阅读说明：本技术 一种钨的提取工艺及其应用 (Tungsten extraction process and application thereof ) 是由 陈星宇 赵中伟 刘旭恒 王鸿 刘朋远 李江涛 何利华 孙丰龙 于 2021-08-30 设计创作，主要内容包括：本发明公开了一种钨的提取工艺及其应用,上述钨的提取工艺包括：将钨矿原料与钨酸盐溶液在酸性条件下混合,加热反应将钨溶出,随后固液分离,再将滤液进行后处理,即得钨产品；后处理至少包括,采用阳离子交换树脂或萃取剂将滤液中的阳离子吸附得到偏钨酸溶液,再将偏钨酸溶液干燥或热解得到钨单质和/或氧化钨产品。本发明利用钨酸根离子在酸性条件下所具有的强自配位能力,直接将钨矿原料中的钨高效溶出,溶出提取率高；本发明的提取工艺流程更加简化,且所得到的钨产品的经济价值更高；本发明的提取工艺设计科学合理,过程可控性强,经济性和环保性好,实际应用前景广阔。(The invention discloses a tungsten extraction process and application thereof, wherein the tungsten extraction process comprises the following steps: mixing tungsten ore raw materials with tungstate solution under an acidic condition, heating to react to dissolve out tungsten, then carrying out solid-liquid separation, and carrying out post-treatment on the filtrate to obtain a tungsten product; and the post-treatment at least comprises adsorbing cations in the filtrate by adopting cation exchange resin or an extracting agent to obtain a metatungstic acid solution, and drying or pyrolyzing the metatungstic acid solution to obtain a tungsten simple substance and/or a tungsten oxide product. According to the invention, the strong self-coordination capacity of tungstate ions under an acidic condition is utilized, so that tungsten in the tungsten ore raw material is directly and efficiently dissolved out, and the dissolution extraction rate is high; the extraction process flow is simplified, and the obtained tungsten product has higher economic value; the extraction process of the invention has scientific and reasonable design, strong process controllability, good economy and environmental protection and wide practical application prospect.)

1. A process for extracting tungsten is characterized in that,

the method comprises the following steps:

mixing tungsten ore raw materials with tungstate solution under an acidic condition, heating to react to dissolve out tungsten, then carrying out solid-liquid separation, and carrying out post-treatment on the filtrate to obtain a tungsten product.

2. The extraction process of tungsten according to claim 1,

the pH of the tungstate solution is 1-7.

3. The extraction process of tungsten according to claim 1,

the concentration of the tungstate solution is 0.1-2 mol/L.

4. The extraction process of tungsten according to claim 3,

the tungstate solution at least contains one of ammonium tungstate, sodium tungstate and potassium tungstate.

5. The extraction process of tungsten according to any one of claims 1 to 4,

the temperature of the heating reaction is controlled to be 50-200 ℃;

and/or the heating reaction time is 0.5-4.0 h.

6. The extraction process of tungsten according to any one of claims 1 to 5,

the addition amount of the tungstate solution is controlled in such a way that the solid-to-liquid ratio of the tungsten ore raw material to the tungstate solution is 1 g: 1-10m 1.

7. The extraction process of tungsten according to any one of claims 1 to 5,

the tungsten ore raw material is at least one of scheelite, artificial scheelite, mixed wolframite and scheelite, wolframite and artificial wolframite.

8. The extraction process of tungsten according to any one of claims 1 to 7,

the post-treatment comprises adsorbing cations in the filtrate by adopting cation exchange resin or an extracting agent to obtain a metatungstic acid solution; and drying or pyrolyzing the metatungstic acid solution to obtain a tungsten simple substance and/or a tungsten oxide product.

9. The extraction process of tungsten according to claim 8,

the post-treatment is specifically that the filtrate is separated into two parts after absorbing the cation to obtain a metatungstic acid solution, one part is dried or pyrolyzed to prepare a tungsten product, and the other part is diluted and/or adjusted in pH value and then returned to react with the tungsten ore raw material.

10. Use of the tungsten extraction process of any one of claims 1 to 9 in tungsten smelting.

Technical Field

The invention belongs to the technical field of extraction of nonferrous metals, and particularly relates to an extraction process of tungsten and application thereof.

Background

Tungsten is widely applied to various industries as a strategic rare metal; the tungsten is mainly extracted from wolframite or scheelite.

The mainstream tungsten smelting technology at present is to use alkali to press and boil tungsten ore or tungsten-containing raw materials to obtain a crude sodium tungstate solution, then use ion exchange or solvent extraction to convert the crude sodium tungstate solution into an ammonium tungstate solution, and then obtain ammonium paratungstate through evaporation and crystallization; the process can treat various types of tungsten raw materials and has strong adaptability.

However, in order to prepare qualified tungsten products, the above process requires the use of an ammonium (ammonia) reagent, thereby causing the discharge of a large amount of ammonia-nitrogen wastewater and causing environmental pollution; moreover, only tungsten metallurgy products can be produced, and the value is low.

In view of this, research and development of a tungsten extraction process with good economical efficiency and environmental protection, simple and controllable process, and high product value is needed.

Disclosure of Invention

In view of this, the present invention provides a tungsten extraction process and applications thereof.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a process for extracting tungsten, comprising:

mixing tungsten ore raw materials with tungstate solution under an acidic condition, heating to react to dissolve out tungsten, then carrying out solid-liquid separation, and carrying out post-treatment on the filtrate to obtain a tungsten product.

In the technical scheme, the pH value of the tungstate solution is 1-7.

In detail, in the above technical scheme, tungsten in the tungsten ore raw material exists in the form of non-polymerized tungstate radical, and the tungstate solution is polymerized under the acidic condition (the stable existence of pH is 1-7, tungstic acid precipitate is formed when the pH is less than 1, and tungstic acid radical is formed when the pH is more than 7); when tungstate radicals with a certain degree of polymerization contact tungsten ore without polymerization, the tungstate radicals in the tungsten ore can generate polymerization reaction with the polymerized tungstate radicals, so that the tungsten ore is dissolved, the lower the pH of a tungstate solution is, the more favorable the dissolution of the tungsten ore is, but the pH of the tungstate solution cannot be lower than 1, otherwise, tungstic acid precipitation can occur, and the tungsten ore cannot be dissolved.

In the technical scheme, the concentration of the tungstate solution is 0.1-2 mol/L.

Specifically, in the above technical solution, the tungstate solution at least contains one of ammonium tungstate, sodium tungstate, and potassium tungstate.

Further, in the above technical scheme, the temperature of the heating reaction is controlled to be 50-200 ℃.

Further, in the above technical scheme, the heating reaction time is 0.5-4.0 h.

Furthermore, in the technical scheme, the addition amount of the tungstate solution is controlled in such a way that the solid-to-liquid ratio of the tungsten ore raw material to the tungstate solution is 1 g: 1-10 ml.

Still further, in the above technical solution, the tungsten ore raw material is at least one of scheelite, artificial scheelite, mixed wolframite and scheelite, wolframite, and artificial wolframite.

Still further, in the above technical solution, the post-treatment comprises adsorbing cations in the filtrate with a cation exchange resin or an extractant to obtain a metatungstic acid solution; and drying or pyrolyzing the metatungstic acid solution to obtain a tungsten simple substance and/or a tungsten oxide product.

In a preferred embodiment of the invention, the post-treatment is specifically that after the filtrate is subjected to cation adsorption to obtain a metatungstic acid solution, the metatungstic acid solution is divided into two parts, wherein one part is dried or pyrolyzed to obtain a tungsten product, and the other part is diluted and/or adjusted in pH value and then returned to react with the tungsten ore raw material.

The invention also provides application of the tungsten extraction process in tungsten smelting.

Compared with the prior art, the invention has the following advantages:

(1) according to the extraction process of tungsten provided by the invention, the strong self-coordination capacity of tungstate ions under an acidic condition is utilized, tungsten in a tungsten ore raw material can be directly and efficiently dissolved out, and the dissolution extraction rate is high;

(2) compared with the existing mainstream tungsten smelting technology, the extraction and smelting process of the tungsten provided by the invention is simpler, and the economic value of the extracted and prepared tungsten product is higher;

(3) the extraction process of tungsten provided by the invention has the advantages of scientific and reasonable design, strong process controllability, good economical efficiency and environmental protection and wide practical application prospect.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.

It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In the examples, the means used are conventional in the art unless otherwise specified.

The terms "comprises," "comprising," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

The embodiment of the invention provides a tungsten extraction process, which specifically comprises the following steps:

mixing tungsten ore raw material (at least one of scheelite, artificial scheelite, mixed wolframite and scheelite, wolframite and artificial wolframite) with tungstate solution with pH of 1.0-7.0, heating to 50-200 ℃, reacting for 0.5-4.0h to dissolve out tungsten, then carrying out solid-liquid separation, and carrying out post-treatment on the filtrate to obtain the tungsten product.

Wherein the concentration of the tungstate solution is 0.1-2 mol/L; the tungstate solution may be one or more of ammonium tungstate aqueous solution, sodium tungstate aqueous solution and potassium tungstate aqueous solution.

In detail, the addition amount of the tungstate solution is controlled in such a way that the solid-to-liquid ratio of the tungsten ore raw material to the tungstate solution is 1 g: 1-10m 1.

In detail, the post-treatment at least comprises adsorbing cations in the filtrate by adopting cation exchange resin or an extracting agent to obtain a metatungstic acid solution; and drying or pyrolyzing the metatungstic acid solution to obtain a tungsten simple substance and/or a tungsten oxide product.

In a preferred embodiment of the present invention, the post-treatment specifically includes that after the filtrate is subjected to cation adsorption to obtain a metatungstic acid solution, the metatungstic acid solution is divided into two parts, one part of the metatungstic acid solution is subjected to spray drying or spray pyrolysis to obtain tungsten products (tungsten oxide, blue tungsten, purple tungsten and tungsten powder), and the other part of the metatungstic acid solution is subjected to dilution and/or pH adjustment and then returned to react with the tungsten ore raw material.

Example 1

The embodiment of the invention provides a tungsten extraction process, which specifically comprises the following steps:

s1, mixing and stirring a sodium metatungstate solution (a tungstate solution with the pH value of 1-4) and powdery artificial scheelite (the content of tungsten trioxide is 72 wt%) at the ratio of 5mL to 1g, wherein the concentration of the sodium metatungstate solution is 200g/L, pH and the concentration of the sodium metatungstate solution is 2.8, and reacting for 2 hours at the reaction temperature of 90 ℃;

s2, after the reaction is finished, carrying out solid-liquid separation to obtain calcium metatungstate filtrate with the tungsten trioxide concentration of 340.8g/L and filter residue with the tungsten trioxide content of 0.48 wt%;

s3, adsorbing the calcium metatungstate filtrate obtained in the step S2 by using a commercial 732 resin to obtain an ion-exchanged metatungstate solution, separating the metatungstate solution by 60%, diluting to 200g/L, adjusting the pH to 2.8, returning to the step S1 to react with artificial scheelite, and directly carrying out spray thermal decomposition on the remaining 40% of metatungstate solution at 300 ℃ to obtain a tungsten trioxide product.

Through detection, the leaching rate of tungsten in the artificial scheelite reaches up to 99.5 percent; the purity of the prepared tungsten trioxide reaches the national 0-grade product requirement.

Example 2

The embodiment of the invention provides a tungsten extraction process, which specifically comprises the following steps:

s1, mixing and stirring a potassium tungstate solution with the concentration of 150g/L, pH of 5.5 and powdery scheelite (the content of tungsten trioxide is 50 wt%) according to the liquid-solid ratio of 8mL to 1g for reaction, controlling the reaction temperature to be 185 ℃, and reacting for 0.5 h;

s2, after the reaction is finished, carrying out solid-liquid separation to obtain calcium paratungstate filtrate with the tungsten trioxide concentration of 212g/L and filter residue with the tungsten trioxide content of 0.72 wt%;

s3, extracting the calcium paratungstate filtrate obtained in the step S2 by using a commercially available P204 extraction agent to obtain an extracted metatungstic acid solution, separating 60% of the metatungstic acid solution, diluting to 150g/L, adjusting the pH value to 5.5, returning to the step S1 to react with scheelite, and directly carrying out spray pyrolysis on the remaining 40% of the metatungstic acid solution at 680 ℃ under the condition of introducing hydrogen to obtain a blue tungsten product.

Through detection, the leaching rate of tungsten in the scheelite reaches up to 99.2 percent; the purity of the prepared blue tungsten reaches the national 0-grade product requirement.

Example 3

The embodiment of the invention provides a tungsten extraction process, which specifically comprises the following steps:

s1, mixing and stirring an ammonium metatungstate solution with a concentration of 250g/L, pH of 3.5 and powdered artificial wolframite (the content of tungsten trioxide is 68 wt%) according to a liquid-solid ratio of 3mL to 1g for reaction, controlling the reaction temperature to be 120 ℃, and reacting for 0.5 h;

s2, after the reaction is finished, carrying out solid-liquid separation to obtain calcium metatungstate filtrate with the tungsten trioxide concentration of 485.2g/L and filter residue with the tungsten trioxide content of 0.35 wt%;

s3, extracting the calcium metatungstate filtrate obtained in the step S2 by using a commercially available P507 extraction agent to obtain an extracted metatungstate solution, separating 60% of the metatungstate solution, diluting to 250g/L, adjusting the pH to 3.5, returning to the step S1 to react with scheelite, and directly carrying out spray pyrolysis on the remaining 40% of the metatungstate solution at 950 ℃ under the condition of introducing hydrogen to obtain spherical tungsten powder.

Through detection, the leaching rate of tungsten in the artificial wolframite reaches up to 99.5 percent; the purity of the prepared spherical tungsten powder is the national 0-grade product requirement.

Example 4

The embodiment of the invention provides a tungsten extraction process, which specifically comprises the following steps:

s1, mixing and stirring a sodium metatungstate solution with the concentration of 180g/L, pH of 2.0 and powdered wolframite (the content of tungsten trioxide is 65 wt%) according to the liquid-solid ratio of 5mL to 1g for reaction, controlling the reaction temperature to be 185 ℃, and reacting for 0.5 h;

s2, after the reaction is finished, carrying out solid-liquid separation to obtain calcium metatungstate filtrate with the tungsten trioxide concentration of 308g/L and filter residue with the tungsten trioxide content of 0.79 wt%;

s3, adsorbing the calcium metatungstate filtrate obtained in the step S2 by using a 732 commercially available resin to obtain an adsorbed metatungstate solution, separating the metatungstate solution by 60%, diluting to 180g/L, adjusting the pH value to 2.0, returning to the step S1 to react with wolframite, and directly carrying out spray thermal decomposition on the remaining 40% of metatungstate solution at 650 ℃ to obtain a tungsten oxide product.

Through detection, the leaching rate of tungsten in the wolframite reaches up to 99.1 percent; the purity of the prepared tungsten oxide reaches the national 0-grade product requirement.

Comparative example 1

The invention provides a tungsten extraction process, which specifically comprises the following steps:

s1, mixing and stirring a sodium tungstate solution with the concentration of 200g/L, pH of 7.2 and powdered artificial scheelite (the content of tungsten trioxide is 72 wt%) according to the liquid-solid ratio of 5mL to 1g for reaction, controlling the reaction temperature to be 90 ℃, and reacting for 2 hours;

s2, after the reaction is finished, carrying out solid-liquid separation to obtain calcium metatungstate filtrate with the tungsten trioxide concentration of 200g/L and filter residue with the tungsten trioxide content of 72 wt%;

s3, adsorbing the sodium metatungstate filtrate obtained in the step S2 by using a 732 commercially available resin to obtain an ion-exchanged metatungstic acid solution, and separating the metatungstic acid solution into 40% of metatungstic acid solution to directly perform spray pyrolysis at 300 ℃ to obtain a tungsten trioxide product.

Through detection, the leaching rate of tungsten in the artificial scheelite is 0 percent; the purity of the prepared tungsten trioxide is a national grade 0 product.

Comparative example 2

The invention provides a tungsten extraction process, which specifically comprises the following steps:

s1, mixing and stirring an ammonium metatungstate solution with a concentration of 250g/L, pH of 3.5 and powdered artificial wolframite (the content of tungsten trioxide is 68 wt%) according to a liquid-solid ratio of 3mL to 1g for reaction, controlling the reaction temperature to be 40 ℃, and reacting for 0.5 h;

s2, after the reaction is finished, carrying out solid-liquid separation to obtain calcium metatungstate filtrate with the tungsten trioxide concentration of 380g/L and filter residue with the tungsten trioxide content of 29 wt%;

s3, extracting the calcium metatungstate filtrate obtained in the step S2 by using a commercially available P507 extraction agent to obtain an extracted metatungstate solution, separating 60% of the metatungstate solution, diluting to 250g/L, adjusting the pH to 3.5, returning to the step S1 to react with scheelite, and directly carrying out spray pyrolysis on the remaining 40% of the metatungstate solution at 950 ℃ under the condition of introducing hydrogen to obtain spherical tungsten powder.

Through detection, the leaching rate of tungsten in the artificial wolframite reaches 57 percent; the purity of the prepared spherical tungsten powder is the national 0-grade product requirement.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention.

It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.