阅读说明：本技术 钨酸盐溶液的深度除锑的方法 (Deep antimony removal method for tungstate solution ) 是由 申雷霆 尹家军 李小斌 匡兵 周秋生 陈升 彭志宏 熊庆 齐天贵 杨利群 于 2021-10-21 设计创作，主要内容包括：本发明属于净化除杂技术领域,公开了一种钨酸盐溶液的深度除锑的方法。本发明在不影响产品质量的情况下,通过调整钨酸盐溶液中游离硫离子的浓度以及pH值,直接调节酸度或者用蒸发赶氨的方式调整pH值并保证该过程种没有仲钨酸铵析出,降低能耗、节约成本。本发明提供的深度除锑的方法,可将钨酸盐溶液的锑除至0.5ppm以下。(The invention belongs to the technical field of purification and impurity removal, and discloses a method for deeply removing antimony from a tungstate solution. Under the condition of not influencing the product quality, the invention directly adjusts the acidity or adjusts the pH value by an evaporation ammonia-removing mode by adjusting the concentration and the pH value of free sulfur ions in the tungstate solution, ensures that no ammonium paratungstate is separated out in the process, reduces the energy consumption and saves the cost. The method for deeply removing antimony can remove the antimony in the tungstate solution to be less than 0.5 ppm.)

1. A method for deeply removing antimony from a tungstate solution is characterized by comprising the following steps:

(1) adding a vulcanizing agent into the tungstate solution to fully and completely vulcanize Mo, Sb, As and Sn in the solution into MoS₄ ^2-、SbS₄ ^3-、AsS₄ ^3-、SnS₃ ^2-(ii) a Then adding a copper-containing precipitator to generate precipitate; carrying out solid-liquid separation to obtain a filtrate A;

(2) adjusting free S in filtrate A^2-Concentration of (2)<100ppm, the pH value is 6-8, the mixture is stirred for a certain time and then is kept stand, and the red precipitate and the tungstate solution with deep antimony removal are obtained after solid-liquid separation.

2. The method for deeply removing antimony from tungstate solution as recited in claim 1, wherein the temperature of the filtrate A in the step (2) is controlled to be 60-95 ℃, and the filtrate A is naturally cooled while being kept stand.

3. A method for deeply removing antimony from a tungstate solution is characterized by comprising the following steps:

(1) adding a vulcanizing agent into the tungstate solution to fully and completely vulcanize Mo, Sb, As and Sn in the solution into MoS₄ ^2-、SbS₄ ^3-、AsS₄ ^3-、SnS₃ ^2-(ii) a Then adding a copper-containing precipitator to generate precipitate; carrying out solid-liquid separation to obtain a filtrate A;

(2) adjusting free S in filtrate A^2-Concentration of (2)<100ppm, then placing filtrate A in a crystallizing pan>Evaporating ammonia at 50 deg.C, standing, naturally cooling when pH of filtrate A is reduced to 7-8, filtering, and separating to obtain red precipitate and deeply removed antimony tungstate solution.

Technical Field

The invention belongs to the technical field of purification and impurity removal, and particularly relates to a method for deeply removing antimony from a tungstate solution.

Background

With continuous development and utilization of tungsten resources, high-quality tungsten resources are continuously consumed, complex polymetallic associated tungsten ores are more and more commonly utilized, the problem of impurity removal is more and more prominent, and higher impurity elements such as antimony, molybdenum, arsenic, tin and the like still exist in the obtained tungstate solution no matter which tungsten ore decomposition and extraction technology is adopted. In recent years, the requirement of users on the content of impurities in the tungsten metallurgy product ammonium paratungstate is increasingly strict, and the content of antimony, molybdenum, arsenic and tin in APT-0 grade products regulated in GB/T10116-2007 in China does not exceed 5ppm, 20ppm, 10ppm and 2ppm respectively. Therefore, the efficient and economic deep removal of the above impurities from tungstate solutions is an important issue in tungsten metallurgy. For the deep removal of the above impurities from tungstate solutions, the main method is now selective precipitation, and for example, patent publication No. CN1203279A discloses a method for removing molybdenum, arsenic, antimony and tin from tungstate solutions by precipitation, which proposes adding S to a tungstate solution having a pH of 6 to 6.5^2-Or HS^-Sulfurizing to convert molybdenum, arsenic, antimony, tin and other impurities into corresponding thioacid radicals, adding copper-containing matter as precipitant into the sulfurized tungstate solution, combining the thioacid radicals with copper to form insoluble compound precipitate, separating the precipitate containing impurity elements from tungstate solution, and filtering to obtain pure tungstate solution. Patent publication No. CN107447119A discloses a method for removing antimony, molybdenum, arsenic and tin from tungstate solution by sulfurizing antimony with molybdenum, arsenic and tinTo differentiate this characteristic, antimony is removed by preferential sulfidation precipitation, which proposes to add a 2-4 times amount of sulfidizing agent to the tungstate solution under alkaline conditions for sulfidation, to let it stand for 6-8h, where antimony is reduced and completely sulfidized, mainly by SbS^2-In the form of copper or iron-containing precipitant is added to react to form copper-antimony ore (CuSbS) with very low solubility product₂) Or iron antimony ore (FeSb)₂S₄) The method comprises the steps of deeply removing antimony in a solution, filtering, further removing molybdenum, arsenic and tin in a filtrate, adding a vulcanizing agent which is 6-10 times of the total amount of molybdenum, arsenic and tin in the filtrate for vulcanizing, standing for 6-8 hours, adding a copper-containing precipitator after full vulcanization, combining corresponding impurity sulfate radicals and copper into insoluble compound precipitates, separating precipitates containing impurity elements from a tungstate solution, and obtaining the filtrate which is a pure tungstate solution.

Disclosure of Invention

Aiming at the problems in the prior art, the invention aims to provide a method for deeply removing antimony from a tungstate solution, which is simple to operate, easy to control conditions and low in cost.

The invention creatively discovers that the technical scheme can be adopted to deeply remove the antimony in the tungstate solution.

A method for deeply removing antimony from tungstate solution comprises the following steps:

(3) adding a vulcanizing agent into the tungstate solution to fully and completely vulcanize Mo, Sb, As and Sn in the solution into MoS₄ ^2-、SbS₄ ^3-、AsS₄ ^3-、SnS₃ ^2-(ii) a Then adding a copper-containing precipitator to generate precipitate; carrying out solid-liquid separation to obtain a filtrate A;

(4) adjusting free S in filtrate A^2-Concentration of (2)<100ppm, the pH value is 6-8, the mixture is stirred for a certain time and then is kept stand, and the red precipitate and the tungstate solution with deep antimony removal are obtained after solid-liquid separation.

Preferably, in the step (2), the temperature of the filtrate A can be further controlled to be 60-95 ℃, and the filtrate A is naturally cooled while standing.

Meanwhile, in the research process, the creative discovery shows that the following steps can be adopted to replace the step (2) in the method when the ammonium tungstate solution is purified and decontaminated:

adjusting free S in filtrate A^2-Concentration of (2)<100ppm, then placing filtrate A in a crystallizing pan>Evaporating ammonia at 50 deg.C, standing, naturally cooling when pH of filtrate A is reduced to 7-8, filtering, and separating to obtain red precipitate and deeply removed antimony tungstate solution.

It should be noted that precipitation of ammonium paratungstate should be prevented while controlling the pH of filtrate a by evaporating ammonia.

Compared with the prior art, the invention has the following technical effects:

the 2 deep antimony removal methods provided by the invention directly adjust the acidity or adjust the pH value in an evaporation crystallization ammonia removal mode by adjusting the concentration and the pH value of free sulfur ions in the tungstate solution under the condition of not influencing the product quality, ensure that no ammonium paratungstate is separated out in the process, reduce the energy consumption and save the cost.

The method for deeply removing antimony can remove the antimony in the tungstate solution to be less than 0.5 ppm.

Detailed Description

The invention is described in detail below, and the description in this section is merely exemplary and explanatory and should not be construed as limiting the scope of the invention in any way.

Example 1

The pH of the sodium tungstate solution was 10, and the content of W and the content of Mo, Sb, As, and Sn in the sodium tungstate solution were measured and analyzed, and the results are shown in table 1.

TABLE 1 content of W and Mo, Sb, As, Sn in sodium tungstate solution (unit: g/L)

② under the condition of normal temperature stirring, adding sodium sulfide into sodium tungstate solution to make vulcanization, according to the dosage according to theory fully vulcanizing Sb, Mo, As and Sn into SbS₄ ^3-、MoS₄ ^2-、AsS₄ ^3-、SnS₃ ^2-Adding 4 times of the amount of the copper sulfate solution, stopping stirring and standing for 3 hours after the addition is finished, adding a copper sulfate solution which is completely precipitated and removed by 4 times of the theoretical amount of Mo, AS, Sn and Sb into the mixture, stirring for 0.5 hour, standing for 8 hours, and performing solid-liquid separation to obtain a filtrate A. The contents of Sb, Mo, As and Sn in the filtrate A were measured and analyzed, and the results are shown in Table 2.

TABLE 2 content of Sb, Mo, As and Sn in the filtrate A (unit: g/L)

Comparing the data in tables 1 and 2, it can be easily found that the removal effect of Sb is very undesirable when the copper sulfate solution is added to remove impurities after the sodium tungstate solution is vulcanized.

Thirdly, heating the filtrate A to 75-80 ℃, adjusting the pH value of the filtrate A to 6.5-7 by hydrochloric acid, stirring for 3 hours, standing, and carrying out solid-liquid separation to obtain a red solid and a sodium tungstate solution after antimony removal.

The red solid was collected and analyzed for phase and the results are shown in Table 3. It was judged that the main component of the red solid was a compound of Sb and S.

TABLE 3 analysis of red solid phase

Further analysis of the Sb content in the sodium tungstate solution after antimony removal showed that the Sb content was 0.0078 g/L.

Example 2

pH of the ammonium tungstate solution was 9, and the content of W and the content of Mo, Sb, As, and Sn in the ammonium tungstate solution were measured and analyzed, and the results are shown in table 4.

TABLE 4W content and Mo, Sb, As, Sn content (unit: g/L) of ammonium tungstate solution

② under the condition of normal temperature stirring, adding sodium sulfide into ammonium tungstate solution to make vulcanization, according to the dosage according to theory fully vulcanizing Sb, Mo, As and Sn into SbS₄ ^3-、MoS₄ ^2-、AsS₄ ^3-、SnS₃ ^2-Adding 4 times of the amount of the copper sulfate solution, stopping stirring and standing for 3 hours after the addition is finished, adding a copper sulfate solution which is completely precipitated and removed by 4 times of the theoretical amount of Mo, AS, Sn and Sb into the mixture, stirring for 0.5 hour, standing for 8 hours, and performing solid-liquid separation to obtain a filtrate A. The contents of Sb, Mo, As and Sn in the filtrate A were measured and analyzed, and the results are shown in Table 5.

TABLE 5 content of Sb, Mo, As and Sn in the filtrate A (unit: g/L)

Comparing the data in tables 3 and 4, it can be easily found that the removal effect of Sb is very undesirable when adding the copper sulfate solution to remove impurities after the ammonium tungstate solution is vulcanized.

Thirdly, placing the filtrate A in a crystallizing pan, heating to 80 ℃ for ammonia distillation, controlling the pH value of the filtrate A to be close to but not lower than 7, standing after red solids appear in the filtrate A, and carrying out solid-liquid separation to obtain the red solids and the ammonium tungstate solution after antimony removal.

The red solid was collected and analyzed for phase and the results are shown in Table 6. It was judged that the main component of the red solid was a compound of Sb and S.

TABLE 6 analysis of red solid phase

Further analysis of the Sb content in the antimony-removed ammonium tungstate solution revealed that the Sb content was 0.008 g/L.

Example 3

The pH of the sodium tungstate solution was 10, and the content of W and the content of Mo, Sb, As, and Sn in the sodium tungstate solution were measured and analyzed, and the results are shown in table 7.

TABLE 7 content of W and Mo, Sb, As, Sn in sodium tungstate solution (unit: g/L)

② under the condition of normal temperature stirring, adding sodium sulfide into sodium tungstate solution to make vulcanization, according to the dosage according to theory fully vulcanizing Sb, Mo, As and Sn into SbS₄ ^3-、MoS₄ ^2-、AsS₄ ^3-、SnS₃ ^2-Adding 4 times of the amount of the copper sulfate solution, stopping stirring and standing for 3 hours after the addition is finished, adding a copper sulfate solution which is completely precipitated and removed by 4 times of the theoretical amount of Mo, AS, Sn and Sb into the mixture, stirring for 0.5 hour, standing for 8 hours, and performing solid-liquid separation to obtain a filtrate A. The contents of Sb, Mo, As and Sn in the filtrate A were measured and analyzed, and the results are shown in Table 8.

TABLE 8 content of Sb, Mo, As and Sn in the filtrate A (unit: g/L)

Comparing the data in tables 7 and 8, it can be easily found that the removal effect of Sb is very undesirable when the copper sulfate solution is added to remove impurities after the sodium tungstate solution is vulcanized.

Thirdly, heating the filtrate A to 75-80 ℃, adjusting the pH value of the filtrate A to 7-8 by hydrochloric acid, stirring for 3 hours, standing, and carrying out solid-liquid separation to obtain a red solid and a sodium tungstate solution after antimony removal.

Further analysis of the Sb content in the sodium tungstate solution after antimony removal showed that it was 0.0046 g/L.

Those not described in detail in the specification are prior art known to those skilled in the art.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.