WO2018192441A1

WO2018192441A1 - Method for use in producing battery-grade vanadium oxide

Info

Publication number: WO2018192441A1
Application number: PCT/CN2018/083185
Authority: WO
Inventors: 何文艺; 彭毅; 李明; 叶露; 陈燕; 申彪
Original assignee: 攀钢集团研究院有限公司
Priority date: 2017-04-17
Filing date: 2018-04-16
Publication date: 2018-10-25
Also published as: CN106834688A; RU2736539C1; ZA201905894B; CN106834688B

Abstract

A method for use in producing battery-grade vanadium oxide, comprising the following steps: A. adding a vanadium-containing leaching solution into a mixed solution of ammonium carbonate, ammonia water and ammonium sulfate, stirring to precipitate, and separating liquid from solid to obtain a crude vanadium-containing product; B. using hot water to wash the crude vanadium-containing product to obtain a purified vanadium-containing leaching solution; C. adjusting the pH of the purified vanadium-containing leaching solution to 1.5-2.5, and adding said solution into a boiling ammonium sulfate solution, heating and stirring, precipitating and separating solid from liquid to obtain high-purity ammonium polyvanadate (APV), washing, drying and calcinating the APV to obtain battery-grade vanadium pentoxide.

Description

Method for producing battery grade vanadium oxide

Technical field

The invention belongs to the technical field of vanadium extraction, and particularly relates to a method for producing a battery-grade vanadium oxide.

Background technique

Vanadium is widely used in steel, aerospace, and catalyst industries due to its excellent performance. At present, most of the world's vanadium plants only produce V ₂ O ₃ or V ₂ O ₅ crude products, and only a few manufacturers produce high-purity vanadium oxide and Other vanadium-containing products, but still have problems such as high production cost, long production process, and high content of impurities in products.

“Vanadium-containing solution→precipitated vanadium→APV, AMV or V ₂ O ₅ →dissolved→depleted→vanadium→dissolved→depleted→vanadium→high-purity vanadium oxide” is the main extraction process of high-purity vanadium oxide. In order to pass the vanadium-containing solution to the high-purity vanadium oxide product, three times of vanadium precipitation, two dissolutions, and two impurity removals are required, and a large amount of sodium-containing wastewater is generated in the production process, and the waste water treatment cost is high, and at the same time, multiple times of impurity removal-subduction Vanadium leads to low yield of vanadium oxide and high energy consumption, which is not conducive to large-scale production, and the obtained vanadium oxide product cannot stably reach the requirements of battery-grade vanadium oxide.

Summary of the invention

The object of the present invention is to overcome the deficiencies of the existing battery-grade vanadium oxide production process, thereby providing a production method of a battery-grade vanadium oxide having a simple production process, low energy auxiliary material consumption and low production cost.

The technical problem to be solved by the present invention is to provide a method for producing a battery-grade vanadium oxide. The method includes the following steps:

A, the calcification roasting vanadium-containing leaching solution is added to a mixed solution of ammonium carbonate, ammonia water and ammonium sulfate, and the precipitate is stirred and precipitated, and the liquid-solid separation is carried out to obtain a crude vanadium-containing product;

B. Washing the crude vanadium containing product with hot water to obtain a purified vanadium-containing leaching solution;

C. Adjust the pH of the purified vanadium-containing leaching solution to 1.5-2.5, add to the ammonium sulfate solution with a pH of 1.5-2.5 and a temperature of 90 ° C to boiling, and keep the temperature stirring, precipitation, solid-liquid separation to obtain high purity. APV, the APV is washed, dried and calcined to obtain battery-grade vanadium pentoxide.

Preferably, in the step A of the above-mentioned battery-grade vanadium oxide production method, the vanadium-containing leaching solution is obtained by acid leaching of vanadium slag after calcination, the pH value is 2.5 to 4.0, and the main component is TV 20-60 g/L, SO ₄ ^{2 -} 40 to 120 g/L, Mn 8 to 24 g/L, Mg 1 to 6 g/L, Si 0.2 to 1.2 g/L, P 0.01 to 0.06 g/L, and Fe < 0.05 g/L.

Preferably, in the step A of the above-mentioned battery-grade vanadium oxide production method, the ratio of the mixed solution of the ammonium carbonate, the ammonia water and the ammonium sulfate to the vanadium-containing leaching solution is: molar ratio, CO ₃ ^2- /Mn+Mg= 1.0 to 1.5, NH ₄ ^{+ /} V = 2.0 to 4.0, and the pH of the mixed system of the mixed solution and the vanadium-containing leaching solution is controlled to be 7.5 to 9.5.

Preferably, in the step A of the above-mentioned battery-grade vanadium oxide production method, the mixed solution of ammonium carbonate, ammonia water and ammonium sulfate is: ammonium carbonate 18-66 g/L, ammonium sulfate 27-220 g/L, pH 7.5-9.5. .

Preferably, in the step A of the above-mentioned production method of the battery-grade vanadium oxide, the ammonium carbonate is replaced by ammonium hydrogencarbonate, sodium carbonate or sodium hydrogencarbonate; and the ammonium sulfate is replaced by ammonium carbonate or ammonium hydrogencarbonate.

Preferably, in the step B of the above-mentioned production method of the battery-grade vanadium oxide, the hot water temperature is 60 to 100 °C.

Further, in the step B of the above-mentioned battery-grade vanadium oxide production method, the hot water temperature is 80 to 100 °C.

Preferably, in the step B of the above-mentioned battery-grade vanadium oxide production method, the hot water volume is 1/4 to 1 of the volume of the vanadium-containing leaching solution.

Further, in the step B of the above-mentioned production method of the battery-grade vanadium oxide, the hot water volume is 1/3 to 1/2 of the volume of the vanadium-containing leaching liquid.

Preferably, in the step C of the above-mentioned battery-grade vanadium oxide production method, the pH of the purified vanadium-containing leaching solution is adjusted with sulfuric acid.

Preferably, in the step C of the above-mentioned battery-grade vanadium oxide production method, the molar ratio of the ammonium in the ammonium sulfate solution to the vanadium in the purified vanadium-containing leaching solution is 1.0 to 4.0.

The method of the invention directly produces high-purity vanadium oxide products from the calcification roasting-sulfuric acid leaching liquid, and has the advantages of simple operation, short process, low cost, less waste water, and easy to ensure that the high-purity vanadium oxide product meets the requirements of the battery-grade raw material. Recycling treatment, high vanadium yield and other advantages. The method of the invention utilizes a vanadium-containing leaching solution to be added to a mixture of ammonium carbonate, ammonia water and ammonium sulfate to skillfully form impurity ions in the vanadium-containing solution to form a water-insoluble precipitate, and vanadium forms a water-soluble AMV. A step is taken to deeply separate the V and impurity elements. All the components of the wastewater of the method of the invention meet the requirements of the leaching process of returning calcification roasting clinker, and realize the low-cost recycling of the wastewater, and are particularly suitable for the vanadium extraction enterprise using the "vanadium slag calcification roasting-sulfuric acid leaching" process.

detailed description

The inventors of the present invention have found through intensive research that the existing high-purity vanadium oxide production processes are mostly further purified based on the vanadium-containing sodium extraction vanadium extraction process and the vanadium-containing vanadium intermediate process. Although a small number of enterprises have the ability to produce battery-grade high-purity vanadium oxide, the production process has many problems of vanadium-dissolving-depleting, and a large amount of sodium-containing wastewater is generated in the process. High, in order to reduce the content of Na and Cr in the product to below 0.008%, it takes a great price. At the same time, when removing Si and Al elements in the system, the corresponding precipitates of silicate and aluminate are formed and filtered. Washing is very difficult and will greatly increase the filtration time.

Therefore, in order to solve the problem of long process and high cost in the production process of battery-grade high-purity vanadium oxide, the vanadium oxide oxide can be directly prepared from the vanadium slag calcification roasting-sulfuric acid leaching solution, thereby avoiding the removal of Na and Cr, etc., or the V property. The puzzle of the elements.

Furthermore, the inventors of the present invention have further intensively studied that a method of "one separation, two purification, three cycles" can be used to directly produce a battery-grade high-purity vanadium oxide product from a calcification roasting-sulfuric acid leaching solution. : Vanadium slag calcification roasting - The main impurity elements in the sulphuric acid leaching solution are cations such as Mn and Mg. The Si, P, Fe plasma content is relatively low, and the difference between the cation and the vanadate anion is used to make V and other in the "one separation" step. Separation of impurity elements, the main method is: adding vanadium-containing leaching solution to a mixture of ammonium carbonate, ammonia water and ammonium sulfate, so that Mn, Mg, Si, P, Fe form MnCO ₃ + Mn(OH) ₂ , MgCO ₃ + Mg(OH) ₂ , silicate, FePO ₄ , Fe(OH) ₃ and other water-insoluble precipitates, while V combines with NH ₄ ⁺ to form a precipitate of AMV that is easily soluble in hot water, and further achieves V by hot water washing. Separation from other impurity elements; in the "two purification" step, the method of adding purified vanadium solution to the >90 ° C, analysis of pure ammonium sulfate solution, so that V, NH ₄ ⁺ combined with other trace impurities to form APV precipitate, Further To the purpose of purification of battery-grade high-purity vanadium oxide; in the "three-cycle" step, P<0.01g/L and Mn<5g/L in the wastewater for producing high-purity vanadium oxide can be directly returned to the leaching cycle. Therefore, the problem of long process and high cost in the current battery-grade high-purity vanadium oxide production process is solved.

Thus, the present invention provides a method of producing a battery-grade vanadium oxide, wherein the method comprises the steps of:

A) adding the calcified calcined vanadium-containing leaching solution to a mixed solution of ammonium carbonate, ammonia water and ammonium sulfate, stirring and precipitating, and liquid-solid separation to obtain a crude vanadium-containing product;

B) washing the crude vanadium-containing precipitate obtained by the step A washing with hot water to obtain a purified vanadium-containing leaching solution;

C) adjusting the pH of the purified vanadium-containing leaching solution obtained in step B to 1.5 to 2.5, and slowly adding it to an ammonium sulfate solution of >90 ° C, analytically pure and having a pH of 1.5 to 2.5 to ensure that the temperature of the system is not lowered. Stirring precipitation, liquid-solid separation to obtain high purity APV;

D) The high-purity APV product obtained in the step C is washed, dried, and calcined to obtain a battery-grade vanadium pentoxide product.

The invention can recycle all the wastewater generated in the whole process as a mother liquor back to the calcification roasting clinker sulfuric acid leaching cycle.

The method for producing a battery-grade vanadium oxide according to the above, wherein the vanadium-containing leaching solution is obtained by calcification of vanadium slag by calcination-sulfuric acid, the pH is 2.5-4.0, and the main components are: TV 20-60 g/L, SO ₄ ^2- 40 ～120g/L, Mn 8～24g/L, Mg 1-6g/L, Si 0.2～1.2g/L, P 0.01～0.06g/L, Fe<0.05g/L.

In the step A, the mixed solution of ammonium carbonate, ammonia water and ammonium sulfate functions as: ammonium carbonate provides carbonate ions, ammonium sulfate provides ammonium ions, and ammonia water adjusts pH. In the ratiometric reaction with the calcification roasting vanadium-containing leaching solution, the carbonate reacts with the manganese ions and magnesium ions in the vanadium-containing leaching solution, and the ammonium ions react with the vanadium ions in the vanadium-containing leaching solution, so the carbonate ions and the ammonium ions It should be sufficient. Further, in order to ensure sufficient quantity and no waste, the ratio of CO ₃ ^2- /Mn+Mg=1.0-1.5, NH ₄ ⁺ /V=2.0-4.0, and the pH of the mixed system should be 7.5-9.5. Further, the mixed solution of ammonium carbonate, ammonia water and ammonium sulfate is: ammonium carbonate 18-66 g/L, ammonium sulfate 27-220 g/L, and pH 7.5-9.5.

In step B, the hot water temperature is 60 to 100 °C. Further, the steam temperature in the step B is preferably 80 to 100 °C.

In step B, the hot water volume is 1/4 to 1 of the volume of the vanadium containing leachate. Further, the hot water volume is 1/3 to 1/2 of the volume of the vanadium-containing leaching solution.

In step C, the pH is adjusted with sulfuric acid.

In step C, the main purpose is to combine the ammonium ion in the vanadate and ammonium sulfate solution in the purified leachate under high temperature conditions (required above 90 ° C, generally controlled in boiling state) to form ammonium polyvanadate precipitate (APV). ). The reason why the vanadium solution is added to the boiling ammonium sulfate solution instead of the ammonium sulfate added to the vanadium solution is that the ammonium sulfate solution is prepared from pure water, has a small amount of impurities, and has a high ammonium concentration. If the vanadium concentration is purified, the vanadium is purified. After the liquid is added to the ammonium sulfate solution, the vanadium can be combined with the ammonium to form a precipitate in preference to the impurities. Further, in order to ensure a sufficient amount and not waste, the molar ratio of NH ₄ ⁺ /V is 1.0 to 4.0 in terms of molar ratio.

Example 1

1 L calcification calcination-sulfuric acid leaching solution (TV 45.38 g/L, Mn 15.21 g/L, Mg 3.77 g/L, Si 0.63 g/L, P 0.02 g/L, Fe 0.04 g/L) was added to a pH of 0.5 L. =9.3, (NH ₄ ) ₂ CO ₃ 82.22g / L, (NH ₄ ) ₂ SO ₄ 178.38g / L mixed solution, stirred and precipitated for 10min, after liquid-solid separation, the crude vanadium-containing precipitate was obtained.

The crude vanadium-containing precipitate was washed with 500 ml of purified water at 80 ° C to obtain 491 mL of purified vanadium solution (TV 86.22 g/L, Mn < 0.10 g/L, Mg 0.15 g/L, Si < 0.10 g/L, P< 0.01 g / L, Fe <0.01 g / L).

The purified vanadium solution was adjusted to pH 1.95 with analytically pure sulfuric acid, and slowly added to a solution of 200 mL, 96 ° C, pH=1.77, (NH ₄ ) ₂ SO ₄ 493.08 g / L, and precipitated for 20 min, after liquid-solid separation. Use high purity APV.

After washing high-purity APV with 1L of pure water, it is dried and calcined to obtain 73.32g of battery-grade high-purity vanadium pentoxide product, of which V ₂ O ₅ 99.95%, P, Al, As, Ca, Cr, Fe, Mn, Si is less than 0.01% and vanadium recovery is 90.51%.

Example 2

1 L calcification calcination-sulfuric acid leaching solution (TV 56.28 g/L, Mn 18.33 g/L, Mg 4.12 g/L, Si 0.86 g/L, P 0.03 g/L, Fe 0.06 g/L) was added to a pH of 0.5 L. =9.0, (NH ₄ ) ₂ CO ₃ 95.74g / L, (NH ₄ ) ₂ SO ₄ 196.38g / L mixed solution, stirred and precipitated for 10min, after liquid-solid separation, the crude vanadium-containing precipitate was obtained.

The crude vanadium-containing precipitate was washed with 600 ml of pure water at 80 ° C to obtain 597 mL of purified vanadium solution (TV 89.11 g/L, Mn<0.10 g/L, Mg 0.18 g/L, Si<0.10 g/L, P< 0.01 g / L, Fe <0.01 g / L).

The purified vanadium solution was adjusted to pH 2.05 with analytically pure sulfuric acid, and slowly added to 300 mL, 96 ° C, pH = 1.82, (NH ₄ ) ₂ SO ₄ 458.97 g / L solution, precipitated for 20 min, after liquid-solid separation Use high purity APV.

After washing high-purity APV with 1L of pure water, it is dried and calcined to obtain 92.13g of battery-grade high-purity vanadium pentoxide product, of which V ₂ O ₅ 99.96%, P, Al, As, Ca, Cr, Fe, Mn, The Si was less than 0.01%, and the vanadium recovery was 91.71%.

Example 3

1 L calcification calcination-sulfuric acid leaching solution (TV 45.38 g/L, Mn 15.21 g/L, Mg 3.77 g/L, Si 0.63 g/L, P 0.02 g/L, Fe 0.04 g/L) was added to a pH of 0.4 L. =9.3, (NH ₄ ) ₂ CO ₃ 94.21g / L, (NH ₄ ) ₂ SO ₄ 155.46g / L mixed solution, stirred and precipitated for 10min, after liquid-solid separation, the crude vanadium-containing precipitate was obtained.

The crude vanadium-containing precipitate was washed with 600 ml of pure water at 80 ° C to obtain 589 mL of purified vanadium solution (TV 71.85 g/L, Mn < 0.10 g/L, Mg 0.22 g/L, Si < 0.10 g/L, P< 0.01 g / L, Fe <0.01 g / L).

The purified vanadium solution was adjusted to pH 2.12 with analytically pure sulfuric acid, and slowly added to 200 mL, 96 ° C, pH = 1.82, (NH 4 ) ₂ SO ₄ 492.91 g / L in a pure aqueous solution, precipitated for 20 min, after liquid-solid separation Use high purity APV. After washing high-purity APV with 1L of pure water, it is dried and calcined to obtain 73.29g of battery-grade high-purity vanadium pentoxide product, of which V ₂ O ₅ 99.95%, P, Al, As, Ca, Cr, Fe, Mn, Si is less than 0.01% and vanadium recovery is 90.48%.

Claims

A method for producing a battery-grade vanadium oxide, comprising the steps of:

A, the calcification roasting vanadium-containing leaching solution is added to a mixed solution of ammonium carbonate, ammonia water and ammonium sulfate, and the precipitate is stirred and precipitated, and the liquid-solid separation is carried out to obtain a crude vanadium-containing product;

B. Washing the crude vanadium containing product with hot water to obtain a purified vanadium-containing leaching solution;

C. Adjust the pH of the purified vanadium-containing leaching solution to 1.5-2.5, add to the ammonium sulfate solution with a pH of 1.5-2.5 and a temperature of 90 ° C to boiling, and keep the temperature stirring, precipitation, solid-liquid separation to obtain high purity. APV, the APV is washed, dried and calcined to obtain battery-grade vanadium pentoxide.
The method for producing a battery-grade vanadium oxide according to claim 1, wherein in the step A, the vanadium-containing leaching solution is obtained by acid leaching of vanadium slag by calcination, and the pH is 2.5 to 4.0, and the main component is TV 20. ～60g/L, SO 4 2- 40～120g/L, Mn 8～24g/L, Mg 1-6g/L, Si 0.2～1.2g/L, P 0.01～0.06g/L, Fe<0.05g/ L.
The method for producing a battery-grade vanadium oxide according to claim 1, wherein in the step A, the ratio of the mixed solution of the ammonium carbonate, the ammonia water and the ammonium sulfate to the vanadium-containing leaching solution is: a molar ratio, CO 3 2- /Mn+Mg=1.0-1.5, NH 4 + /V=2.0-4.0, and the pH of the mixing system of the mixed solution and the vanadium-containing leaching solution is controlled to be 7.5-9.5.
The method for producing a battery-grade vanadium oxide according to claim 1, wherein in the step A, the mixed solution of ammonium carbonate, ammonia water and ammonium sulfate is: ammonium carbonate 18-66 g/L, ammonium sulfate 27-220 g. /L, pH is 7.5 to 9.5.
The method for producing a battery-grade vanadium oxide according to claim 1, wherein in the step A, the ammonium carbonate is replaced with ammonium hydrogencarbonate, sodium carbonate or sodium hydrogencarbonate; and the ammonium sulfate is ammonium carbonate or Ammonium bicarbonate replacement.
The method for producing a battery-grade vanadium oxide according to claim 1, wherein in the step B, the hot water temperature is 60 to 100 ° C; and further, the hot water temperature is 80 to 100 ° C.
The method for producing a battery-grade vanadium oxide according to claim 1, wherein in the step B, the hot water volume is 1/4 to 1 of the volume of the vanadium-containing leaching solution; further, the hot water volume is The volume of vanadium leaching solution is 1/3 to 1/2.
The method for producing a battery-grade vanadium oxide according to claim 1, wherein in step C, the pH of the purified vanadium-containing leaching solution is adjusted with sulfuric acid.
The method for producing a battery-grade vanadium oxide according to claim 1, wherein in the step C, the molar ratio of the ammonium in the ammonium sulfate solution to the vanadium in the purified vanadium-containing leaching solution is 1.0 to 4.0.