Method for efficiently extracting vanadium from vanadium slag

Abstract

The invention discloses a method for efficiently extracting vanadium from vanadium slag, which comprises the following steps: mixing the vanadium slag with an oxalate additive, roasting, treating roasted clinker with water or acid to obtain a vanadium ion-containing solution and primary residues, and treating the vanadium ion-containing solution to obtain a vanadium product with high vanadium content. The method can efficiently and quickly realize separation and purification of vanadium in the vanadium slag, simplifies the existing vanadium extraction process, improves the vanadium extraction rate, reduces the temperature and time required for roasting the vanadium slag, solves the problems of low vanadium extraction rate, high energy consumption, complex process and the like in the traditional vanadium extraction process of the vanadium slag, is free of harmful waste discharge, simple in process, energy-saving and environment-friendly, and is suitable for industrial production. The method is high in operability and has a wide application prospect.

Description

Technical Field

[0001] The invention belongs to the fields of chemical industry, energy and metallurgy, and particularly relates to a method for efficiently extracting vanadium from vanadium slag. Background Art

[0002] Vanadium is a high melting point, rare and refractory metal that exhibits a wide range of uses in different industries such as steel production, chemicals, aerospace and batteries. Given the key role of vanadium in multiple fields, vanadium has acquired the status of a "critical metal". In the steel industry, trace amounts of vanadium can significantly improve the strength, wear resistance and explosion resistance of steel, making it an indispensable alloying component. In recent years, driven by the evolution of new energy policies, the importance of vanadium in the energy storage industry has been amplified. All-vanadium liquid flow batteries have significant advantages, including high energy efficiency, safety, environmental protection and long cycle life, making them an environmentally conscious intermittent energy storage solution. In the vanadium smelting process, the key steps include roasting of vanadium slag, leaching of vanadium and precipitation of vanadium. The roasting process involves phase changes of elements such as vanadium, iron, calcium, manganese and magnesium. The traditional roasting process converts vanadium spinel phase into easily soluble vanadate, but the vanadium recovery rate is low. The vanadium recovery rate of a single roasting is low (about 70%), and the vanadium recovery rate after multiple roastings is only 85%. The roasting temperature is high (850-950℃), and multiple roastings are required, the energy consumption is high, and harmful HCl and Cl are generated during the roasting process. 2 , and other corrosive gases, polluting the environment. Summary of the invention

[0003] The purpose of the present invention is to provide a method for efficiently extracting vanadium from vanadium slag in view of the above-mentioned deficiencies in the prior art. The method adopts a single roasting and a single leaching method to efficiently and quickly separate and purify vanadium from vanadium slag, simplify the existing vanadium extraction process, improve the vanadium extraction rate, reduce the temperature and time required for vanadium slag roasting, and solve the problems of low vanadium extraction rate, high energy consumption, and complex process in the traditional vanadium slag vanadium extraction process. There is no emission of harmful waste, the process is simple, energy-saving and environmentally friendly, and the operability is strong, which has broad application prospects.

[0004] In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is: A method for efficiently extracting vanadium from vanadium slag is provided, comprising the following steps: S1. Mixing vanadium slag of a certain particle size and oxalate additive of a certain particle size in a certain mass ratio, and roasting at a certain temperature for a certain time to obtain vanadium slag oxalate roasted clinker; S2, leaching the vanadium slag oxalate roasted clinker with water or acid of a certain concentration under certain conditions, and obtaining a solution containing vanadium ions and a primary residue after solid-liquid separation; S3, treating the solution containing vanadium ions to obtain a vanadium-containing product.

[0005] Furthermore, the method for efficiently extracting vanadium from vanadium slag described in step S1 is characterized in that: in step S1, the certain mass ratio refers to the mass ratio of vanadium slag to oxalate additive is 10:(0.1-5).

[0006] Furthermore, the method for efficiently extracting vanadium from vanadium slag described in step S1 is characterized in that: in step S1, the certain temperature refers to 200-800°C.

[0007] Furthermore, the method for efficiently extracting vanadium from vanadium slag described in step S1 is characterized in that: in step S1, the certain time mentioned is 10 to 180 minutes.

[0008] Furthermore, the method for efficiently extracting vanadium from vanadium slag described in step S1 is characterized in that: in step S2, the certain acid refers to at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and the like, and the concentration of the acid solution is 0 to 10 mol / L.

[0009] Furthermore, the method for efficiently extracting vanadium from vanadium slag described in step S1 is characterized in that: in step S2, the certain conditions refer to a leaching temperature of 10 to 90° C., a leaching time of 0 to 180 minutes, and a leaching liquid-to-solid ratio of 1 to 20 mL / g.

[0010] Furthermore, the method for efficiently extracting vanadium from vanadium slag described in step S1 is characterized in that: in step S1, the vanadium slag of a certain particle size refers to the vanadium slag particle size not exceeding 0.3 mm, and the oxalate additive of a certain particle size refers to the oxalate additive particle size not exceeding 0.50 mm.

[0011] Furthermore, the method for efficiently extracting vanadium from vanadium slag described in step S1 is characterized in that: in step S3, the solution treatment includes chemical unit operations such as precipitation, extraction, adsorption, and calcination.

[0012] Furthermore, the method for efficiently extracting vanadium from vanadium slag described in step S1 is characterized in that: in step S1, the oxalate additive in the oxalate additive is at least one of oxalates such as sodium oxalate, oxalic acid, calcium oxalate, potassium oxalate, and ammonium oxalate.

[0013] Furthermore, the method for efficiently extracting vanadium from vanadium slag in step S1 is characterized in that: in step S1, the main components of the vanadium slag are: V 2 0 5 9.9%~25%, Si0 2 12~22%, Fe 2 O 3 25~43%, MnO 4%~7%, MgO 1%~3%, Ca0 5%~11%.

[0014] The beneficial effects of the present invention are: The present invention adopts a single co-roasting of vanadium slag and oxalate additive to obtain roasted clinker, wherein the vanadium exists in the form of easily soluble vanadic acid, and water leaching or acid leaching can be used to simply and efficiently extract vanadium from the vanadium slag, and further precipitation of vanadium ions can obtain vanadium pentoxide. The existing vanadium extraction process is simplified, the vanadium extraction rate is improved, the temperature required for vanadium slag roasting is reduced, and the problem of the complex vanadium extraction process of the traditional vanadium slag is solved, which is of great significance for vanadium extraction from vanadium slag. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the description of the embodiments of the present application will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0016] Figure 1 A schematic flow chart of a method for efficiently extracting vanadium by co-roasting vanadium slag and oxalate provided by the present invention. DETAILED DESCRIPTION

[0017] The specific implementation modes of the present invention are described below so that those skilled in the art can understand the present invention. However, it should be clear that the present invention is not limited to the scope of the specific implementation modes. For those of ordinary skill in the art, as long as various changes are within the spirit and scope of the present invention as defined and determined by the attached claims, these changes are obvious, and all inventions and creations utilizing the concept of the present invention are protected.

[0018] A method for efficiently extracting vanadium from vanadium slag is provided, comprising the following steps: S1. Mixing vanadium slag of a certain particle size and oxalate additive of a certain particle size in a certain mass ratio, and roasting at a certain temperature for a certain time to obtain vanadium slag oxalate roasted clinker; S2, leaching the vanadium slag oxalate roasted clinker with water or acid of a certain concentration under certain conditions, and obtaining a solution containing vanadium ions and a primary residue after solid-liquid separation; S3, treating the solution containing vanadium ions to obtain a vanadium-containing product.

[0019] Furthermore, the method for efficiently extracting vanadium from vanadium slag described in step S1 is characterized in that: in step S1, the certain mass ratio refers to the mass ratio of vanadium slag to oxalate additive is 10:(0.1-5).

[0020] Furthermore, the method for efficiently extracting vanadium from vanadium slag described in step S1 is characterized in that: in step S1, the certain temperature refers to 200-800°C.

[0021] Furthermore, the method for efficiently extracting vanadium from vanadium slag described in step S1 is characterized in that: in step S1, the certain time mentioned is 10 to 180 minutes.

[0022] Furthermore, the method for efficiently extracting vanadium from vanadium slag described in step S1 is characterized in that: in step S2, the certain acid refers to at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and the like, and the concentration of the acid solution is 0 to 10 mol / L.

[0023] Furthermore, the method for efficiently extracting vanadium from vanadium slag described in step S1 is characterized in that: in step S2, the certain conditions refer to a leaching temperature of 10 to 90° C., a leaching time of 0 to 180 minutes, and a leaching liquid-to-solid ratio of 1 to 20 mL / g.

[0024] Furthermore, the method for efficiently extracting vanadium from vanadium slag described in step S1 is characterized in that: in step S1, the vanadium slag of a certain particle size refers to the vanadium slag particle size not exceeding 0.3 mm, and the oxalate additive of a certain particle size refers to the oxalate additive particle size not exceeding 0.50 mm.

[0025] Furthermore, the method for efficiently extracting vanadium from vanadium slag described in step S1 is characterized in that: in step S3, the solution treatment includes chemical unit operations such as precipitation, extraction, adsorption, and calcination.

[0026] Furthermore, the method for efficiently extracting vanadium from vanadium slag described in step S1 is characterized in that: in step S1, the oxalate additive in the oxalate additive is at least one of oxalates such as sodium oxalate, oxalic acid, calcium oxalate, potassium oxalate, and ammonium oxalate.

[0027] Furthermore, the method for efficiently extracting vanadium from vanadium slag in step S1 is characterized in that: in step S1, the main components of the vanadium slag are: V 2 0 5 9.9%~25%, Si0 2 12~22%, Fe 2 O 3 25~43%, MnO 4%~7%, MgO 1%~3%, Ca0 5%~11%.

[0028] The above contents of the present invention are further described in detail below through specific implementation modes in the form of embodiments, but the present invention is not limited thereto. Example

[0029] Take 100g of vanadium slag powder, weigh 30g of sodium oxalate according to the mass ratio of vanadium slag to sodium oxalate of 1:0.3, mix them evenly and heat them to 800℃ in a muffle furnace at 5℃ / min, roast for 120min, cool to room temperature to get clinker, grind the clinker to 100-120 mesh. Take 20g of clinker, add oxalic acid solution as leaching agent at a liquid-solid ratio of 20:1, the concentration is 0.1mol / L, stir and leach at 60℃ for 60min, filter, and get the primary leaching vanadium leachate and tailings. From vanadium slag powder to tailings, the comprehensive leaching rate of vanadium is 95.3%. The vanadium leachate is heated at boiling for 60min with an ammonium addition coefficient (mass ratio of ammonium oxalate to vanadium content) of 2.5 and pH=1.8 to precipitate vanadium, and obtain ammonium polyvanadate and vanadium precipitation wastewater. After evaporation of the wastewater, sodium oxalate is obtained, which can be recycled for roasting. The vanadium precipitation rate is 97.3%, and the ammonium polyvanadate is calcined at 500℃ for 120min to obtain vanadium pentoxide product. From vanadium slag powder to vanadium pentoxide product, the vanadium yield is 92.7%. Example

[0030] Take 100g of vanadium slag powder, weigh 30g of potassium oxalate according to the mass ratio of vanadium slag to potassium oxalate of 1:0.3, mix them evenly and heat to 800℃ in a muffle furnace at 5℃ / min, roast for 120min, cool to room temperature to get clinker, grind the clinker to 100-120 mesh. Take 20g of clinker, add leaching agent hydrochloric acid solution with a liquid-solid ratio of 20:1, and the concentration is 0.01mol / L. Stir and leach for 60min at 20℃, filter, and obtain a primary leaching vanadium leachate and tailings. From vanadium slag powder to tailings, the comprehensive leaching rate of vanadium is 95.2%. The vanadium leachate is heated at boiling for 60min with an ammonium addition coefficient (mass ratio of ammonium oxalate to vanadium content) of 2.5 and pH=1.8 to precipitate vanadium, obtain polyvanadate and vanadium precipitation wastewater, and potassium oxalate is obtained after the wastewater is evaporated, which can be recycled for roasting. The vanadium precipitation rate is 98.5%, and the ammonium polyvanadate is calcined at 500℃ for 120min to obtain vanadium pentoxide product. From vanadium slag powder to vanadium pentoxide product, the vanadium yield is 93.9%. Example

[0031] Take 100g of vanadium slag powder, weigh 40g of sodium oxalate according to the mass ratio of vanadium slag to sodium oxalate of 1:0.4, mix them evenly and heat to 800℃ in a muffle furnace at 5℃ / min, roast for 120min, cool to room temperature to get clinker, grind the clinker to 100-120 mesh. Take 20g of clinker, add sulfuric acid solution as leaching agent at a liquid-solid ratio of 20:1, the concentration is 0.01mol / L, stir and leach for 60min at 30℃, filter, and get the primary leaching vanadium leachate and tailings. From vanadium slag powder to tailings, the comprehensive leaching rate of vanadium is 96.3%. The vanadium leachate is heated at boiling for 60min with an ammonium addition coefficient (mass ratio of ammonium oxalate to vanadium content) of 2.5 and pH=1.8 to precipitate vanadium, and obtain ammonium polyvanadate and vanadium precipitation wastewater. Sodium oxalate is obtained after evaporation of the wastewater, which can be recycled for roasting. The vanadium precipitation rate is 97.5%, and the ammonium polyvanadate is calcined at 500℃ for 120min to obtain vanadium pentoxide product. From vanadium slag powder to vanadium pentoxide product, the vanadium yield is 93.9%. Example

[0032] Take 100g of vanadium slag powder, weigh 40g of potassium oxalate according to the mass ratio of vanadium slag to potassium oxalate of 1:0.4, mix them evenly and heat to 800℃ in a muffle furnace at 5℃ / min, roast for 120min, cool to room temperature to get clinker, grind the clinker to 100-120 mesh. Take 20g of clinker, add leaching agent phosphoric acid solution at a liquid-solid ratio of 20:1, the concentration is 0.01mol / L, stir and leach for 60min at 40℃, filter, and get the primary leaching vanadium leachate and tailings. From vanadium slag powder to tailings, the comprehensive leaching rate of vanadium is 96.3%. The vanadium leachate is heated at boiling for 60min with an ammonium addition coefficient (mass ratio of ammonium oxalate to vanadium content) of 2.5 and pH=1.8 to precipitate vanadium, obtain ammonium polyvanadate and vanadium precipitation wastewater, and potassium oxalate is obtained after the wastewater is evaporated, which can be recycled for roasting. The vanadium precipitation rate is 96.7%, and the ammonium polyvanadate is calcined at 500℃ for 120min to obtain vanadium pentoxide product. From vanadium slag powder to vanadium pentoxide product, the vanadium yield is 93.1%. Example

[0033] Take 100g of vanadium slag powder, weigh 50g of sodium oxalate according to the mass ratio of vanadium slag to sodium oxalate of 1:0.5, mix them evenly and heat to 800℃ in a muffle furnace at 5℃ / min, roast for 120min, cool to room temperature to get clinker, grind the clinker to 100-120 mesh. Take 20g of clinker, add leaching agent nitric acid solution with a liquid-solid ratio of 20:1, and the concentration is 0.01mol / L. Stir and leach for 60min at 50℃, filter, and get the primary leaching vanadium leachate and tailings. From vanadium slag powder to tailings, the comprehensive leaching rate of vanadium is 99.3%. The vanadium leachate is heated at boiling for 60min with an ammonium addition coefficient (mass ratio of ammonium oxalate to vanadium content) of 2.5 and pH=1.8 to precipitate vanadium, and obtain polyvanadate and vanadium precipitation wastewater. After evaporation of the wastewater, sodium oxalate is obtained, which can be recycled for roasting. The vanadium precipitation rate is 97.8%, and the ammonium polyvanadate is calcined at 500℃ for 120min to obtain vanadium pentoxide product. From vanadium slag powder to vanadium pentoxide product, the vanadium yield is 97.1%. Example

[0034] Take 100 grams of vanadium slag powder, weigh 50 grams of potassium oxalate according to the mass ratio of vanadium slag to potassium oxalate of 1:0.5, mix them evenly and heat them to 800℃ in a muffle furnace at 5℃ / min, roast for 120min, cool to room temperature to obtain clinker, and grind the clinker to 100-120 mesh. Take 20 grams of clinker, add leaching agent water at a liquid-solid ratio of 20:1, stir and leach for 60min at 10℃, filter, and obtain a single leaching vanadium leachate and tailings. From vanadium slag powder to tailings, the comprehensive leaching rate of vanadium is 96.5%. The vanadium leachate is heated at boiling for 60min with an ammonium addition coefficient (mass ratio of ammonium oxalate to vanadium content) of 2.5 and pH=1.8 to precipitate vanadium, obtain ammonium polyvanadate and vanadium precipitation wastewater, and obtain potassium oxalate after evaporation of the wastewater, which can be recycled for roasting. The vanadium precipitation rate is 97.6%, and ammonium polyvanadate is calcined at 500℃ for 120min to obtain vanadium pentoxide product. From vanadium slag concentrate to vanadium pentoxide product, the vanadium recovery rate is 97.3%.

Claims

1. A method for efficiently extracting vanadium from vanadium slag, characterized in that: The following steps are involved: S1. Mixing vanadium slag of a certain particle size and oxalate additive of a certain particle size in a certain mass ratio, and roasting at a certain temperature for a certain time to obtain vanadium slag oxalate roasted clinker; S2, leaching the vanadium slag oxalate roasted clinker with water or acid of a certain concentration under certain conditions, and obtaining a solution containing vanadium ions and a primary residue after solid-liquid separation; S3, treating the solution containing vanadium ions to obtain a vanadium-containing product.

2. The method for efficiently extracting vanadium from vanadium slag according to claim 1, characterized in that: In step S1, the certain mass ratio refers to the mass ratio of vanadium slag to oxalate additive being 10:(0.1-5).

3. The method for efficiently extracting vanadium from vanadium slag according to claim 1, characterized in that: In step S1, the certain temperature is 200-800°C.

4. The method for efficiently extracting vanadium from vanadium slag according to claim 1, characterized in that: In step S1, the certain time is 10 to 180 minutes.

5. The method for efficiently extracting vanadium from vanadium slag according to claim 1, characterized in that: In step S2, the certain acid refers to at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and the like, and the concentration of the acid solution is 0 to 10 mol / L.

6. The method for efficiently extracting vanadium from vanadium slag according to claim 1, characterized in that: In step S2, the certain conditions refer to a leaching temperature of 10 to 90°C, a leaching time of 0 to 180 minutes, and a leaching liquid-to-solid ratio of 1 to 20 mL / g.

7. The method for efficiently extracting vanadium from vanadium slag according to claim 1, characterized in that: In step S1, the vanadium slag of a certain particle size refers to the vanadium slag having a particle size not exceeding 0.3 mm, and the oxalate additive of a certain particle size refers to the oxalate additive having a particle size not exceeding 0.50 mm.

8. The method for efficiently extracting vanadium from vanadium slag according to claim 1, characterized in that: In step S3, the solution treatment includes chemical unit operations such as precipitation, extraction, adsorption, and calcination.

9. The method for efficiently extracting vanadium from vanadium slag according to claim 1, characterized in that: In step S1, the oxalate additive in the oxalate additive is at least one of oxalates such as sodium oxalate, oxalic acid, calcium oxalate, potassium oxalate, and ammonium oxalate.

10. The method for efficiently extracting vanadium from vanadium slag according to claim 1, characterized in that: In step S1, the main components of the vanadium slag are: V2O5 9.9%-25%, SiO2 12-22%, Fe2O3 25-43%, MnO 4%-7%, MgO 1%-3%, and CaO5%-11%.

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