阅读说明：本技术 新型萃取剂及其从磷钨杂多酸中提取钨并转化为钨酸铵/钨酸钠溶液的方法 (Novel extracting agent and method for extracting tungsten from phosphotungstic heteropoly acid and converting tungsten into ammonium tungstate/sodium tungstate solution ) 是由 叶晓龙 苏志宏 于 2020-06-19 设计创作，主要内容包括：本发明公开了一种新型萃取剂及从磷钨杂多酸溶液萃取钨的方法,所述新型萃取剂其是由体积份乙酸丁酯0.1-0.4份、正丁醇0.2-0.4份、磺化煤油0.3-0.6份组成,能够在酸性条件下快速提取磷钨杂多酸中的钨并转化为钨酸铵/钨酸钠溶液,为钨转化为钨酸铵/钨酸钠提供新路径；同时该方法能萃取的磷钨杂多酸浓度较高,萃取效果可达90％以上；相对离子交换法大大节约了水量。(The invention discloses a novel extracting agent and a method for extracting tungsten from a phosphotungstic acid solution, wherein the novel extracting agent consists of 0.1-0.4 part by volume of butyl acetate, 0.2-0.4 part by volume of n-butyl alcohol and 0.3-0.6 part by volume of sulfonated kerosene, can quickly extract tungsten in phosphotungstic acid under an acidic condition and convert the tungsten into an ammonium tungstate/sodium tungstate solution, and provides a new path for converting tungsten into ammonium tungstate/sodium tungstate; meanwhile, the concentration of the phosphotungstic heteropoly acid extracted by the method is higher, and the extraction effect can reach more than 90 percent; compared with the ion exchange method, the water quantity is greatly saved.)

1. A novel extracting agent is composed of, by volume, 0.1-0.4 part of butyl acetate, 0.2-0.4 part of n-butyl alcohol and 0.3-0.6 part of sulfonated kerosene, and can extract a tungsten-containing solution.

2. The extractant as claimed in claim 1, which consists of 0.1-0.15 part of butyl acetate, 0.3-0.4 part of n-butanol and 0.45-0.55 part of sulfonated kerosene by volume, preferably 0.15 part of butyl acetate, 0.3-0.4 part of n-butanol and 0.45-0.55 part of sulfonated kerosene.

3. The extractant as claimed in claim 2, which consists of 0.15 part by volume of butyl acetate, 0.35 part by volume of n-butanol and 0.50 part by volume of sulfonated kerosene.

4. The extractant of any one of claims 1 to 3, characterized in that: the tungsten-containing solution is a phosphotungstic heteropoly acid solution.

5. The extractant of claim 4, wherein: the volume ratio of the extracting agent to the phosphorus-tungsten heteropoly acid solution is more than or equal to 1-2: 1.

6. the extractant of claim 5, wherein: the volume ratio of the extracting agent to the phosphorus-tungsten heteropoly acid solution is 2-5: 1.

7. the extractant of claim 4, wherein the phosphotungstic heteropoly acid concentration is from 50g/l to 250 g/l.

8. The extractant as claimed in claim 4, characterized in that, at concentrations of phosphotungstic heteropoly acid < 50g/l, the volume ratio of extractant to phosphotungstic heteropoly acid solution is > 2: 1; or when the concentration of the phosphotungstic heteropoly acid is more than 250g/l, the volume ratio of the extracting agent to the phosphotungstic heteropoly acid solution is more than 5: 1.

9. a method for extracting tungsten from phosphotungstic heteropoly acid by using a novel extracting agent is characterized by comprising the following steps: the novel extractant is put into the phosphotungstic heteropoly acid solution, magnetically stirred for 2 to 10 minutes at the speed of 1000-2000rpm and kept stand for 1 to 10 minutes.

10. A method for extracting a tungsten-converted ammonium tungstate/sodium tungstate solution from phosphotungstic heteropoly acid by using a novel extracting agent is characterized by comprising the following steps: the novel extractant is called a blank organic phase, and the organic matter obtained after the blank organic phase is mixed with the heteropoly acid and extracted is called a loaded organic phase; mixing and stirring the loaded organic phase and sodium hydroxide lye with the concentration of 50-100g/l according to the volume ratio of 10-2:1 (preferably 5:1), separating liquid, wherein the lower layer is back-extracted sodium tungstate solution, and the loaded organic phase is changed into a blank organic phase as the upper layer; returning the blank organic phase to the process for re-extraction; or

The novel extractant is called a blank organic phase, and the organic matter obtained after the blank organic phase is mixed with the heteropoly acid and extracted is called a loaded organic phase; uniformly pouring the loaded organic phase into ammonia water, and performing mixing and stirring according to the volume ratio of 10-2:1 (preferably 5:1) to obtain an ammonium tungstate solution; meanwhile, the loaded organic phase is changed into a blank organic phase as an upper layer; the blank organic phase is returned to the process for re-extraction.

Technical Field

The invention relates to the field of metallurgy, in particular to a novel extracting agent and a method for extracting tungsten from phosphotungstic heteropoly acid and converting the tungsten into ammonium tungstate/sodium tungstate solution.

Background

At present, most of tungsten smelting is alkaline leaching and purification and concentration are realized through ion exchange; in the prior art, more amine anion exchange resin is used for adsorbing tungsten, and then ammonia solution is adopted for elution. As the alkalinity can not be thoroughly analyzed relative to the amido on the anion exchange resin, in order to obtain the ammonium tungstate solution with high concentration, high-concentration ammonia water is adopted for desorption, but the desorption rate is lower, so that the desorption solution with high concentration is more difficult to obtain, and the problem of lower resin utilization rate is caused. Meanwhile, the requirement of alkaline ion exchange on tungsten feed liquid (namely, phosphorus-tungsten heteropoly acid solution) is high, and the concentration of tungsten in the tungsten feed liquid is required to be less than (30 g/l); if the concentration of the tungsten feed liquid is higher than (30g/l), water is needed to dilute the tungsten feed liquid, so that the waste of water resources is caused.

Disclosure of Invention

In order to solve the technical problems, the invention provides a novel extracting agent and a method for extracting tungsten from phosphotungstic heteropoly acid and converting the tungsten into ammonium tungstate/sodium tungstate solution. The method can rapidly extract tungsten in the phosphotungstic heteropoly acid under an acidic condition and convert the tungsten into ammonium tungstate/sodium tungstate, and a new path is provided for converting the tungsten into the ammonium tungstate/sodium tungstate; meanwhile, the concentration of the phosphotungstic heteropoly acid extracted by the method is higher, and the extraction effect can reach more than 90 percent; compared with the ion exchange method, the water quantity is greatly saved.

The invention is realized by the following technical scheme:

a method for extracting tungsten from phosphotungstic heteropoly acid and converting the tungsten into ammonium tungstate/sodium tungstate solution comprises the steps of extracting the phosphotungstic heteropoly acid solution by using a novel extracting agent to obtain tungsten, and hydrolyzing the tungsten by using ammonia to obtain the ammonium tungstate solution or hydrolyzing the tungsten by using alkali liquor to obtain the sodium tungstate solution; the novel extractant is composed of 0.1-0.4 part of butyl acetate, 0.2-0.4 part of n-butyl alcohol and 0.3-0.6 part of sulfonated kerosene by volume.

Preferably, the novel extracting agent consists of 0.1 to 0.15 portion of butyl acetate, 0.3 to 0.4 portion of n-butyl alcohol and 0.45 to 0.55 portion of sulfonated kerosene by volume portion.

Preferably, the novel extracting agent consists of 0.15 part by volume of butyl acetate, 0.3-0.4 part by volume of n-butyl alcohol and 0.45-0.55 part by volume of sulfonated kerosene.

Preferably, the novel extracting agent consists of 0.15 part by volume of butyl acetate, 0.35 part by volume of n-butyl alcohol and 0.5 part by volume of sulfonated kerosene.

The butyl acetate is used for extracting tungsten, and the n-butyl alcohol has the function of preventing tungsten precipitation; sulfonated kerosene is used as diluent to increase fluidity.

The addition amount of the extracting agent is more than 1-2 times of the volume of the phosphotungstic acid solution. The dosage of the extracting agent has obvious influence on the extraction effect, and when the concentration of the phosphotungstic heteropoly acid is higher, the volume ratio of the extracting agent is larger; however, when the concentration of the phosphotungstic heteropoly acid is lower (less than or equal to 50g/l), the volume of the extracting agent cannot be reduced, and the extraction rate of 90 percent can be achieved only by the minimum requirement that the extracting agent is equal to the phosphotungstic heteropoly acid solution. Once the concentration of the phosphotungstic heteropoly acid is more than 50g/l, the extraction effect can be ensured only when the volume ratio of the extracting agent to the phosphotungstic heteropoly acid is more than or equal to 2:1, and the extraction effect of the novel extracting agent to the phosphotungstic heteropoly acid is more than 90 percent. Preferably, the concentration of the phosphotungstic heteropoly acid is 50g/l to 250 g/l.

More preferably, the addition amount of the extracting agent is 2-5 times (volume) of the phosphotungstic heteropoly acid solution.

For example, when the phosphotungstic heteropoly acid concentration is less than 50g/l, the volume ratio of the extracting agent to the phosphotungstic heteropoly acid solution is more than 2: 1; or when the concentration of the phosphotungstic heteropoly acid is more than 250g/l, the volume ratio of the extracting agent to the phosphotungstic heteropoly acid solution is more than 5: 1.

the extraction process of the invention adopts magnetic stirring, stirring for 2-10 minutes, standing for 1-10 minutes, and separating liquid.

The magnetic stirring speed is 1000-2000rpm, preferably 2000 rpm.

The method for converting tungsten into sodium tungstate comprises the following steps:

the extractant is called a blank organic phase, and the organic matter obtained after the blank organic phase is mixed with phosphotungstic heteropoly acid and extracted is called a loaded organic phase (organic phase after tungsten extraction); mixing and stirring the loaded organic phase and sodium hydroxide lye with the concentration of 50-100g/l according to the volume ratio of 10-2:1 (preferably 5:1), separating liquid, wherein the lower layer is back-extracted sodium tungstate solution, and the loaded organic phase is changed into a blank organic phase as the upper layer; the blank organic phase can be returned to the process for re-extraction.

The concentration of alkali liquor can be adjusted, the volume ratio of back extraction is 2: 1-10: 1, and the concentration of the alkali liquor is not beyond the range, and the back extraction is specifically adjusted according to the required residual alkalinity of sodium tungstate and the concentration of tungsten tungstate; the volume of the alkali liquor needed by (100g/l) high-alkalinity back extraction is less than that of the low alkalinity (50 g/l).

The method for converting tungsten into ammonium tungstate comprises the following steps:

the extractant is called a blank organic phase, and the organic matter obtained after the blank organic phase is mixed with heteropoly acid and extracted is called a loaded organic phase (organic phase after tungsten extraction); uniformly pouring the loaded organic phase into ammonia water, and performing mixing and stirring according to the volume ratio of 10-2:1, preferably 5:1 (the loaded organic phase: the ammonia water) to obtain an ammonium tungstate solution by back extraction; meanwhile, the loaded organic phase is changed into a blank organic phase as an upper layer; the blank organic phase can be returned to the process for re-extraction.

In the process of converting the ammonium tungstate solution, attention must be paid to a mixing mode of the loaded organic phase and the ammonia water, and if the loaded organic phase and the ammonia water are mixed reversely, a large amount of ammonium tungstate solids are separated out.

Has the advantages that:

1. the extraction agent of the invention has 3 components with different and indispensable effects, butyl acetate is used for extracting tungsten, n-butyl alcohol is used for preventing tungsten precipitation, sulfonated kerosene is used as a diluent to increase fluidity, and the three components are compounded to generate synergistic effect.

2. The novel extractant can quickly extract tungsten in phosphotungstic heteropoly acid under an acidic condition, and then reacts with ammonia water to convert the tungsten into ammonium tungstate, so that a new path is provided for converting the tungsten into the ammonium tungstate. In the process of converting ammonium tungstate/sodium tungstate, the extracting agent can be returned to the process again for repeated use, so that the cost is reduced.

3. The concentration of the phosphotungstic heteropoly acid extracted by the novel extracting agent is higher (50-250 g/l), and the extraction effect can reach more than 90%; even if the concentration is higher than 250g/l, higher extraction rate can be realized by directly increasing the addition amount of the extracting agent. Compared with the ion exchange method for extracting high-concentration phosphotungstic heteropoly acid, the method greatly saves water, can quickly extract, has short standing time and is easy to operate, thereby being more suitable for industrialized use.

Detailed Description

The following detailed description of specific embodiments of the invention is provided, but it should be understood that the scope of the invention is not limited to the specific embodiments.