Process for the extraction separation of nickel from a copper sulfate solution

Abstract

This invention discloses a method for the extraction and separation of nickel from copper sulfate solution. The method includes pretreatment, extraction, and back-extraction steps, specifically: adjusting the pH of the nickel-containing copper sulfate solution to 3.0-4.5 by adding a pH adjuster to obtain material a; extracting material a with a composite extractant to obtain an organic phase b and an aqueous phase c; back-extracting organic phase b with sulfuric acid solution to obtain a nickel-containing solution d and raffinate e. This invention achieves the extraction and separation of nickel from copper sulfate solution, with the organic phase being repeatedly recycled. This process can successfully achieve highly efficient extraction and separation of nickel from copper sulfate solution, with a nickel extraction rate of over 96-98.5% and a back-extraction rate of over 99%. The organic phase can be repeatedly recycled, and the cost is low.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of metallurgy, and particularly relates to a method for extracting and separating nickel in a copper sulfate solution. BACKGROUND

[0002] Nickel impurities in the copper sulfate solution are harmful and have significant systematicity, which is particularly prominent in the preparation of electrolytic copper, the production of electronic-grade copper sulfate, electroplating processing and high-end chemical applications. The traditional precipitation nickel removal process (such as sulfide nickel removal) can remove nickel, but has core pain points such as long process flow, high copper loss rate and high energy consumption. Based on the above industry pain points, the present research focuses on the development of efficient nickel ion removal technology in the copper sulfate solution, and plans to use a composite extractant system as the core technical means to optimize the extraction and separation kinetics and thermodynamic behavior of nickel ions by systematically controlling the key process parameters (pH value, reaction temperature, extraction time, etc.) of the extraction process, so as to realize efficient and stable removal of nickel. The ultimate goal is to build a new nickel removal process that is environmentally friendly, economically feasible and suitable for industrial application. SUMMARY

[0003] The application aims to provide a method for extracting and separating nickel in a copper sulfate solution.

[0004] The purpose of the present application is achieved by the method for extracting and separating nickel in a copper sulfate solution, which comprises pretreatment, extraction and stripping steps, and specifically comprises: A. Pretreatment: adding a nickel-containing copper sulfate solution to be treated to a pH adjuster to adjust the pH value to 3.0-4.5 to obtain material a; B. Extraction: adding a composite extractant to material a for extraction to obtain organic phase b and aqueous phase c; C. Stripping: adding a sulfuric acid solution to organic phase b for stripping to obtain nickel-containing liquid d and raffinate e; The composite extractant is composed of hypophosphorous acid and sulfonated kerosene.

[0005] Specifically, a copper sulfate solution containing 0.1-0.3 g / L of nickel is taken, and an acidic solution (sulfuric acid, hydrochloric acid, nitric acid, etc.) or an alkaline solution (sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia, etc.) is added to adjust the pH to 3.0-4.5. Then, 10-30% (v / v) of bis(2,4,4-trimethylpentyl)phosphonic acid (Cyanex272) + 70-90% of sulfonated kerosene composite extractant is added for extraction, with a ratio of O / A = 1:1-1:3, at room temperature (25-30℃), stirring for 5-15 min at a stirring speed of 250-300 r / min, clarifying and separating the layers for 5-8 min, and then back-extracting with 0.5-2 mol / L sulfuric acid; thus, the nickel in the copper sulfate solution is extracted and separated, and the organic phase is recycled. This process can successfully achieve efficient extraction and separation of nickel from copper sulfate solution, with a nickel extraction rate of over 96-98.5% and a back-extraction rate of over 99%. The organic phase can be repeatedly recycled, and the cost is low. Detailed Implementation

[0006] The present invention will be further described below with reference to embodiments, but this is not intended to limit the present invention in any way. Any modifications or substitutions made based on the teachings of the present invention shall fall within the protection scope of the present invention.

[0007] The extraction and separation method for nickel in copper sulfate solution according to the present invention includes pretreatment, extraction, and back-extraction steps, specifically including: A. Pretreatment: The pH value of the nickel-containing copper sulfate solution to be treated is adjusted to 3.0~4.5 by adding a pH adjuster to obtain material a; B. Extraction: Add a composite extractant to material a to obtain organic phase b and aqueous phase c; C. Back-extraction: Add sulfuric acid solution to organic phase b and back-extract to obtain nickel-containing solution d and raffinate e; The composite extractant is composed of phosphonic acid and sulfonated kerosene.

[0008] The volume ratio of the hypophosphonic acid and sulfonated kerosene is (10~30):(70~90).

[0009] The pH adjuster mentioned in step A is an acidic or alkaline solution.

[0010] The acidic solution is a sulfuric acid solution, a hydrochloric acid solution, or a nitric acid solution.

[0011] The alkaline solution is a sodium hydroxide solution, an ammonium carbonate solution, a sodium bicarbonate solution, or an ammonia solution.

[0012] The extraction temperature described in step B is 25~30℃.

[0013] The extraction described in step B uses a ratio O / A of (1:1) to (1:3).

[0014] The extraction described in step B is carried out under stirring conditions.

[0015] The stirring speed is 250~300 r / min.

[0016] The concentration of the sulfuric acid solution mentioned in step C is 0.5~2 mol / L.

[0017] The present invention will be further described below with reference to specific embodiments: Comparative Example 1 Chinese patent CN112607813B discloses a method for co-extracting nickel from nickel plating wastewater. The method involves preparing a 0.5–15 mol / L di(2-ethylhexyl)phosphoric acid (D2EHPA) solution, then adding an alkaline solution to the D2EHPA solution and stirring for 15–40 minutes to induce a saponification reaction. The amount of alkaline solution added is such that the saponification rate of D2EHPA is 30–70%. After stirring, the reaction solution is separated into layers, and the upper layer is collected. A diluent, sulfonated coal, is then added to the upper layer. Add oil, stir, and control the temperature at 15–35°C; then add methyl isobutyl ketone (Methyl isobutyl ketone) to the upper reaction solution, the amount of Methyl isobutyl ketone added being 15–50% of the oil phase, more preferably 30%, stir, and control the temperature at 15–35°C to obtain the extractant; add the extractant to nickel plating wastewater (nickel ion concentration of 3.3–3.5 g / L), the volume ratio of nickel plating wastewater to extractant is 1:0.6–1.02, stir for 15–40 min, mix evenly, and after stirring, allow the reaction solution to separate into layers, Ni 2+ The extraction rate can reach 93.6-97.25%. The supernatant is collected. An acid solution is added to the supernatant for back-extraction. The acid solution can be one or more of sulfuric acid, hydrochloric acid, and nitric acid, with a volume ratio of acid solution to supernatant solution of 1:0.8-1.5. Finally, a nickel-containing recoverable product is obtained. 2+ The back-extraction rate can reach 95.4%-100%.

[0018] Example 1

[0019] A copper sulfate solution containing 4.52 g / L of nickel was measured, and the pH was adjusted to 3.0 with sulfuric acid. Extraction was then performed using a composite extractant of 10% (v / v) di(2,4,4-trimethylpentyl)phosphonic acid (Cyanex 272) and 90% sulfonated kerosene, with a ratio of O / A = 1:1. The mixture was stirred for 15 min at room temperature (25-30℃) at a stirring speed of 300 r / min, followed by clarification and separation for 8 min. The organic and aqueous phases were then separated. The Ni content in the raffinate was determined. 2+The content was reduced to only 0.11 g / L, and the gallium extraction rate reached 97.36%. Further back-extraction with 0.5 mol / L sulfuric acid resulted in a back-extraction rate of 99.6%, achieving the extraction and separation of nickel from the copper sulfate solution.

[0020] Example 2

[0021] A copper sulfate solution containing 5.0 g / L nickel was measured, and sulfuric acid was added to adjust the pH to 4.5. Extraction was then performed using a composite extractant of 30% (v / v) di(2,4,4-trimethylpentyl)phosphonic acid (Cyanex 272) and 70% sulfonated kerosene, with a ratio of O / A = 1:3. The mixture was stirred for 10 min at room temperature (25-30℃) at a stirring speed of 250 r / min, followed by clarification and separation for 7 min. The organic and aqueous phases were then separated. The resulting raffinate contained Ni... 2+ The content was reduced to only 0.118 g / L, and the gallium extraction rate reached 97.82%. Further back-extraction with 2 mol / L sulfuric acid resulted in a back-extraction rate of 99.3%, achieving the extraction and separation of nickel from the copper sulfate solution.

[0022] Example 3

[0023] A copper sulfate solution containing 4.8 g / L of nickel was measured, and sulfuric acid was added to adjust the pH to 4.0. Extraction was then performed using a composite extractant of 20% (v / v) di(2,4,4-trimethylpentyl)phosphonic acid (Cyanex 272) and 80% sulfonated kerosene, with a ratio of O / A = 1:2. The mixture was stirred for 6 min at room temperature (25-30℃) at a stirring speed of 270 r / min, followed by clarification and separation for 6 min. The organic and aqueous phases were then separated. The resulting raffinate contained Ni... 2+ The content was reduced to only 0.108 g / L, and the gallium extraction rate reached 97.91%. Further back-extraction with 1.5 mol / L sulfuric acid resulted in a back-extraction rate of 98.98%, achieving the extraction and separation of nickel from the copper sulfate solution.

[0024] Example 4

[0025] A copper sulfate solution containing 4.9 g / L of nickel was measured, and sulfuric acid was added to adjust the pH to 3.5. Extraction was then performed using a composite extractant of 25% (v / v) di(2,4,4-trimethylpentyl)phosphonic acid (Cyanex 272) and 75% sulfonated kerosene, with a ratio O / A of 1:2. The mixture was stirred for 10 min at room temperature (25-30℃) at a stirring speed of 260 r / min, followed by clarification and separation of the organic and aqueous phases for 6 min. The resulting raffinate contained Ni. 2+ The content was reduced to only 0.103 g / L, and the gallium extraction rate reached 97.88%. Further back-extraction with 1.5 mol / L sulfuric acid resulted in a back-extraction rate of 99.18%, achieving the extraction and separation of nickel from the copper sulfate solution.

Claims

1. A method for extracting and separating nickel from copper sulfate solution, characterized in that, The extraction and separation method for nickel in copper sulfate solution includes pretreatment, extraction, and back-extraction steps, specifically including: A. Pretreatment: The pH value of the nickel-containing copper sulfate solution to be treated is adjusted to 3.0~4.5 by adding a pH adjuster to obtain material a; B. Extraction: Add a composite extractant to material a to obtain organic phase b and aqueous phase c; C. Back-extraction: Add sulfuric acid solution to organic phase b and back-extract to obtain nickel-containing solution d and raffinate e; The composite extractant is composed of phosphonic acid and sulfonated kerosene.

2. The method for extraction and separation of nickel from copper sulfate solution according to claim 1, characterized in that, The volume ratio of the hypophosphonic acid and sulfonated kerosene is (10~30):(70~90).

3. The method for extraction and separation of nickel from copper sulfate solution according to claim 1, characterized in that, The pH adjuster mentioned in step A is an acidic or alkaline solution.

4. The method for extracting and separating nickel from copper sulfate solution according to claim 3, characterized in that, The acidic solution is a sulfuric acid solution, a hydrochloric acid solution, or a nitric acid solution.

5. The method for extracting and separating nickel from copper sulfate solution according to claim 3, characterized in that, The alkaline solution is a sodium hydroxide solution, an ammonium carbonate solution, a sodium bicarbonate solution, or an ammonia solution.

6. The method for extracting and separating nickel from copper sulfate solution according to claim 1, characterized in that, The extraction temperature described in step B is 25~30℃.

7. The method for extraction and separation of nickel from copper sulfate solution according to claim 1, characterized in that, The extraction described in step B uses a ratio O / A of (1:1) to (1:3).

8. The method for extraction and separation of nickel from copper sulfate solution according to claim 1, characterized in that, The extraction described in step B is carried out under stirring conditions.

9. The method for extracting and separating nickel from copper sulfate solution according to claim 8, characterized in that, The stirring speed is 250~300 r / min.

10. The method for extraction and separation of nickel from copper sulfate solution according to claim 1, characterized in that, The concentration of the sulfuric acid solution mentioned in step C is 0.5~2 mol / L.