A method for efficiently and deeply removing copper from a nickel-containing solution

Abstract

The present application relates to a kind of from the method for efficiently deep copper removal in nickel-containing solution, the method includes the following steps: the pH of nickel-containing solution is adjusted to 3-5, by mass ratio M 含硫氨基酸 :M 铜 =2~10:1 ratio, sulfur-containing amino acid is added to nickel-containing solution, control solution temperature is 5-50 ℃, fully mixed until completely dissolved, obtain mixed solution;The mixed solution is heated to 50~95 ℃, adjust pH to 0.5-1.5 to react;After reaction is completed, solid-liquid separation is obtained, and copper removal after liquid and copper removal residue;The present application can realize the deep removal of copper in nickel-containing solution, provides high-quality raw material for the preparation of high-purity nickel product;While effectively controlling the loss of nickel in the process of copper removal, the obtained copper removal residue can be directly treated as copper smelting raw material;In addition, the process of the present method is short, simple operation, easy to industrial application.

Description

Technical Field

[0001] This invention relates to the field of hydrometallurgical technology for nickel, and more specifically, to a method for efficient and deep removal of copper from nickel-containing solutions. Background Technology

[0002] With the continuous development of technology, the demand for high-quality nickel is increasing. For example, in the preparation of high-purity nickel targets, the purity control requirements are extremely high. For high-purity nickel targets used in processes below 65nm, the purity has been gradually increased from 4N5 (99.995%) to 5N (99.999%) and above. In the electrolytic refining process of metallic nickel, the composition of the electrolyte significantly affects product quality, especially the impact of copper impurities. Because copper preferentially deposits on the electrode compared to nickel, it is necessary to thoroughly remove copper from the electrolyte before nickel electrolysis; otherwise, the quality of the electrolytic nickel product will be severely affected. Traditional copper removal methods mainly involve sulfide precipitation, the basic principle of which is to use sulfiding agents such as sodium sulfide and hydrogen sulfide to react with copper ions to generate copper sulfide precipitate, thereby removing copper. Based on this, methods such as active nickel sulfide copper removal and nickel thiocarbonate copper removal have been developed. These methods all have drawbacks, such as insufficient copper removal depth, making it difficult to achieve a residual copper concentration in the solution below 2 mg / L; some nickel is co-precipitated, resulting in a large loss of nickel, with the nickel-copper ratio in the copper removal slag even reaching 2:1, making the copper removal slag unusable in copper smelting systems and causing subsequent copper removal slag treatment to be very cumbersome; and the addition of a large amount of sulfides poses a safety risk of hydrogen sulfide release. Summary of the Invention

[0003] Based on the aforementioned technical problems in the prior art, the present invention provides a method for efficient and deep removal of copper from nickel-containing solutions. This method involves adjusting the pH of the nickel-containing solution to ensure that sulfur-containing amino acids are completely dissolved in the solution, then adjusting the pH of the mixed solution containing the dissolved sulfur-containing amino acids to decrease and raising the temperature to carry out the reaction, thereby effectively removing copper ions from the nickel-containing solution with a low loss rate of nickel ions.

[0004] To achieve the above objectives, the technical solution of the present invention is as follows:

[0005] A method for efficient and deep removal of copper from a nickel-containing solution includes the following steps:

[0006] S1. Adjust the pH of the nickel-containing solution to 3-5, according to mass ratio M 含硫氨基酸 :M 铜 Sulfur-containing amino acids are added to a nickel-containing solution in a ratio of 2 to 10:1, and the solution temperature is controlled at 5-50℃. The mixture is thoroughly mixed until completely dissolved to obtain a mixed solution.

[0007] S2. Heat the mixed solution to 50-95°C and adjust the pH to 0.5-1.5 to carry out the reaction; after the reaction is completed, separate the solid and liquid to obtain the copper-removed liquid and copper-removed slag.

[0008] In some embodiments, the sulfur-containing amino acid is at least one of methionine, cysteine, and cystine.

[0009] In some embodiments, in step S1, the nickel-containing solution contains Ni 2+ Concentration of 10-100 g / L, Cu 2+ The concentration is 0.01-1 g / L.

[0010] In some embodiments, in step S1, the pH of the nickel-containing solution is adjusted to 3-5 using an acid, a base, or nickel carbonate.

[0011] In some embodiments, the acid is hydrochloric acid and / or sulfuric acid.

[0012] In some embodiments, the alkali is at least one selected from NaOH, Na2CO3, and NaHCO3.

[0013] In some embodiments, in step S2, the pH of the mixed solution is adjusted to 0.5-1.5 using hydrochloric acid and / or sulfuric acid.

[0014] In some embodiments, in step S2, the Cu content in the copper-removed solution is ≤1 mg / L.

[0015] In some embodiments, in step S2, the Cu content in the copper removal slag is ≥30wt% and the Ni content is ≤1wt%.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0017] This invention uses sulfur-containing amino acids as copper removal agents. By adjusting the physicochemical environment of the solution system, the sulfur-containing amino acids selectively react with copper ions to form precipitates, achieving targeted deep removal of copper from nickel-containing solutions. This reduces the copper content in nickel-containing solutions to below 1 mg / L, while significantly reducing nickel loss during the copper removal process. The copper-removed slag can be used as copper concentrate for smelting, providing a short-process, low-cost new approach for the efficient deep removal of copper from nickel-containing solutions.

[0018] The method of this invention achieves deep removal of copper from nickel-containing solutions while significantly reducing nickel loss. This not only provides high-quality nickel raw materials for the preparation of high-purity nickel products, but also ensures that the copper content in the copper-removed slag is ≥30wt% with low nickel content, making it suitable as a raw material for copper smelting and realizing the resource utilization of copper, resulting in significant economic benefits. Furthermore, the method of this invention has low process requirements, greatly reducing production costs and making it suitable for industrial application. Detailed Implementation

[0019] Numerous specific details are set forth in the following description to provide a full understanding of the invention. However, the invention can be practiced in many other ways different from those described herein, and similar modifications can be made by those skilled in the art without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0020] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0021] Example 1

[0022] A method for efficient and deep removal of copper from a nickel-containing solution includes the following steps:

[0023] S1. Adjust the pH of the nickel-containing solution to 3 using hydrochloric acid and / or NaOH, according to the mass ratio M. 半胱氨酸 :M 铜 Cysteine ​​was added to a nickel-containing solution in a ratio of 5:1, the solution temperature was controlled at 25°C, and the mixture was stirred thoroughly until it was completely dissolved to obtain a mixed solution.

[0024] S2. Heat the mixed solution to 60°C with hydrochloric acid and adjust the pH to 1 to carry out the reaction; after the reaction is completed, separate the solid and liquid to obtain the copper-removed liquid and copper-removed slag.

[0025] Among them, in nickel-containing solutions, Ni 2+ The concentration is 100 g / L, Cu 2+ The concentration is 1 g / L.

[0026] Example 2

[0027] A method for efficient and deep removal of copper from a nickel-containing solution includes the following steps:

[0028] S1. Adjust the pH of the nickel-containing solution to 3 using hydrochloric acid and / or NaOH, according to the mass ratio M. 蛋氨酸 :M 铜 Methionine was added to a nickel-containing solution in a ratio of 3:1, and the solution temperature was controlled at 25°C. The solution was stirred thoroughly until completely dissolved to obtain a mixed solution.

[0029] S2. Heat the mixed solution to 60°C with hydrochloric acid and adjust the pH to 1 to carry out the reaction; after the reaction is completed, separate the solid and liquid to obtain the copper-removed liquid and copper-removed slag.

[0030] Among them, in nickel-containing solutions, Ni 2+ The concentration is 100 g / L, Cu2+ The concentration is 1 g / L.

[0031] Example 3

[0032] A method for efficient and deep removal of copper from a nickel-containing solution includes the following steps:

[0033] S1. Adjust the pH of the nickel-containing solution to 3 using hydrochloric acid and / or NaOH, according to the mass ratio M. 半胱氨酸 :M 铜 Add cysteine ​​to a nickel-containing solution in a ratio of 10:1, control the solution temperature at 25°C, and stir thoroughly until completely dissolved to obtain a mixed solution;

[0034] S2. Heat the mixed solution to 60°C with hydrochloric acid and adjust the pH to 1 to carry out the reaction; after the reaction is completed, separate the solid and liquid to obtain the copper-removed liquid and copper-removed slag.

[0035] Among them, in nickel-containing solutions, Ni 2+ The concentration is 100 g / L, Cu 2+ The concentration is 1 g / L.

[0036] Example 4

[0037] A method for efficient and deep removal of copper from a nickel-containing solution includes the following steps:

[0038] S1. Adjust the pH of the nickel-containing solution to 3 using hydrochloric acid and / or NaOH, according to the mass ratio M. 半胱氨酸 :M 铜 Cysteine ​​was added to a nickel-containing solution in a ratio of 5:1, the solution temperature was controlled at 25°C, and the mixture was stirred thoroughly until it was completely dissolved to obtain a mixed solution.

[0039] S2. Heat the mixed solution to 90°C with hydrochloric acid and adjust the pH to 1 to carry out the reaction; after the reaction is completed, separate the solid and liquid to obtain the copper-removed liquid and copper-removed slag.

[0040] Among them, in nickel-containing solutions, Ni 2+ The concentration is 100 g / L, Cu 2+ The concentration is 1 g / L.

[0041] Example 5

[0042] A method for efficient and deep removal of copper from a nickel-containing solution includes the following steps:

[0043] S1. Adjust the pH of the nickel-containing solution to 5 using hydrochloric acid and / or NaOH, according to the mass ratio M. 胱氨酸 :M 铜 Cystine was added to a nickel-containing solution in a ratio of 5:1, and the solution temperature was controlled at 25°C. The solution was stirred thoroughly until completely dissolved to obtain a mixed solution.

[0044] S2. Heat the mixed solution to 60°C with hydrochloric acid and adjust the pH to 1 to carry out the reaction; after the reaction is completed, separate the solid and liquid to obtain the copper-removed liquid and copper-removed slag.

[0045] Among them, in nickel-containing solutions, Ni 2+ The concentration is 100 g / L, Cu 2+ The concentration is 1 g / L.

[0046] Example 6

[0047] A method for efficient and deep removal of copper from a nickel-containing solution includes the following steps:

[0048] S1. Adjust the pH of the nickel-containing solution to 3 using hydrochloric acid and / or NaOH, according to the mass ratio M. 半胱氨酸 :M 铜 Cysteine ​​was added to a nickel-containing solution in a ratio of 5:1, the solution temperature was controlled at 25°C, and the mixture was stirred thoroughly until it was completely dissolved to obtain a mixed solution.

[0049] S2. Heat the mixed solution to 60°C with hydrochloric acid and adjust the pH to 0.5 to carry out the reaction; after the reaction is completed, separate the solid and liquid to obtain the copper-removed liquid and copper-removed slag.

[0050] Among them, in nickel-containing solutions, Ni 2+ The concentration is 100 g / L, Cu 2+ The concentration is 1 g / L.

[0051] Comparative Example 1

[0052] A method for efficient and deep removal of copper from a nickel-containing solution includes the following steps:

[0053] S1. Adjust the pH of the nickel-containing solution to 3 using hydrochloric acid and / or NaOH, according to the mass ratio M. 福美钠 :M 铜 Sodium thiocarbamate (sodium dimethyl dithiocarbamate) was added to a nickel-containing solution in a ratio of 5:1. The solution temperature was controlled at 25°C, and the mixture was stirred thoroughly until it was completely dissolved to obtain a mixed solution.

[0054] S2. Heat the mixed solution to 60°C with hydrochloric acid and adjust the pH to 1 to carry out the reaction; after the reaction is completed, separate the solid and liquid to obtain the copper-removed liquid and copper-removed slag.

[0055] Among them, in nickel-containing solutions, Ni 2+ The concentration is 100 g / L, Cu 2+ The concentration is 1 g / L.

[0056] Comparative Example 2

[0057] A method for efficient and deep removal of copper from a nickel-containing solution includes the following steps:

[0058] Adjust the pH of the nickel-containing solution to 3 using hydrochloric acid and / or NaOH, according to mass ratio M 福美钠 :M 铜 Sodium formaldehyde sulfoxylate was added to a nickel-containing solution in a ratio of 5:1, and the solution was heated to 60°C to carry out the reaction. After the reaction was completed, the solid and liquid were separated to obtain a copper-removed liquid and copper-removed slag.

[0059] Among them, in nickel-containing solutions, Ni 2+ The concentration is 100 g / L, Cu 2+ The concentration is 1 g / L.

[0060] Comparative Example 3

[0061] A method for efficient and deep removal of copper from a nickel-containing solution includes the following steps:

[0062] Adjust the pH of the nickel-containing solution to 1 using hydrochloric acid and / or NaOH, according to mass ratio M. 半胱氨酸 :M 铜 Cysteine ​​was added to a nickel-containing solution in a ratio of 5:1, and the solution was heated to 60°C to carry out the reaction. After the reaction was completed, the solid and liquid were separated to obtain a copper-removed liquid and copper-removed slag.

[0063] Among them, in nickel-containing solutions, Ni 2+ The concentration is 100 g / L, Cu 2+ The concentration is 1 g / L.

[0064] The contents of Ni and Cu in the copper-removed liquid and copper-removed slag obtained in Examples 1-6 and Comparative Examples 1-3 were detected, and the results are shown in Table 1 below.

[0065] Table 1. Ni and Cu content in copper removal solution and copper removal slag

[0066]

[0067] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0068] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the appended claims.

Claims

1. A method for efficient and deep removal of copper from a nickel-containing solution, characterized in that, Includes the following steps: S1. Adjust the pH of the nickel-containing solution to 3-5, according to mass ratio M 含硫氨基酸 :M 铜 Sulfur-containing amino acids are added to a nickel-containing solution in a ratio of 2 to 10:1, and the solution temperature is controlled at 5-50℃. The mixture is thoroughly mixed until completely dissolved to obtain a mixed solution. S2. Heat the mixed solution to 50-95°C and adjust the pH to 0.5-1.5 to carry out the reaction; after the reaction is completed, separate the solid and liquid to obtain the copper-removed liquid and the copper-removed slag. The sulfur-containing amino acid is at least one of methionine, cysteine, and cystine. In step S1, in the nickel-containing solution, Ni 2+ Concentration of 10-100 g / L, Cu 2+ The concentration is 0.01-1 g / L; In step S2, the Cu content in the copper-removed liquid is ≤1 mg / L, and the Cu content in the copper-removed slag is ≥30 wt% and the Ni content is ≤1 wt%.

2. The method for efficient and deep removal of copper from nickel-containing solutions according to claim 1, characterized in that, In step S1, the pH of the nickel-containing solution is adjusted to 3-5 using acid, alkali, or nickel carbonate.

3. The method for efficient and deep removal of copper from nickel-containing solutions according to claim 2, characterized in that, The acid is hydrochloric acid and / or sulfuric acid.

4. The method for efficient and deep removal of copper from nickel-containing solutions according to claim 2, characterized in that, The alkali is at least one of NaOH, Na2CO3, and NaHCO3.

5. The method for efficient and deep removal of copper from nickel-containing solutions according to claim 1, characterized in that, In step S2, the pH of the mixed solution is adjusted to 0.5-1.5 using hydrochloric acid and / or sulfuric acid.

Images