Low-cost green vanadium extraction method

Abstract

The invention discloses a low-cost green vanadium extraction method, and relates to green, zero-carbon and efficient vanadium extraction from vanadium slag, which is realized by the following steps: mixing the vanadium slag with a blast furnace ferronickel slag additive, roasting, treating the roasted clinker with 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. According to the method, waste is treated with waste, vanadium in the vanadium slag can be separated and purified in a green, zero-carbon and efficient mode, the existing vanadium extraction technology is simplified, the vanadium extraction rate is increased, the cost needed by vanadium slag roasting is reduced, and the problems that in the traditional vanadium slag vanadium extraction process, carbon emission is high, the vanadium extraction rate is low, energy consumption is high, the technology is complex, and cost is high are solved; the whole process is free of emission of harmful waste, carbon dioxide and the like, and the method is simple in process, energy-saving, environment-friendly, high in operability and wide in application prospect.

Description

Technical Field

[0001] This invention belongs to the fields of energy, resources, environmental protection and metallurgy, and specifically relates to a green, zero-carbon and efficient method for extracting vanadium from vanadium slag. Background Technology

[0002] Vanadium is a strategically important metal in emerging energy technologies, widely used in the manufacture of hypersonic aircraft, missiles, superconductors, nuclear reactors, special steels, and energy storage materials. With the advancement of energy storage policies, the demand for vanadium has surged, particularly driven by the deployment of all-vanadium redox flow batteries. Currently, the global vanadium supply mainly comes from vanadium-titanium magnetite ore. Vanadium slag, a byproduct of steelmaking, is subsequently the primary raw material for vanadium extraction. Traditional vanadium smelting processes include roasting, leaching, and precipitation of vanadium slag. Roasting is a crucial step in the entire process, involving the oxidation and phase transformation of vanadium. A typical roasting process oxidizes vanadium spinel into easily soluble vanadates. Depending on the roasting additives, the roasting products include sodium vanadate, calcium vanadate, magnesium vanadate, and manganese vanadate, all readily soluble in water or acids and alkalis. Current problems include: low vanadium recovery rate; high roasting temperature and the need for multiple roasting processes; high energy consumption; harmful acidic corrosive gases such as SO2, SO3, HCl, and C12 are generated during the roasting process, polluting the environment; the biggest problem is carbon emissions, as sodium carbonate and calcium carbonate are commonly used additives. Summary of the Invention

[0003] The purpose of this invention is to address the aforementioned shortcomings of existing technologies by providing a green, zero-carbon, and highly efficient method for vanadium extraction from vanadium slag. Employing a single-stage roasting and leaching method, this invention achieves green and efficient separation and purification of vanadium from vanadium slag, simplifying existing vanadium extraction processes, increasing vanadium extraction rates, reducing the cost of vanadium slag roasting, and solving the problems of high carbon emissions, low vanadium extraction rates, high energy consumption, complex processes, and high costs in traditional vanadium slag extraction processes. The entire process generates no harmful waste or carbon dioxide emissions, is simple, energy-saving, environmentally friendly, highly operable, and has broad application prospects.

[0004] To achieve the above-mentioned objectives, the technical solution adopted by this invention is as follows: A green, zero-carbon, and highly efficient method for vanadium extraction from vanadium slag is provided, comprising the following steps: S1. Vanadium slag of a certain particle size and blast furnace nickel-iron slag additive of a certain particle size are mixed in a certain mass ratio and roasted at a certain temperature for a certain time to obtain vanadium slag blast furnace nickel-iron slag roasted clinker. S2. The vanadium slag blast furnace nickel-iron slag clinker is leached with acid of a certain concentration under certain conditions. After solid-liquid separation, a solution containing vanadium ions and primary residue are obtained. S3. Treat the solution containing vanadium ions to obtain a vanadium-containing product.

[0005] Furthermore, the low-cost green vanadium extraction method described in step S1 is characterized in that: in step S1, the certain mass ratio refers to the mass ratio of vanadium slag and blast furnace nickel-iron slag additives being 1:(0.1~1).

[0006] Furthermore, the low-cost green vanadium extraction method described in step S1 is characterized in that: in step S1, the certain temperature refers to 200-1000℃.

[0007] Furthermore, the low-cost green vanadium extraction method described in step S1 is characterized in that: in step S1, the certain time refers to 10 to 180 minutes.

[0008] Furthermore, the low-cost green vanadium extraction method described in step S1 is characterized in that: in step S2, the certain acid refers to at least one of the following acids: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, etc., and the concentration of the acid solution is 5-30%.

[0009] Furthermore, the low-cost green vanadium extraction method described in step S1 is characterized in that: in step S2, the certain conditions refer to a leaching temperature of 10-90℃, a leaching time of 0-180 minutes, and a leaching liquid-to-solid ratio of 1-20 mL / g.

[0010] Furthermore, the low-cost green vanadium extraction method described in step S1 is characterized in that: in step S1, the vanadium slag of a certain particle size refers to vanadium slag with a particle size not exceeding 1 mm, and the blast furnace nickel-iron slag additive of a certain particle size refers to the blast furnace nickel-iron slag additive with a particle size not exceeding 1 mm.

[0011] Furthermore, the low-cost, green vanadium extraction method 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. Furthermore, the low-cost green vanadium extraction method described in step S1 is characterized in that: in step S1, the main components of the vanadium slag are: V2O 55.3%~25.3%, SiO 29.6%~21.6%, Fe2O3 24.9%~46.5%, MnO 2.3%~6.6%, MgO 2.9%~3.5%, and CaO 1.3%~4.9%.

[0012] Further, in step S1, the blast furnace nickel-iron slag in the blast furnace nickel-iron slag additive is a type of blast furnace ironmaking waste slag, with the following main components: SiO2 23.5-35.6%, MgO 12.6%-19.5%, CaO 22.1%-35.6%, Al2O3 8.5-18.5%, Fe2O3 2.3-6.5%, and MnO 2.3%-6.6%.

[0013] The beneficial effects of this invention are as follows: This invention utilizes a single co-calcination process of vanadium slag and blast furnace nickel-iron slag additives to obtain roasted clinker. The vanadium in this clinker exists in the form of easily soluble vanadate, allowing for simple and efficient extraction from the vanadium slag using acid leaching. Further precipitation of vanadium ions yields vanadium pentoxide. This simplifies existing vanadium extraction processes, achieves zero carbon emissions during vanadium slag extraction, improves the vanadium extraction rate, reduces the temperature required for vanadium slag roasting, and solves the complexities of traditional vanadium slag extraction processes, thus possessing significant implications for vanadium slag extraction. Attached Figure Description

[0014] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the description of the embodiments of this application will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Figure 1 This is a schematic flowchart of a method for efficiently extracting vanadium from vanadium slag and blast furnace nickel-iron slag provided by the present invention. Detailed implementation method: The specific embodiments of the present invention are described below to enable those skilled in the art to understand the present invention. However, it should be understood that the present invention is not limited to the scope of the specific embodiments. For those skilled in the art, various changes are obvious as long as they are within the spirit and scope of the present invention as defined and determined by the appended claims. All inventions utilizing the concept of the present invention are protected.

[0015] A method for efficiently extracting vanadium from vanadium slag is provided, comprising the following steps: S1. Vanadium slag of a certain particle size and blast furnace nickel-iron slag additive of a certain particle size are mixed in a certain mass ratio and roasted at a certain temperature for a certain time to obtain vanadium slag blast furnace nickel-iron slag roasted clinker. S2. The vanadium slag blast furnace nickel-iron slag clinker is leached with acid of a certain concentration under certain conditions. After solid-liquid separation, a solution containing vanadium ions and primary residue are obtained. S3. Treat the solution containing vanadium ions to obtain a vanadium-containing product.

[0016] Furthermore, the low-cost green vanadium extraction method described in step S1 is characterized in that: in step S1, the certain mass ratio refers to the mass ratio of vanadium slag and blast furnace nickel-iron slag additives being 1:(0.1~1).

[0017] Furthermore, the low-cost green vanadium extraction method described in step S1 is characterized in that: in step S1, the certain temperature refers to 200-1000℃.

[0018] Furthermore, the low-cost green vanadium extraction method described in step S1 is characterized in that: in step S1, the certain time refers to 10 to 180 minutes.

[0019] Furthermore, the low-cost green vanadium extraction method described in step S1 is characterized in that: in step S2, the certain acid refers to at least one of the following acids: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, etc., and the concentration of the acid solution is 5-30%.

[0020] Furthermore, the low-cost green vanadium extraction method described in step S1 is characterized in that: in step S2, the certain conditions refer to a leaching temperature of 10-90℃, a leaching time of 0-180 minutes, and a leaching liquid-to-solid ratio of 1-20 mL / g.

[0021] Furthermore, the low-cost green vanadium extraction method described in step S1 is characterized in that: in step S1, the vanadium slag of a certain particle size refers to vanadium slag with a particle size not exceeding 1 mm, and the blast furnace nickel-iron slag additive of a certain particle size refers to the blast furnace nickel-iron slag additive with a particle size not exceeding 1 mm.

[0022] Furthermore, the low-cost, green vanadium extraction method 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. Furthermore, the low-cost green vanadium extraction method described in step S1 is characterized in that: in step S1, the main components of the vanadium slag are: V2O 55.3%~25.3%, SiO 29.6%~21.6%, Fe2O3 24.9%~46.5%, MnO 2.3%~6.6%, MgO 2.9%~3.5%, and CaO 1.3%~4.9%.

[0023] Further, in step S1, the blast furnace nickel-iron slag in the blast furnace nickel-iron slag additive is a type of blast furnace ironmaking waste slag, with the following main components: SiO2 23.5-35.6%, MgO 12.6%-19.5%, CaO 22.1%-35.6%, Al2O3 8.5-18.5%, Fe2O3 2.3-6.5%, and MnO 2.3%-6.6%.

[0024] The following detailed embodiments further illustrate the above-mentioned content of the present invention, but do not limit the present invention.

[0025] Example 1 Take 100g of vanadium slag concentrate, and weigh 10g of blast furnace nickel-iron slag according to a vanadium slag to blast furnace nickel-iron slag mass ratio of 1:0.1. Mix evenly and calcine in a muffle furnace at 4℃ / min to 800℃ for 120min. Cool to room temperature to obtain clinker, which is then ground to 80-140 mesh. Take 40g of clinker and add 10% sulfuric acid solution as a leaching agent at a liquid-to-solid ratio of 15:1. Leach at 60℃ with stirring for 60min, filter, and obtain primary vanadium leaching solution and tailings. The overall vanadium leaching rate from vanadium slag concentrate to tailings is 97.35%. The vanadium leaching solution is boiled at 60℃ for 60min with an ammonium addition coefficient (ammonium salt to vanadium content mass ratio) of 3 and pH=1.7 to precipitate vanadium, yielding ammonium polyvanadate and vanadium precipitation wastewater. The vanadium precipitation rate is 97.56%. The ammonium polyvanadate is calcined at 500℃ for 120min to obtain vanadium pentoxide product. From vanadium slag concentrate to vanadium pentoxide product, the vanadium yield is 92.35%.

[0026] Example 2 Take 100g of vanadium slag concentrate, and weigh 20g of blast furnace nickel-iron slag according to a vanadium slag to blast furnace nickel-iron slag mass ratio of 1:0.2. Mix them evenly and calcine them in a muffle furnace at 4℃ / min to 850℃ for 120min. Cool to room temperature to obtain clinker, which is then ground to 80-140 mesh. Take 40g of clinker and add 10% sulfuric acid solution as a leaching agent at a liquid-to-solid ratio of 15:1. Leach at 60℃ with stirring for 60min, filter, and obtain primary vanadium leaching solution and tailings. The overall vanadium leaching rate from vanadium slag concentrate to tailings is 97.84%. The vanadium leaching solution is boiled at 60℃ for 60min with an ammonium addition coefficient (ammonium salt to vanadium content mass ratio) of 3 and pH=1.7 to precipitate vanadium, yielding ammonium polyvanadate and vanadium precipitation wastewater. The vanadium precipitation rate is 98.54%. The ammonium polyvanadate is calcined at 500℃ for 120min to obtain vanadium pentoxide product. From vanadium slag concentrate to vanadium pentoxide product, the vanadium yield is 94.21%.

[0027] Example 3 Take 100g of vanadium slag concentrate, and weigh 30g of blast furnace nickel-iron slag according to a vanadium slag to blast furnace nickel-iron slag mass ratio of 1:0.3. Mix them evenly and calcine them in a muffle furnace at 4℃ / min to 900℃ for 120min. Cool to room temperature to obtain clinker, and grind the clinker to 80-140 mesh. Take 40g of clinker and add 10% sulfuric acid solution as the leaching agent at a liquid-to-solid ratio of 15:1. Leach at 60℃ with stirring for 60min, filter, and obtain primary vanadium leaching solution and tailings. The overall vanadium leaching rate from vanadium slag concentrate to tailings is 97.35%. The vanadium leaching solution is boiled and heated for 60min at an ammonium addition coefficient (ammonium to vanadium content mass ratio) of 3 and pH=1.7 to precipitate vanadium, obtaining ammonium polyvanadate and vanadium precipitation wastewater. The vanadium precipitation rate is 97.56%. The ammonium polyvanadate is calcined at 500℃ for 120min to obtain vanadium pentoxide product. From vanadium slag concentrate to vanadium pentoxide product, the vanadium yield is 92.35%.

[0028] Example 4 Take 100g of vanadium slag concentrate, and weigh 10g of blast furnace nickel-iron slag according to a vanadium slag to blast furnace nickel-iron slag mass ratio of 1:0.4. Mix evenly and calcine in a muffle furnace at 950℃ at 4℃ / min for 120min. Cool to room temperature to obtain clinker, which is then ground to 80-140 mesh. Take 40g of clinker and add 10% sulfuric acid solution as a leaching agent at a liquid-to-solid ratio of 15:1. Leach at 60℃ with stirring for 60min, filter, and obtain primary vanadium leaching solution and tailings. The overall vanadium leaching rate from vanadium slag concentrate to tailings is 95.34%. The vanadium leaching solution is boiled at 60℃ for 60min with an ammonium addition coefficient (ammonium salt to vanadium content mass ratio) of 3 and pH=1.7 to precipitate vanadium, yielding ammonium polyvanadate and vanadium precipitation wastewater. The vanadium precipitation rate is 96.26%. The ammonium polyvanadate is calcined at 500℃ for 120min to obtain vanadium pentoxide. From vanadium slag concentrate to vanadium pentoxide product, the vanadium yield is 91.58%.

[0029] Example 5 Take 100g of vanadium slag concentrate, and weigh 10g of blast furnace nickel-iron slag at a mass ratio of vanadium slag to blast furnace nickel-iron slag of 1:0.1. Mix them evenly and calcine in a muffle furnace at 4℃ / min to 950℃ for 120min. Cool to room temperature to obtain clinker, which is then ground to 80-140 mesh. Take 40g of clinker and add 10% sulfuric acid solution as a leaching agent at a liquid-to-solid ratio of 15:1. Leach at 60℃ with stirring for 60min, filter, and obtain primary vanadium leaching solution and tailings. The overall vanadium leaching rate from vanadium slag concentrate to tailings is 92.38%. The vanadium leaching solution is boiled at 60℃ for 60min with an ammonium addition coefficient (mass ratio of ammonium salt to vanadium content) of 3 and pH=1.7 to precipitate vanadium, yielding ammonium polyvanadate and vanadium precipitation wastewater. The vanadium precipitation rate is 97.31%. The ammonium polyvanadate is calcined at 500℃ for 120min to obtain vanadium pentoxide. From vanadium slag concentrate to vanadium pentoxide product, the vanadium yield is 92.54%.

[0030] Example 6 Take 100g of vanadium slag concentrate, and weigh 10g of blast furnace nickel-iron slag according to a vanadium slag to blast furnace nickel-iron slag mass ratio of 1:0.2. Mix evenly and calcine in a muffle furnace at 4℃ / min to 900℃ for 120min. Cool to room temperature to obtain clinker, which is then ground to 80-140 mesh. Take 40g of clinker and add 10% sulfuric acid solution as a leaching agent at a liquid-to-solid ratio of 15:1. Leach at 60℃ with stirring for 60min, filter, and obtain primary vanadium leaching solution and tailings. The overall vanadium leaching rate from vanadium slag concentrate to tailings is 96.58%. The vanadium leaching solution is boiled at 60℃ for 60min with an ammonium addition coefficient (ammonium salt to vanadium content mass ratio) of 3 and pH=1.7 to precipitate vanadium, yielding ammonium polyvanadate and vanadium precipitation wastewater. The vanadium precipitation rate is 93.89%. The ammonium polyvanadate is calcined at 500℃ for 120min to obtain vanadium pentoxide. From vanadium slag concentrate to vanadium pentoxide product, the vanadium yield is 93.45%.

Claims

1. A low-cost, green method for vanadium extraction, characterized in that, Includes the following steps: S1. Vanadium slag of a certain particle size and blast furnace nickel-iron slag additive of a certain particle size are mixed in a certain mass ratio and roasted at a certain temperature for a certain time to obtain vanadium slag blast furnace nickel-iron slag roasted clinker. S2. The vanadium slag blast furnace nickel-iron slag clinker is leached with acid of a certain concentration under certain conditions. After solid-liquid separation, a solution containing vanadium ions and primary residue are obtained. S3. Treat the solution containing vanadium ions to obtain a vanadium-containing product.

2. The low-cost, green vanadium extraction method according to claim 1, characterized in that: In step S1, the certain mass ratio refers to the mass ratio of vanadium slag and blast furnace nickel-iron slag additive being 1:(0.1~1).

3. The low-cost, green vanadium extraction method according to claim 1, characterized in that: In step S1, the certain temperature refers to 200-1000℃.

4. The low-cost, green vanadium extraction method according to claim 1, characterized in that: In step S1, the "certain time" refers to 10 to 180 minutes.

5. The low-cost, green vanadium extraction method according to claim 1, characterized in that: In step S2, the "certain acid" refers to at least one of the following acids: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, etc., and the concentration of the acid solution is 5-30%.

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

7. The low-cost, green vanadium extraction method according to claim 1, characterized in that: In step S1, the vanadium slag of a certain particle size refers to vanadium slag with a particle size not exceeding 1 mm, and the blast furnace nickel-iron slag additive of a certain particle size refers to blast furnace nickel-iron slag additive with a particle size not exceeding 1 mm.

8. The low-cost, green vanadium extraction method 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 low-cost, green vanadium extraction method according to claim 1, characterized in that: In step S1, the main components of the vanadium slag are: V2O5 5.3%~25.3%, SiO2 9.6~21.6%, Fe2O3 24.9~46.5%, MnO 2.3%~6.6%, MgO 2.9%~3.5%, and CaO 1.3%~4.9%.

10. A low-cost, green vanadium extraction method according to claim 1, characterized in that: In step S1, the blast furnace nickel-iron slag in the blast furnace nickel-iron slag additive is a type of blast furnace ironmaking waste slag, with the following main components: SiO2 23.5-35.6%, MgO 12.6%-19.5%, CaO 22.1%-35.6%, Al2O3 8.5-18.5%, Fe2O3 2.3-6.5%, and MnO 2.3%-6.6%.

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