A method for inhibiting tungstate colloidation

Abstract

This application belongs to the field of tungsten hydrometallurgy technology, specifically to a method for inhibiting tungsten acid gelation, comprising the following steps: mixing a first tungstic acid and a benzene series compound to form a reaction system; heating the reaction system until the water in the first tungstic acid and the benzene series form an azeotrope to obtain a second tungstic acid; separating the second tungstic acid and subjecting the second tungstic acid to ultrasonic treatment to obtain a third tungstic acid. Tungsten acid treated with the present method for inhibiting tungsten acid gelation is not prone to gelation and can be stored for a long time while maintaining its unique physical and chemical properties. The method can improve the performance of tungstic acid and reduce production costs. The method is highly applicable and can meet the needs of inhibiting tungsten acid gelation under different production conditions.

Description

Technical Field

[0001] The present application belongs to the technical field of tungsten hydrometallurgy, and specifically relates to a method for inhibiting tungstic acid gelation. Background Art

[0002] Tungsten acid gelation is a common problem in the production and application of tungstic acid, seriously affecting product performance and production costs. This can lead to decreased product performance, increased production costs, environmental pollution, and reduced sustainable utilization of tungsten resources. Therefore, effectively preventing tungstic acid gelation, improving product performance, and reducing production costs have become important research areas in the field of tungstic acid technology.

[0003] Currently, the main methods used to suppress tungstic acid gelation include chemical additives, high-temperature treatment, and mechanical pulverization. For example, chemical additives are added to modify the physical properties of tungstic acid to reduce gelation; high-temperature treatment is used to destroy the gelled structure and restore the fluidity of tungstic acid; and mechanical pulverization is used to break up the gelled particles and improve the dispersibility of tungstic acid. However, these methods have certain limitations and shortcomings.

[0004] While existing technologies have improved the problem of tungsten acid gelation to some extent, several issues and shortcomings remain. First, chemical additives may introduce new impurities, affecting the purity and performance of tungstic acid. Second, high-temperature treatment methods are energy-intensive and costly, and may damage the crystal structure of tungstic acid. Third, mechanical pulverization methods are inefficient and difficult to implement on a large scale. Furthermore, existing technical solutions have certain limitations in practical application and are unable to meet the anti-gelation requirements under various production conditions. Therefore, developing a new method to inhibit tungstic acid gelation has important practical significance and application value. Summary of the Invention

[0005] The present application provides a method for inhibiting tungstate gelation, which solves the technical problems of product performance degradation and increased production costs caused by tungstate gelation, and can also meet the needs of inhibiting tungstate gelation under different production conditions.

[0006] The method for inhibiting tungstate colloidation of the present application comprises the following steps:

[0007] S1, mixing the first tungstic acid and the benzene series to form a reaction system;

[0008] S2, heating the reaction system until the water in the first tungstic acid and the benzene series form an azeotropic reaction to obtain a second tungstic acid;

[0009] S3. Separate the second tungstic acid and perform ultrasonic treatment on the second tungstic acid to obtain third tungstic acid.

[0010] In the above technical solution, the first tungstic acid contains water or crystal water. After being mixed with the benzene series, when heated, the water or crystal water in the first tungstic acid will form an azeotropic phenomenon with the benzene series. The azeotropic temperature depends on the specific benzene series reagent added. This step can avoid the decomposition of tungstic acid caused by direct high-temperature heating. In addition, the benzene series will not react with tungstic acid to destroy the structure of tungstic acid. Among them, by adding an excess of benzene series, the water in the first tungstic acid can be evaporated as much as possible during the azeotropic reaction. In step S3, the second tungstic acid is treated with ultrasound to further separate the water, benzene series and other liquids remaining in the second tungstic acid from the tungstic acid to obtain a purer tungstic acid.

[0011] As a preferred embodiment of the method for inhibiting tungstic acid gelation of the present application, step S3 further includes: repeating step S2 three to five times; for tungstic acid with a high water content, it can be mixed with a benzene series and heated multiple times to azeotropic state to achieve a better water removal effect.

[0012] As a preferred solution of the method for inhibiting tungstate gelation of the present application, before step S1, the method further includes: drying the benzene series with a desiccant for 2 to 24 hours; drying the benzene series can avoid the introduction of additional moisture, thereby improving the dehydration efficiency.

[0013] As a preferred solution of the method for inhibiting tungstic acid gelation of the present application, the desiccant includes 3A molecular sieve, 4A molecular sieve, anhydrous magnesium sulfate or anhydrous calcium chloride.

[0014] As a preferred solution of the method for inhibiting tungstic acid gelation of the present application, the water content of the first tungstic acid is 10 wt % to 50 wt %.

[0015] As a preferred solution of the method for inhibiting tungstic acid gelation in the present application, the benzene series compound includes benzene or toluene.

[0016] As a preferred solution of the method for inhibiting tungstic acid gelation of the present application, in step S2, the azeotropic time is 10 to 30 minutes.

[0017] As a preferred solution of the method for inhibiting tungstate gelation of the present application, in step S3, the ultrasonic frequency used is 20-40 kHz and the power is 500-1000 W.

[0018] As a preferred embodiment of the method for inhibiting tungstic acid gelation of the present application, in step S3, the ultrasonic treatment time is 10 to 15 minutes per 500 grams of the second tungstic acid.

[0019] As a preferred embodiment of the method for inhibiting the gelation of tungstic acid in the present application, the time when the tertiary tungstic acid begins to gel is greater than 3 months; when stored for 3 months, the tertiary tungstic acid is washed with acid to obtain a washing solution containing the tertiary tungstic acid, and the filtration time per liter of washing solution is ≤2 minutes.

[0020] The present application provides a method for inhibiting the gelation of tungstic acid, which has the following beneficial effects: the treated tungstic acid is not easy to gel and can be stored for a long time while maintaining its unique physical and chemical properties; the performance of tungstic acid can be improved and the production cost can be reduced; the application is strong and can meet the needs of inhibiting the gelation of tungstic acid under different production conditions. DETAILED DESCRIPTION

[0021] The following will be a clear and complete description of the technical solutions in the embodiments. Obviously, the embodiments described are only part of the embodiments of this application, not all of them. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0022] The technical solution proposed in this application includes the following steps:

[0023] S1, mixing the first tungstic acid and the benzene series to form a reaction system;

[0024] Specifically, the benzene series is dried with a desiccant for 2 to 24 hours, and then the first tungstic acid and the benzene series are mixed to form a reaction system; wherein the desiccant includes 3A molecular sieve, 4A molecular sieve, anhydrous magnesium sulfate or anhydrous calcium chloride;

[0025] S2, heating the reaction system until the water in the first tungstic acid and the benzene series form an azeotropic reaction to obtain a second tungstic acid;

[0026] Specifically, the reaction system is heated until the water and benzene series in the first tungstic acid form an azeotropic state. This step can be repeated three to five times depending on the water content in the first tungstic acid.

[0027] S3, separating the second tungstic acid and subjecting the second tungstic acid to ultrasonic treatment to obtain third tungstic acid;

[0028] Specifically, the second tungstic acid is separated by ultrasonic treatment at a frequency of 20-40 kHz and a power of 500-1000 W. The ultrasonic treatment time is 10-15 minutes per 500 grams of the second tungstic acid.

[0029] The technical solution of this application is further described below with reference to specific embodiments.

[0030] Example 1

[0031] A first tungstic acid having a water content of 10 wt% is mixed with excess toluene to form a reaction system, and the reaction system is heated until the water and toluene in the first tungstic acid form an azeotrope to obtain a second tungstic acid; the second tungstic acid is separated, and 500 g of the second tungstic acid is subjected to ultrasonic treatment at a frequency of 40 kHz and a power of 1000 W for 15 minutes to obtain a third tungstic acid.

[0032] The tertiary tungstic acid was placed for 3 months without gelling. The tertiary tungstic acid was washed with acid to obtain a washing solution containing the tertiary tungstic acid. The filtration time for each liter of the washing solution was 2 minutes, and the physical and chemical properties were normal.

[0033] Example 2

[0034] A first tungstic acid having a water content of 50 wt% is mixed with excess toluene to form a reaction system, the reaction system is heated until the water and toluene in the first tungstic acid form an azeotrope, and the reaction system is repeatedly heated until the azeotrope forms five times to obtain a second tungstic acid; the second tungstic acid is separated, and 500 g of the second tungstic acid is taken and ultrasonically treated with a frequency of 20 kHz and a power of 500 W for 12 minutes to obtain a third tungstic acid.

[0035] The tertiary tungstic acid was placed for 3 months without gelling. The tertiary tungstic acid was washed with acid to obtain a washing solution containing the tertiary tungstic acid. The filtration time for each liter of the washing solution was 2 minutes, and the physical and chemical properties were normal.

[0036] Example 3

[0037] Toluene was dried over 3A molecular sieves for 24 hours; a first tungstic acid having a water content of 30 wt% was mixed with excess toluene to form a reaction system, the reaction system was heated until the water and toluene in the first tungstic acid formed an azeotrope, and the reaction system was repeatedly heated until the azeotrope formed three times to obtain a second tungstic acid; the second tungstic acid was separated, 500 g of the second tungstic acid was taken, and the second tungstic acid was treated with ultrasound at a frequency of 30 kHz and a power of 750 W for 10 minutes to obtain a third tungstic acid.

[0038] The tertiary tungstic acid was placed for 3 months without gelling. The tertiary tungstic acid was washed with acid to obtain a washing solution containing the tertiary tungstic acid. The filtration time for each liter of the washing solution was 2 minutes, and the physical and chemical properties were normal.

[0039] Example 4

[0040] Benzene was dried over 3A molecular sieves for 2 hours; a first tungstic acid having a water content of 30 wt% was mixed with excess benzene to form a reaction system, the reaction system was heated until the water and benzene in the first tungstic acid formed an azeotrope, and the reaction system was repeatedly heated until the azeotrope formed three times to obtain a second tungstic acid; the second tungstic acid was separated, 500 g of the second tungstic acid was taken, and the second tungstic acid was treated with ultrasound at a frequency of 30 kHz and a power of 750 W for 10 minutes to obtain a third tungstic acid.

[0041] The tertiary tungstic acid was left for 3 months without gelling. The tertiary tungstic acid was washed with acid to obtain a washing liquid containing the tertiary tungstic acid. The filtration time for each liter of washing liquid was 2 minutes, and the physical and chemical properties were normal.

[0042] Comparative Example 1

[0043] Toluene was dried over 3A molecular sieves for 24 hours. A first tungstic acid having a water content of 30 wt% was mixed with excess toluene to form a reaction system. The reaction system was heated until the water and toluene in the first tungstic acid formed an azeotrope. The reaction system was repeatedly heated until the azeotrope formed three times to obtain a second tungstic acid.

[0044] The difference between this comparative example and Example 3 is that, without ultrasonic treatment, the second tungstic acid gelled within 3 months; the second tungstic acid was washed with acid to obtain a washing solution containing the second tungstic acid, the filtration time per liter of the washing solution was 10 minutes, and the physical and chemical properties were normal.

[0045] Comparative Example 2

[0046] 500 g of first tungstic acid with a water content of 30 wt % was taken and ultrasonically treated with a frequency of 30 kHz and a power of 750 W for 10 minutes to obtain second tungstic acid.

[0047] The difference between this comparative example and Example 3 is that no azeotropic treatment is performed, and the second tungstic acid gels within one month; the second tungstic acid is washed with acid to obtain a washing liquid containing the second tungstic acid, the filtration time per liter of the washing liquid is 20 minutes, and the physical and chemical properties are normal.

[0048] Comparative Example 3

[0049] 500g of tungstic acid with a water content of 30wt% was allowed to stand naturally. This comparative example differs from Example 3 in that, without treatment, the tungstic acid gelled within one day. The tungstic acid was washed with acid to obtain a washing solution containing tungstic acid, and the filtration time per liter of washing solution was 40 minutes.

[0050] Comparative Example 4

[0051] 500g of tungstic acid with a water content of 50wt% was allowed to stand naturally. The difference between this comparative example and Example 2 is that, without treatment, the tungstic acid gelled within 20 minutes. When the tungstic acid was washed with acid, a washing solution containing tungstic acid was obtained, and the filtration time per liter of washing solution was 135 minutes.

[0052] Comparative Example 5

[0053] The ethanol was dried over 3A molecular sieves for 24 hours; a first tungstic acid having a water content of 30 wt% was mixed with excess ethanol to form a reaction system, the reaction system was heated until the water and ethanol in the first tungstic acid formed an azeotrope, and the heating of the reaction system until the azeotrope was repeated three times to obtain a second tungstic acid; 500 g of the second tungstic acid was taken and ultrasonically treated with a frequency of 30 kHz and a power of 750 W for 10 minutes to obtain a third tungstic acid.

[0054] The difference between this comparative example and Example 3 is that ethanol is used to perform azeotropic treatment with water in the first tungstic acid, and the third tungstic acid gels within 3 months; the third tungstic acid is washed with acid to obtain a washing liquid containing the third tungstic acid, the filtration time per liter of the washing liquid is 10 minutes, and the physical and chemical properties are normal.

[0055] It can be seen from the examples and comparative examples that the tungstic acid produced by azeotroping with benzene or toluene and then ultrasonically treated is stable and can be stored for a long time without gelling while retaining its unique physical and chemical properties.

[0056] The tungsten acid treated by the method for inhibiting tungsten acid gelation in the present application is not easy to gel and can be stored for a long time while maintaining its unique physical and chemical properties; it can improve the performance of tungsten acid and reduce production costs; it has strong applicability and can meet the needs of inhibiting tungsten acid gelation under different production conditions.

[0057] The above description is only a preferred embodiment of the present application and does not limit the patent scope of the present application. All equivalent structural transformations made using the contents of the present application specification under the inventive concept of the present application, or direct / indirect application in other related technical fields are included in the patent protection scope of the present application.

Claims

1. A method for inhibiting tungstic acid colloidation, characterized in that: The following steps are involved: S1, mixing the first tungstic acid and the benzene series to form a reaction system; S2, heating the reaction system until the water in the first tungstic acid and the benzene series form an azeotropic reaction to obtain a second tungstic acid; S3, separating the second tungstic acid and subjecting the second tungstic acid to ultrasonic treatment to obtain third tungstic acid; Before step S1, the method further includes: drying the benzene series with a desiccant, and the drying time is 2 to 24 hours.

2. The method for inhibiting tungstic acid colloidation according to claim 1, characterized in that: Before step S3, the method further includes: repeating step S2 three to five times.

3. The method for inhibiting tungstic acid colloidation according to claim 1, characterized in that: The desiccant includes 3A molecular sieve, 4A molecular sieve, anhydrous magnesium sulfate or anhydrous calcium chloride.

4. The method for inhibiting tungstic acid colloidation according to claim 1, wherein: The water content of the first tungstic acid is 10 wt % to 50 wt %.

5. The method for inhibiting tungstic acid colloidation according to claim 1, characterized in that: The benzene series includes benzene or toluene.

6. The method for inhibiting tungstate gelation according to claim 1, characterized in that: In step S2, the azeotropic time is 10 to 30 minutes.

7. The method for inhibiting tungstic acid colloidation according to claim 1, characterized in that: In step S3, the ultrasonic frequency used is 20-40 kHz and the power is 500-1000 W.

8. The method for inhibiting tungstic acid colloidation according to claim 1, characterized in that: In step S3, the ultrasonic treatment time is 10 to 15 minutes per 500 grams of the second tungstic acid.

9. The method for inhibiting tungstic acid colloidation according to claim 1, characterized in that: The time when the third tungstic acid begins to gel is greater than 3 months. When the third tungstic acid is stored for 3 months, the third tungstic acid is washed with acid to obtain a washing solution containing the third tungstic acid, and the filtration time per liter of the washing solution is ≤2 minutes.