阅读说明：本技术 一种锌湿法冶炼除铜剂及其应用方法 (Copper removing agent for zinc hydrometallurgy and application method thereof ) 是由 孙伟 杨越 宋绍乐 韩海生 王丽 吕斐 于 2020-06-23 设计创作，主要内容包括：本发明涉及一种锌湿法冶炼除铜剂及其应用方法,属于溶液除铜技术领域。所述除铜剂所述除铜剂中含有活化的硫化锌；所述活化的硫化锌为制备好,且储存时间小于等于4天的硫化锌。其应用为：将所述除铜剂加入到含铜的锌冶炼浸出液中,搅拌反应,反应后过滤。采用本发明所设计的除铜剂用于除去锌湿法冶炼浸出液中的铜,铜的去除率可达99％以上、同时锌的损失率小于1％。本发明组分设计合理,应用工艺简单可控,所得效果优良,便于大规模的工业化应用。(The invention relates to a copper removing agent for zinc hydrometallurgy and an application method thereof, belonging to the technical field of solution copper removal. The copper removing agent contains activated zinc sulfide; the activated zinc sulfide is prepared and has a storage time of less than or equal to 4 days. The application is as follows: and adding the copper removing agent into the copper-containing zinc smelting leaching solution, stirring for reaction, and filtering after the reaction. The copper removing agent designed by the invention is used for removing copper in zinc hydrometallurgy leaching solution, the removal rate of copper can reach more than 99%, and the loss rate of zinc is less than 1%. The invention has reasonable component design, simple and controllable application process, excellent effect and convenient large-scale industrial application.)

1. A copper removing agent for zinc hydrometallurgy is characterized in that: the copper removing agent contains activated zinc sulfide; the activated zinc sulfide is prepared and stored for less than or equal to 4 days;

the activated zinc sulfide is prepared by the following method:

adding a soluble zinc salt and a soluble sulfide to water; stirring; filtering to obtain the activated zinc sulfide; wherein the molar ratio of the zinc element to the sulfur element in the sulfide is not less than 1, preferably not less than 1.

2. The zinc hydrometallurgical decoppering agent of claim 1, wherein: the soluble zinc salt is at least one selected from zinc sulfate, zinc nitrate and zinc chloride.

3. The zinc hydrometallurgical decoppering agent of claim 1, wherein: the soluble sulfide is at least one selected from calcium sulfide, sodium sulfide, barium sulfide and manganese sulfide.

4. The zinc hydrometallurgical decoppering agent of claim 1, wherein: the mol ratio of the zinc element to the sulfur element in the sulfide is 1.05: 1-1.2: 1. Zinc sulfate: sulfide 1.1: 1.

5. The zinc hydrometallurgical decoppering agent of claim 1, wherein: when preparing the activated zinc sulfide, the liquid-solid ratio is 4-6 mL: 1g of the total weight of the composition.

6. The use of the zinc hydrometallurgical decoppering agent of any one of claims 1 to 5, characterized in that: and adding the copper removing agent into the copper-containing zinc smelting leaching solution, stirring for reaction, and filtering after the reaction.

7. The use of a zinc hydrometallurgical decoppering agent according to claim 6; the method is characterized in that: the adding amount of the copper removing agent for zinc hydrometallurgy is 1.1-1.3 times of the molar amount of copper in the solution.

8. The use of a zinc hydrometallurgical decoppering agent according to claim 6; the method is characterized in that: the stirring reaction time is 10-30 min.

9. The use of a zinc hydrometallurgical decoppering agent according to claim 7; the method is characterized in that: when stirring reaction is carried out, the pH value of the system is controlled to be 1-2.

10. The use of a zinc hydrometallurgical decoppering agent according to claim 7; the method is characterized in that: the copper removal rate is more than 99%, and the zinc loss rate is less than 1%.

Technical Field

The invention relates to a copper removing agent for zinc hydrometallurgy and an application method thereof, belonging to the technical field of solution copper removal.

Technical Field

As the consumption of zinc increases, the content and grade of primary zinc resources are decreasing. Therefore, from the aspects of resource utilization and environmental protection, the smelting slag with high zinc content as a secondary resource must be further processed and recycled to promote the sustainable development of the zinc industry in the future.

However, there are many impurity elements contained in zinc smelting slag, including particularly a large amount of copper. When zinc slag is leached, copper inevitably enters the leaching solution together with zinc, and the concentration of the copper in the leaching solution is higher, usually more than 500mg/L, but the ion requirement of zinc electrolysis on the solution is higher, and the electrolytic extraction of zinc is seriously damaged by the existence of copper ions. Therefore, in the hydrometallurgical process of zinc dross, copper ions need to be removed by various methods prior to zinc electrolysis.

The traditional copper removal method generally comprises a displacement copper removal method and a hydrolysis precipitation copper removal method. The displacement copper removing method is that according to different metal activities, copper ions in solution are displaced by metal with high flexibility, zinc powder is generally used for displacement copper removing in a wet smelting process, but the price of zinc metal is gradually increased, and the cost of copper removing by using the zinc powder is high in the process. The hydrolysis precipitation copper-removing method utilizes the hydrolyzability of copper ions in a solution to generate insoluble and stable copper hydroxide precipitation for copper removal by adjusting the pH value of the solution, but when the solution contains a large amount of zinc ions, zinc hydroxide precipitation can be preferentially generated due to too high zinc concentration during pH adjustment, so that the purpose of copper removal cannot be achieved. In recent years, many researchers have attempted to improve the conventional methods by removing copper through extraction, adsorption, ion exchange, etc., but they have not achieved the desired results. The extraction method has good copper removal effect, more thorough copper removal and high metal recovery rate, but has more extraction stages, long extraction line, complex operation, large equipment investment and higher power consumption. The adsorption method is to use porous solid material to make copper in solution adsorbed on the surface of the solid material. However, this method requires a large number of control conditions, such as particle size of the adsorbent, addition amount, and composition of the solution, which increase the difficulty of operation.

The invention aims to solve the technical problem of overcoming the defects of the existing copper removal process and provide the purification and copper removal method which has the advantages of short process flow, thorough copper removal, simple and convenient operation and low operation cost.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a copper removing agent for zinc hydrometallurgy and an application method thereof.

In order to achieve the above object, the present invention adopts the following aspects.

The invention relates to a copper removing agent for zinc hydrometallurgy, which is characterized in that: the copper removing agent contains activated zinc sulfide; the activated zinc sulfide is prepared and stored for less than or equal to 4 days;

the activated zinc sulfide is prepared by the following method:

adding a soluble zinc salt and a soluble sulfide to water; stirring; filtering to obtain the activated zinc sulfide; wherein the molar ratio of the zinc element to the sulfur element in the sulfide is not less than 1, preferably not less than 1.

In the present invention, the activated zinc sulphide is used in the copper-containing zinc smelting leach solution preferably within 24 hours after its preparation. As a further preference, the copper-containing zinc smelt leach solution is used within 12 hours. Over time, the copper removal effect is significantly reduced.

The invention relates to a zinc hydrometallurgy decoppering agent, wherein soluble zinc salt is selected from at least one of zinc sulfate, zinc chloride and zinc nitrate. More preferably zinc sulfate.

The invention relates to a copper removing agent for zinc hydrometallurgy, wherein soluble sulfide is selected from at least one of calcium sulfide, sodium sulfide, barium sulfide and manganese sulfide.

The invention relates to a copper removing agent for zinc hydrometallurgy, which contains amorphous zinc sulfide.

The invention relates to a copper removing agent for zinc hydrometallurgy, wherein the mol ratio of zinc element to sulfur element in sulfide is 1.05: 1-1.3: 1. Preferably 1.1: 1-1.3: 1.

The invention relates to a zinc hydrometallurgy decoppering agent, which is prepared by distributing and taking zinc sulfate and sulfide according to a design group, stirring the zinc sulfate, the sulfide and water at normal temperature for 5-30 minutes, and separating solids after filtering to obtain the decoppering agent. The copper removing agent is used for subsequent copper removal.

The invention relates to a copper removing agent for zinc hydrometallurgy, which is characterized in that when activated zinc sulfide is prepared, the liquid-solid ratio is 4-6 mL: 1g of the total weight of the composition.

The invention relates to an application of a copper removing agent for zinc hydrometallurgy. In industrial application, the following options are provided: firstly, zinc sulfate and sulfide react in water to prepare active zinc sulfide, then the active zinc sulfide is added into a copper-containing zinc solution for copper removal within 4 days, and after the reaction, the solution is separated from precipitate through filtration, so that the purpose of copper removal is achieved. As a further preferable scheme, after zinc sulfate and sulfide react in water to prepare active zinc sulfide, the zinc sulfide and the solution are added into a copper-containing zinc solution together to remove copper, and after the reaction, the solution is filtered to separate from precipitate, so that the purpose of removing copper is achieved.

The application of the copper removing agent for zinc hydrometallurgy is characterized in that the adding amount of the copper removing agent for zinc hydrometallurgy is 1.1-1.3 times of the molar amount of copper in the solution. When the copper removing agent is applied to the industry, the copper removing rate is low and the copper is not completely removed due to too little copper removing agent; if the zinc is excessively added, the components in the solution are not affected, but precipitation is increased, the grade of precipitated slag is reduced, and the loss of zinc during filtration is increased.

The application of the copper removing agent for zinc hydrometallurgy is characterized in that the stirring reaction time is 10-30 min.

In a preferable scheme, the concentration of zinc in the copper-containing zinc smelting leachate is 140g/L, and the concentration of copper is 500-1000 mg/L.

Preferably, the reaction is carried out with stirring at a rate of 250-350 rpm.

The application of the copper removing agent for zinc hydrometallurgy provided by the invention is characterized in that the pH value of a system is controlled to be 1-2 during stirring reaction.

According to the application of the copper removing agent for zinc hydrometallurgy, the removal rate of copper is more than 99%, the loss rate of zinc is less than 1%, the removal rate of copper after optimization is more than 99.5%, and the loss rate of zinc is less than 0.5%. The invention realizes the high-efficiency and quick removal of copper on the premise of ensuring the trace loss of zinc.

The invention relates to a zinc hydrometallurgy decoppering agent and an application method thereof, wherein water-soluble zinc salt (preferably zinc sulfate) reacts with sulfide in water to prepare active zinc sulfide, and the solid-liquid separation is realized by utilizing the infusible characteristic of the zinc sulfide in the water; the surface of the separated solid zinc sulfide carries water and contains a certain amount of amorphous zinc sulfide; when the zinc sulfide with moisture and a certain amount of amorphous zinc sulfide is used for removing copper in a zinc leaching solution within a specified time, new impurity ions cannot be introduced into a zinc smelting system; and the copper removal speed and efficiency are obviously improved. When the sodium sulfide is directly used for precipitating copper, the copper sulfide is precipitated from the solution and can be filtered and separated, but sodium ions can enter the solution and are accumulated all the time when water is recycled, and the sodium ion concentration in the solution reaches dozens of grams per liter, and the sodium ions can be crystallized out, so that the loss of the zinc ions is caused. In addition, the copper removal effect of directly using sodium sulfide is not as good as the copper removal effect of active zinc sulfide prepared with the same amount of sodium sulfide.

Detailed Description