Use method of vanadium precipitation agent for vanadium-containing leaching mother liquor

Abstract

The invention discloses a use method of a vanadium precipitation agent for vanadium-containing leaching mother liquor, and belongs to the technical field of non-ferrous metallurgy. The use method comprises the following steps that S1, the vanadium precipitation agent is prepared; s2, preparing a vanadium precipitate; and S3, preparing a vanadium pentoxide finished product. According to the use method of the vanadium precipitation agent for the vanadium-containing leaching mother liquor, the use amount of ammonium sulfate in the vanadium precipitation process can be effectively reduced, and the vanadium recovery rate is increased.

Description

Technical Field

[0001] The invention relates to the technical field of nonferrous metal metallurgy, and 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 uses. It is called "modern industrial MSG". Adding a small amount of vanadium to steel can significantly improve the strength of the steel. The main vanadium products include vanadium pentoxide, vanadium nitrogen alloy, etc., which are mainly used in the steel industry, chemical industry, aerospace and other fields. Vanadium-titanium magnetite (vanadium-containing slag) is the main resource for producing vanadium, accounting for more than 80% of the world's vanadium products. At present, the main raw material for vanadium extraction is vanadium slag. The vanadium slag vanadium extraction process mainly includes sodium roasting-water leaching process and calcium roasting-acid leaching process. No matter which vanadium extraction process is adopted, vanadium needs to be extracted from the vanadium leaching mother liquor. The current mainstream extraction process is the ammonium salt vanadium precipitation process, that is, under certain conditions, ammonium salt is added to the vanadium-containing solution, and a double decomposition reaction occurs, so that vanadium is precipitated from the solution in the form of ammonium metavanadate or ammonium polyvanadate.

[0003] According to the different pH values ​​of vanadium precipitation, it can be divided into weak alkaline ammonium salt precipitation, weak acidic ammonium salt precipitation and acidic ammonium salt precipitation. The acidic ammonium salt precipitation has high product purity, relatively simple process, and is conducive to subsequent filtration and other steps. Therefore, whether it is the sodium roasting-water leaching process or the calcium roasting-acid leaching process for vanadium precipitation, the ammonium salt selected is mainly ammonium sulfate. In general, the total vanadium concentration of the vanadium-containing acid leaching mother liquor obtained by vanadium product enterprises from the calcium roasting and leaching process is 18-28g / L, and the amount of ammonium sulfate required in the ammonium salt precipitation process is about: 16g of ammonium sulfate is added to each 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. With the increase in the amount of ammonium sulfate, the following two problems will occur:

[0005] (1) Since some concentrated ammonium sulfate does not participate in vanadium precipitation, the concentration of ammonium sulfate 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, the residual ammonium sulfate and sodium sulfate are precipitated together, which directly affects the purity of the sodium sulfate precipitation, resulting in a large amount of substandard sodium sulfate that cannot be used.

[0006] (2) Ammonium sulfate is the mainstream 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 benefits of enterprises. Summary of the invention

[0007] The purpose of the present invention is 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 vanadium-containing leaching mother solution, 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 precipitator in S1 is in a solution or powder state, and the specific operation of preparing the vanadium precipitator solution is: adding the vanadium precipitator to clean water or the supernatant obtained in the vanadium precipitation process, and heating to obtain the vanadium precipitator solution.

[0013] Preferably, the specific operation of S2 is: heating the vanadium leaching mother liquor, and adding the vanadium precipitating agent solution or vanadium precipitating agent 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, filtering it again, and drying and calcining it to obtain the finished vanadium pentoxide product.

[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 at a ratio of g:L=0.1-1.6:1, ammonium sulfate is added at a ratio of 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 precipitating agent and ammonium sulfate to the vanadium leaching mother liquor in S2, the temperature is continuously heated and maintained at 90-100° C., and 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 h.

[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 solution, 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 0.1-1.6 g of vanadium precipitation agent per liter of vanadium leaching mother liquor, from the original 16 g of ammonium sulfate per liter of vanadium leaching mother liquor to 5 g of ammonium sulfate 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 agent significantly improves the vanadium recovery rate. The vanadium content of 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 of the present invention 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 be involved 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 flow chart of an embodiment of a method for using a vanadium precipitating agent for vanadium-containing leaching mother solution. DETAILED DESCRIPTION

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

[0029] Unless otherwise defined, technical or scientific terms used in the present invention shall have the common meanings understood by one having ordinary skills in the field to which the present invention belongs.

[0030] Example

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

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

[0033] The main component of the vanadium precipitator 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. The dosage of the vanadium precipitator is 0.1-1.6 g / L, that is, 0.1-1.6 g of the vanadium precipitator needs to be added to each liter of vanadium leaching mother liquor. The mass ratio of the vanadium precipitator to the volume of the clean water or supernatant in which the vanadium precipitator is dissolved is g:mL=1:25-200.

[0034] The vanadium precipitator and the wastewater generated during the vanadium precipitation process can be involved 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 represented by melamine have significant advantages in improving vanadium recovery rate. The mechanism of action is that these compounds can form low-solubility complexes with vanadium ions, effectively capturing a large number of vanadate ions through complexation and causing them to precipitate, thereby 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, and the vanadium precipitant is added at a ratio of g:L=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 g:L=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 temperature is continuously heated to 90-100° C. and maintained, and the reaction is continuously stirred for 10-90 min, and the stirring speed is 300-400 rpm, and the vanadium precipitate is obtained by filtration.

[0037] Vanadium complexes have different solubility under different pH conditions. By adjusting the pH value, the dissolution and precipitation of vanadium compounds can be controlled, thereby achieving effective separation and purification of vanadium. By accurately controlling the pH value, the possibility of other metal ions or other impurities precipitating with vanadium can be reduced, thereby improving the purity of the product.

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

[0039] Embodiment 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 was 2.68.

[0041] The specific steps include:

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

[0043] 2) 1L of vanadium leaching mother liquor was heated to 90°C, the above vanadium precipitant solution and 5g 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 1h, stirred continuously at 300rpm, filtered, and vanadium precipitate was obtained.

[0044] 3) Wash the vanadium precipitate with clean water once, filter and dry it, and calcine the dried vanadium precipitate 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 can be seen from Table 1, the vanadium pentoxide content of the product is 98.27%, 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.

[0048] Embodiment 2

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

[0050] The specific steps include:

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

[0052] 2) Take 1L of vanadium leaching mother liquor and heat it to 50°C, add 12.5g of ammonium sulfate to the vanadium leaching mother liquor, continue heating to 90°C, add vanadium precipitant powder and add sulfuric acid to adjust the pH to 2.2, continue heating to make the vanadium leaching mother liquor boil and keep it for 45min, continue stirring at 300rpm, filter and obtain vanadium precipitate.

[0053] 3) Wash the vanadium precipitate with clean water once, filter and dry it, and calcine the dried vanadium precipitate 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 can be seen from 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 value of the national standard, indicating that the impurity control in the production process is very strict.

[0057] Embodiment 3

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

[0059] The specific steps include:

[0060] 1) Take 1L of vanadium leaching mother liquor and heat it to 90°C, add 5g of ammonium sulfate to the vanadium leaching mother liquor and react for 15min, then add 0.4g of vanadium precipitant powder and use sulfuric acid to adjust the pH to 2.2, boil the vanadium leaching mother liquor and continue heating for 25min, continue stirring at 300rpm, filter and obtain vanadium precipitate.

[0061] 2) Wash the vanadium precipitate with clean water once, filter and dry it, and calcine the dried vanadium precipitate 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 can be seen from 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 usage of ammonium sulfate 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 solution of the present invention rather than to limit it. 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 solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. A method for using a vanadium precipitating agent for vanadium-containing leaching mother solution, characterized in that: The following steps are involved: S1. Prepare vanadium precipitation agent; S2, preparing vanadium precipitate; S3, preparing vanadium pentoxide finished product.

2. The method for using a vanadium precipitating agent for vanadium-containing leaching mother solution according to claim 1, characterized in that: The vanadium precipitator in S1 is in a solution or powder state. The specific operation of preparing the vanadium precipitator solution is: adding the vanadium precipitator to clean water or the supernatant obtained in the vanadium precipitation process, and heating to obtain the vanadium precipitator solution.

3. The method for using a vanadium precipitating agent for vanadium-containing leaching mother solution according to claim 1, characterized in that: The specific operation of S2 is: heating the vanadium leaching mother liquor, and adding the vanadium precipitating agent solution or vanadium precipitating agent 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.

4. The method for using a vanadium precipitating agent for vanadium-containing leaching mother solution according to claim 1, characterized in that: The specific operation of S3 is: washing the vanadium precipitate and filtering it again, and then drying and calcining it to obtain the finished vanadium pentoxide product.

5. The method for using a vanadium precipitating agent for vanadium-containing leaching mother solution according to claim 2, characterized in that: When a vanadium precipitant solution is used, the mass ratio 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.

6. The method for using a vanadium precipitating agent for vanadium-containing leaching mother solution according to claim 5, characterized in that: 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.

7. The method for using a vanadium precipitating agent for vanadium-containing leaching mother solution according to claim 3, characterized in that: The heating temperature of the vanadium leaching mother liquor in S2 is 50-90°C, and the vanadium precipitant is added at a ratio of g:L=0.1-1.6:1 to the weight of the vanadium precipitant and the volume of the vanadium leaching mother liquor, and ammonium sulfate is added at a ratio of g:L=1-15:1 to the weight 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 300-400rpm.

8. The method for using a vanadium precipitating agent for vanadium-containing leaching mother solution according to claim 7, characterized in that: After adding vanadium precipitating 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.

9. The method for using a vanadium precipitating agent for vanadium-containing leaching mother solution according to claim 4, characterized in that: The calcination temperature in S3 is 550-600°C and the calcination time is 2-3h.

10. The method for using a vanadium precipitating agent for vanadium-containing leaching mother solution according to claim 3, characterized in that: The TV concentration of vanadium leaching mother liquor is 10-100g / L.

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