3＝k3×{(3C ₂ ×V)/n+(2C ₃ ×V)/n} (3) Wherein, W represents the molar number of impurity remover B based on the anion that reacts with aluminum ions and calcium ions to form a precipitate, C ₂ represents the molar concentration of aluminum ions in the vanadium liquid, and the unit is mol/liter, and C ₃ represents the molar concentration in the vanadium liquid The molar concentration of calcium ions, the unit is mol/liter, V represents the volume of the vanadium liquid, the unit is liters, n represents the valence state of the anion that reacts with aluminum ions and calcium ions in the impurity remover B to form a precipitate, k3=0.9-1.1 . 10. The method according to claim 9, wherein the impurity remover B is sodium carbonate. 11. The method according to claim 1, wherein, in the vanadium liquid, the total vanadium content is 5-80g/L, the phosphate ion content is 0.035-0.055g/L, and the silicate ion content is 1.18-1.25g/L L, the aluminum ion content is 0.03-0.05g/L, and the calcium ion content is 0.115-0.129g/L.