Method for using a vanadium precipitant for vanadium-containing leaching mother liquor

Abstract

The present invention discloses a method for using a vanadium precipitating agent for vanadium-containing leaching mother liquor, belonging to the technical field of nonferrous metallurgy, and comprises the following steps: S1, preparing a vanadium precipitating agent; S2, preparing a vanadium precipitate; and S3, preparing a finished vanadium pentoxide product. The present invention utilizes the aforementioned method for using a vanadium precipitating agent for vanadium-containing leaching mother liquor to effectively reduce the amount of ammonium sulfate used in the vanadium precipitation process and improve the vanadium recovery rate.

Description

Technical Field

[0001] The invention relates to the technical field of nonferrous metal metallurgy, in particular to a method for using a vanadium precipitation agent for vanadium-containing leaching mother liquor. Background Art

[0002] Vanadium is a strategic metal with important applications, known as the "modern industrial MSG." Adding a small amount of vanadium to steel can significantly increase its strength. Vanadium products primarily include vanadium pentoxide and vanadium-nitrogen alloys, which are used primarily in the steel, chemical, aerospace, and other industries. Vanadium-titanium magnetite (vanadium-containing slag) is the primary resource for vanadium production, accounting for over 80% of global vanadium production. Currently, the primary raw material for vanadium extraction is vanadium slag, and the main vanadium extraction processes include sodium roasting-water leaching and calcium roasting-acid leaching. Regardless of the vanadium extraction process employed, vanadium must be extracted from the vanadium leaching mother liquor. The current mainstream extraction process is ammonium salt precipitation, where ammonium salts are added to a vanadium-containing solution under certain conditions, causing a double decomposition reaction to precipitate vanadium from the solution as ammonium metavanadate or ammonium polyvanadate.

[0003] Vanadium precipitation can be categorized as weakly alkaline ammonium salt precipitation, weakly acidic ammonium salt precipitation, and acidic ammonium salt precipitation, depending on the pH value. Acidic ammonium salt precipitation offers high product purity, a relatively simple process, and facilitates subsequent filtration steps. Therefore, whether using the sodium roasting-water leaching process or the calcium roasting-acid leaching process, the primary ammonium salt of choice for vanadium precipitation is ammonium sulfate. Typically, vanadium product manufacturers obtain a vanadium-containing acid leaching mother liquor from the calcium roasting-leaching process with a total vanadium concentration of 18-28 g / L. The ammonium salt precipitation process requires approximately 16 g of ammonium sulfate per liter of mother liquor.

[0004] In order to stabilize the vanadium precipitation recovery rate, the company generally uses more ammonium sulfate than the theoretical demand. However, even so, the vanadium concentration in the residual vanadium wastewater is still around 0.2g / L. As the amount of ammonium sulfate increases, the following two problems will occur:

[0005] (1) Because some concentrated ammonium sulfate does not participate in vanadium precipitation, the ammonium sulfate concentration in vanadium precipitation wastewater can reach 4-8g / L, increasing the cost of wastewater treatment for enterprises. In particular, during the evaporation treatment of vanadium precipitation wastewater from the sodium roasting-water leaching process, residual ammonium sulfate and sodium sulfate are precipitated together, directly affecting the purity of the sodium sulfate precipitate, resulting in a large amount of substandard sodium sulfate that cannot be used.

[0006] (2) Ammonium sulfate is the main raw material for vanadium precipitation and is also an excellent nitrogen fertilizer. Its price is greatly affected by agriculture. The price fluctuation of ammonium sulfate will have a significant impact on the company's profitability. Summary of the Invention

[0007] The present invention aims to provide a method for using a vanadium precipitation agent for vanadium-containing leaching mother liquor, which can effectively reduce the amount of ammonium sulfate used in the vanadium precipitation process and improve the vanadium recovery rate.

[0008] To achieve the above object, the present invention provides a method for using a vanadium precipitating agent for a vanadium-containing leaching mother liquor, comprising the following steps:

[0009] S1. Prepare vanadium precipitation agent;

[0010] S2, preparing vanadium precipitate;

[0011] S3, preparing vanadium pentoxide finished product.

[0012] Preferably, the vanadium precipitant in S1 is in solution or powder form, and the specific operation of preparing the vanadium precipitant solution is: adding the vanadium precipitant to clean water or the supernatant obtained during the vanadium precipitation process, and heating to obtain the vanadium precipitant solution.

[0013] Preferably, the specific operation of S2 is: heating the vanadium leaching mother liquor, and adding the vanadium precipitant solution or vanadium precipitant powder obtained in S1 and ammonium sulfate to the vanadium leaching mother liquor respectively, adding sulfuric acid to adjust the pH, continuously heating and stirring, and filtering to obtain vanadium precipitate.

[0014] Preferably, the specific operation of S3 is: washing the vanadium precipitate and filtering it again, drying and calcining it to obtain the finished vanadium pentoxide.

[0015] Preferably, when a vanadium precipitant solution is used, the volume ratio of the mass of the vanadium precipitant in S1 to the clean water or supernatant in which the vanadium precipitant is dissolved is g:mL=1:25-200, the dosage of the vanadium precipitant is 0.1-1.6 g / L, that is, 0.1-1.6 g of the vanadium precipitant is added to each liter of vanadium leaching mother liquor, and the heating temperature is 25-100°C.

[0016] Preferably, the main component of the vanadium precipitant is an organic amine compound represented by melamine, including any one or more of aliphatic amines, alcohol amines, amides, alicyclic amines, aromatic amines, naphthyl amines and other amines.

[0017] Preferably, the heating temperature of the vanadium leaching mother liquor in S2 is 50-90°C, the vanadium precipitant is added according to the weight of the vanadium precipitant and the volume ratio of the vanadium leaching mother liquor g:L=0.1-1.6:1, and ammonium sulfate is added according to the weight of the ammonium sulfate and the volume ratio of the vanadium leaching mother liquor g:L=1-15:1, and then sulfuric acid is added to adjust the pH to 1.5-3, and the stirring speed is continuously 300-400rpm.

[0018] Preferably, after adding the vanadium precipitation agent and ammonium sulfate to the vanadium leaching mother liquor in S2, the mixture is continuously heated and maintained at a temperature of 90-100° C. The temperature is maintained at 90-100° C. and the stirring reaction time is 10-90 minutes.

[0019] Preferably, the calcination temperature in S3 is 550-600° C., and the calcination time is 2-3 hours.

[0020] Preferably, the TV concentration of the vanadium leaching mother solution is 10-100 g / L.

[0021] Therefore, the present invention adopts the above-mentioned method of using a vanadium precipitation agent for vanadium-containing leaching mother liquor, which has the following beneficial effects:

[0022] (1) Compared with the existing calcination roasting-acid leaching process for vanadium precipitation, the present invention reduces the amount of ammonium sulfate used by adding 0.1-1.6g of vanadium precipitation agent per liter of vanadium leaching mother liquor, reducing the amount of ammonium sulfate used from 16g per liter of vanadium leaching mother liquor to 5g per liter of vanadium leaching mother liquor, thereby reducing the raw material cost to less than half of the original process;

[0023] (2) The participation of vanadium precipitation agents significantly improves the vanadium recovery rate. The vanadium content of the vanadium precipitation wastewater produced by the calcination roasting-acid leaching process is 0.2g / L, while the untaxed residual vanadium content produced by the vanadium precipitation method is below 0.1g / L, which can significantly improve the vanadium recovery rate of the enterprise;

[0024] (3) Through the participation of vanadium precipitation agents, the use of ammonium sulfate is greatly reduced, thereby greatly reducing the amount of ammonia nitrogen in vanadium precipitation wastewater and reducing the cost of residual vanadium wastewater treatment;

[0025] (4) Vanadium precipitation can be completed simply and efficiently to obtain high-purity vanadium pentoxide products. The vanadium precipitation agent and the wastewater generated during the vanadium precipitation process can participate in the process of preparing the vanadium precipitation agent solution, thereby reducing the discharge of ammonia nitrogen wastewater.

[0026] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The present invention is a flowchart of an embodiment of a method for using a vanadium precipitating agent for vanadium-containing leaching mother liquor. DETAILED DESCRIPTION

[0028] The technical solution of the present invention is further described below with reference to the accompanying drawings and embodiments.

[0029] Unless otherwise defined, technical or scientific terms used in the present invention shall have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs.

[0030] Example

[0031] like Figure 1 As shown, the present invention provides a method for using a vanadium precipitation agent for vanadium-containing leaching mother liquor, comprising the following steps:

[0032] S1. Prepare a vanadium precipitant. The vanadium precipitant is in a solution or powder state. The preparation of the vanadium precipitant solution comprises the following steps: adding the vanadium precipitant to clean water or the supernatant obtained during the vanadium precipitation process, and heating to 25-100° C. to obtain a vanadium precipitant solution.

[0033] The main component of the vanadium precipitant is an organic amine compound, represented by melamine, and includes any one or more of aliphatic amines, alcoholamines, amides, alicyclic amines, aromatic amines, naphthylamines, and other amines. The dosage of the vanadium precipitant is 0.1-1.6 g / L, meaning 0.1-1.6 g of vanadium precipitant is added per liter of vanadium leaching mother liquor. The volume ratio of the vanadium precipitant to the water or supernatant in which it is dissolved is 1:25-200 (g:mL).

[0034] The vanadium precipitator and the wastewater generated during the vanadium precipitation process can be used in the process of preparing the vanadium precipitator solution, reducing the discharge of ammonia nitrogen wastewater. The participation of the vanadium precipitator greatly reduces the use of ammonium sulfate, thereby greatly reducing the amount of ammonia nitrogen in the vanadium precipitation wastewater and reducing the cost of vanadium precipitation wastewater treatment.

[0035] Organic amine compounds, such as melamine, offer significant advantages in improving vanadium recovery. Their mechanism of action lies in their ability to form low-solubility complexes with vanadium ions. This complexation effectively captures a large number of vanadate ions, causing them to precipitate, significantly improving vanadium recovery efficiency.

[0036] S2. Preparation of vanadium precipitate: The TV concentration of the vanadium leaching mother liquor is 10-100 g / L. The vanadium leaching mother liquor is first heated to 50-90° C., and the vanadium precipitant solution or vanadium precipitant powder obtained in S1 and ammonium sulfate are respectively added to the vanadium leaching mother liquor. The vanadium precipitant is added at a ratio of g:L to the volume of the vanadium leaching mother liquor of 0.1-1.6:1. Ammonium sulfate is added at a ratio of g:L to the volume of the vanadium leaching mother liquor of 1-15:1. Subsequently, sulfuric acid is added to adjust the pH to 1.5-3. The mixture is heated to 90-100° C. and maintained at this temperature. The mixture is stirred for 10-90 minutes at a stirring speed of 300-400 rpm. The vanadium precipitate is filtered to obtain the vanadium precipitate.

[0037] Vanadium complexes have varying solubility under different pH conditions. By adjusting the pH, the dissolution and precipitation of vanadium compounds can be controlled, enabling effective separation and purification of vanadium. Precise pH control reduces the likelihood of other metal ions or other impurities co-precipitating with vanadium, thereby improving product purity.

[0038] S3. Preparation of vanadium pentoxide product: washing the vanadium precipitate, filtering it again, drying it, and calcining it to obtain the vanadium pentoxide product, wherein the calcination temperature is 550-600° C. and the calcination time is 2-3 hours.

[0039] Example 1

[0040] The vanadium-containing leaching mother liquor TV=24.6 g / L, Si=0.319 g / L, P=0.022 g / L, Mn=7.83 g / L, Fe=0.048 g / L, Na=6 g / L, and pH is 2.68.

[0041] The specific steps include:

[0042] 1) First, take 0.4g of vanadium precipitant and add it to 50ml of clean water, and heat it to about 90℃ to obtain a vanadium precipitant solution.

[0043] 2) 1 L of the vanadium leaching mother liquor was heated to 90° C. The above-mentioned vanadium precipitant solution and 5 g of ammonium sulfate were added to the vanadium leaching mother liquor. Sulfuric acid was added to adjust the pH to 2.2. The vanadium leaching mother liquor was naturally boiled and heated for 1 hour. The mixture was stirred at 300 rpm and filtered to obtain a vanadium precipitate.

[0044] 3) The vanadium precipitate was washed once with clean water, filtered and dried, and the dried vanadium precipitate was calcined at 570° C. for 2 h to obtain a vanadium pentoxide product. The quality of the obtained product is shown in Table 1 below:

[0045] Table 1 Product quality

[0046] Element / % <![CDATA[V2O5]]> Mn Si Fe P S <![CDATA[K2O+Na2O]]> National Standard ≥98.0 / ≤0.20 ≤0.25 ≤0.03 ≤0.10 ≤1.0 product 98.27 0.48 <0.001 0.12 0.02 <0.001 0.16

[0047] As shown in Table 1, the vanadium pentoxide content of the product is 98.27%, exceeding the minimum requirement of the national standard, indicating that the product has high purity. The contents of other impurities are far lower than the maximum allowable values ​​of the national standard, indicating that the impurity control in the production process is very strict.

[0048] Example 2

[0049] The vanadium-containing leaching mother liquor TV=62.5 g / L, Si=0.302 g / L, P=0.017 g / L, Mn=7.13 g / L, Fe=0.058 g / L, Na=34.7 g / L, and pH is 2.70.

[0050] The specific steps include:

[0051] 1) First, take 1g of vanadium precipitant and add it to 80ml of clean water, and heat it to about 90℃ to obtain a vanadium precipitant solution.

[0052] 2) 1 L of the vanadium leaching mother liquor was heated to 50° C., 12.5 g of ammonium sulfate was added to the vanadium leaching mother liquor, and the mixture was continuously heated to 90° C., vanadium precipitant powder was added, and sulfuric acid was added to adjust the pH to 2.2. The vanadium leaching mother liquor was further heated to a boil and maintained at a boil for 45 minutes. The mixture was continuously stirred at 300 rpm and filtered to obtain a vanadium precipitate.

[0053] 3) The vanadium precipitate was washed once with clean water, filtered and dried, and the dried vanadium precipitate was calcined at 570° C. for 2 h to obtain a vanadium pentoxide product. The quality of the obtained product is shown in Table 2 below:

[0054] Table 2 Product quality

[0055] Element / % <![CDATA[V2O5]]> Mn Si Fe P S <![CDATA[K2O+Na2O]]> National Standard ≥98.0 / ≤0.20 ≤0.25 ≤0.03 ≤0.10 ≤1.0 product 98.45 0.36 <0.001 0.11 0.012 <0.001 0.70

[0056] As shown in Table 2, the content of vanadium pentoxide in the product is 98.45%, which exceeds the minimum requirement of the national standard, indicating that the product has high purity. The contents of other impurities are far lower than the maximum allowable values ​​of the national standard, indicating that the impurity control in the production process is very strict.

[0057] Example 3

[0058] The vanadium-containing leaching mother liquor TV=23.3 g / L, Si=0.310 g / L, P=0.014 g / L, Mn=7.21 g / L, Fe=0.051 g / L, Na=8.2 g / L, and pH is 2.66.

[0059] The specific steps include:

[0060] 1) 1 L of vanadium leaching mother liquor was heated to 90° C. 5 g of ammonium sulfate was added to the vanadium leaching mother liquor and reacted for 15 min. 0.4 g of vanadium precipitant powder was then added and the pH was adjusted to 2.2 using sulfuric acid. The vanadium leaching mother liquor was boiled and heated continuously for 25 min. The mixture was stirred continuously at 300 rpm and filtered to obtain a vanadium precipitate.

[0061] 2) The vanadium precipitate was washed once with clean water, filtered and dried, and the dried vanadium precipitate was calcined at 570° C. for 2 h to obtain a vanadium pentoxide product. The quality of the obtained product is shown in Table 3 below:

[0062] Table 3 Product quality

[0063] Element / % <![CDATA[V2O5]]> Mn Si Fe P S <![CDATA[K2O+Na2O]]> National Standard ≥98.0 / ≤0.15 ≤0.2 ≤0.03 ≤0.01 ≤1.0 product 98.60 0.40 <0.001 0.14 0.011 <0.001 0.36

[0064] As shown in Table 3, the content of vanadium pentoxide in the product is 98.60%, which exceeds the minimum requirement of the national standard, indicating that the product has high purity. The contents of other impurities are far lower than the maximum allowable values ​​of the national standard, indicating that the impurity control in the production process is very strict.

[0065] Therefore, the present invention adopts the method of using the above-mentioned vanadium precipitation agent for vanadium-containing leaching mother liquor, which can effectively reduce the amount of ammonium sulfate used in the vanadium precipitation process and improve the vanadium recovery rate.

[0066] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the same. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solutions of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for using a vanadium precipitating agent for vanadium-containing leaching mother liquor, characterized by: The following steps are involved: S1. Prepare vanadium precipitation agent; The vanadium precipitating agent in S1 is in a solution or powder state. The specific operation of preparing the vanadium precipitating agent solution is: adding the vanadium precipitating agent to clean water or the supernatant obtained during the vanadium precipitation process, and heating to obtain the vanadium precipitating agent solution; The vanadium precipitation agent includes any one or more of aliphatic amines, alcohol amines, amides, alicyclic amines, aromatic amines, and naphthyl amines; S2, preparing vanadium precipitate; The specific operation of S2 is: heating the vanadium leaching mother liquor, and adding the vanadium precipitant solution or vanadium precipitant powder obtained in S1 and ammonium sulfate to the vanadium leaching mother liquor respectively, adding sulfuric acid to adjust the pH, continuing heating and stirring, and filtering to obtain vanadium precipitate; When using a vanadium precipitant solution, the volume ratio of the mass of the vanadium precipitant in S1 to the clean water or supernatant in which the vanadium precipitant is dissolved is g:mL=1:25-200, and the dosage of the vanadium precipitant is 0.1-1.6 g / L, that is, 0.1-1.6 g of the vanadium precipitant is added to each liter of vanadium leaching mother liquor, and the heating temperature is 25-100°C; The vanadium leaching mother liquor in S2 is heated to a temperature of 50-90°C, and a vanadium precipitant is added at a ratio of 0.1-1.6:1 by weight of the vanadium precipitant and the volume of the vanadium leaching mother liquor, and ammonium sulfate is added at a ratio of 1-15:1 by weight of the ammonium sulfate and the volume of the vanadium leaching mother liquor, and then sulfuric acid is added to adjust the pH to 1.5-3, and the stirring speed is continuously maintained at 300-400 rpm; The TV concentration of vanadium leaching mother liquor is 10-100g / L; S3, preparing a vanadium pentoxide product. The specific operation of S3 is: washing the vanadium precipitate and filtering it again, drying and calcining it to obtain the vanadium pentoxide product.

2. The method for using a vanadium precipitation agent for vanadium-containing leaching mother liquor according to claim 1, characterized in that: After adding vanadium precipitation agent and ammonium sulfate to the vanadium leaching mother liquor in S2, continue heating and maintain the temperature at 90-100°C. The temperature is maintained at 90-100°C and the stirring reaction time is 10-90 minutes.

3. The method for using a vanadium precipitation agent for vanadium-containing leaching mother liquor according to claim 1, characterized in that: The calcination temperature in S3 is 550-600°C, and the calcination time is 2-3h.

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