Method for removing Ca ions in nickel aminosulfonate solution based on extraction method

Abstract

The invention relates to a method for removing Ca ions in a nickel aminosulfonate solution based on an extraction method, which comprises the following steps: (1) preparing a sodium soap organic solution, namely diluting P204 by using light white oil to obtain a solution before saponification with the hydrogen ion concentration of 0.2 g / L, adding a sodium hydroxide solution into the solution before saponification to carry out sodium soap reaction, the sodium soap organic solution with the hydrogen ion concentration of 0.02-0.04 g / L is obtained; (2) preparing a nickel soap organic solution: adding a diluted nickel aminosulfonate solution into the sodium soap organic solution for extraction to obtain the nickel soap organic solution; (3) nickel soap organic sodium washing: carrying out sodium washing on the nickel soap organic solution by using a sulfamic acid solution to respectively obtain a pre-solution and a sodium washing solution; (4) extraction and impurity removal: extracting the nickel aminosulfonate solution by adopting the pre-solution to obtain a raffinate solution of which the nickel content is greater than 170g / L, the Ca ion content is less than 4mg / L and the pH value is greater than 3.5; and (5) backwashing with an extracting agent: adding a saturated sulfamic acid solution into the organic solution extracted in the step (4) for backwashing. The method is efficient and environment-friendly.

Description

Technical Field

[0001] The invention relates to the technical field of hydrometallurgy and chemical separation, and in particular to a method for removing Ca ions in a nickel sulfamate solution based on an extraction method. Background Art

[0002] Nickel sulfamate is widely used in electroplating, battery manufacturing, catalysis and other fields due to its excellent electrodeposition performance and good catalytic activity. However, nickel sulfamate solution often contains a certain amount of impurities such as calcium ions, which not only affect the purity of nickel salts, but may also have an adverse effect on subsequent process, such as reducing the quality of the electroplating layer and reducing the activity of the catalyst.

[0003] At present, most calcium removal methods use precipitation, but precipitation easily introduces anionic impurities into the nickel sulfamate solution, which affects the nickel sulfamate solution. Therefore, developing an efficient and environmentally friendly calcium ion removal technology is crucial to improving the quality of nickel sulfamate products. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide an efficient and environmentally friendly method for removing Ca ions in a nickel sulfamate solution based on an extraction method.

[0005] To solve the above problems, the present invention discloses a method for removing Ca ions from a nickel sulfamate solution based on an extraction method, comprising the following steps: ⑴Preparation of sodium soap organic solution: P204 is diluted with light white oil to obtain a pre-saponification solution with a hydrogen ion concentration of 0.2 g / L, a sodium hydroxide solution with a mass concentration of 32% is added to the pre-saponification solution, and a sodium soap reaction is carried out at 25-30°C to obtain a sodium soap organic solution with a hydrogen ion concentration of 0.02-0.04 g / L; (2) Preparation of nickel soap organic solution: Adding a dilute nickel sulfamate solution having a nickel content of 20 to 30 g / L to the sodium soap organic solution, performing 5 to 10 extraction steps at 25 to 30° C. to convert the sodium soap organic solution into nickel soap organic solution, thereby obtaining a nickel soap organic solution; ⑶Nickel soap organic washing sodium: Using an aminosulfonic acid solution with a hydrogen ion concentration of 0.5-1 g / L to extract and wash the nickel soap organic solution at 25-30° C. for 5-10 steps to obtain a pre-liquid and a sodium washing solution, respectively; the sodium washing solution is returned to step (2) for repeated use; ⑷ Extraction and impurity removal: The fore-liquid is used to extract a nickel sulfamate solution having a nickel content of 180-200 g / L, a Ca ion content of 20-50 mg / L, and a pH value of 4.0-4.5, to obtain a raffinate solution having a nickel content of greater than 170 g / L, a Ca ion content of less than 4 mg / L, and a pH value of greater than 3.5; ⑸ Extraction agent backwash: A saturated aminosulfonic acid solution is added to the organic solution after extraction in step (4) for backwashing, and the organic solution after backwashing is returned to step (1) for sodium soap reaction with sodium hydroxide solution to achieve repeated use.

[0006] In the step (1), the pH of the solution before saponification is 0.2, the saponification rate is 80-90%, and the pH of the solution after saponification is 0.02-0.04.

[0007] In the step (2), the volume ratio of the sodium soap organic solution to the dilute nickel sulfamate solution is 5-10:1.

[0008] In the step (3), the volume ratio of the nickel soap organic solution to the aminosulfonic acid solution is 5-10:1.

[0009] The sodium content of the sodium washing solution in step (3) is less than 10 mg / L, and the nickel content is 20-30 g / L.

[0010] The extraction conditions in step (4) are that the temperature is 25-30° C., the extraction level is 5-10, and the volume ratio of the nickel sulfamate solution to the pre-liquid is 1:1-2.

[0011] In the step (5), the backwashing temperature is 25-30° C., the volume ratio of the organic solution to the aminosulfonic acid solution is 1-2:1, and the washing is performed until the organic solution is clear and transparent.

[0012] Compared with the prior art, the present invention has the following advantages: 1. The present invention selects P204 as an extractant and light white oil as a diluent, thereby being able to efficiently capture and separate calcium ions in a nickel sulfamate solution and significantly improving the purity of the product.

[0013] 2. Environmentally friendly: No harmful gas is generated during the extraction process, and the organic solvent and sodium washing solution can be recycled, which reduces the processing cost and conforms to the concept of green chemistry.

[0014] 3. The process flow of the present invention is simple and easy to control: the extraction operation is simple and easy to realize industrial production. DETAILED DESCRIPTION

[0015] A method for removing Ca ions from a nickel sulfamate solution based on an extraction method comprises the following steps: ⑴Preparation of sodium soap organic solution: P204 was diluted with light white oil to obtain a pre-saponification solution with a hydrogen ion concentration of 0.2 g / L. A sodium hydroxide solution with a mass concentration of 32% was added to the pre-saponification solution, and a sodium soap reaction was carried out at 25-30°C to obtain a sodium soap organic solution with a hydrogen ion concentration of 0.02-0.04 g / L.

[0016] Among them: the pH of the solution before saponification is 0.2, the saponification rate is 80~90%, and the pH of the solution after saponification is 0.02~0.04.

[0017] (2) Preparation of nickel soap organic solution: Add a dilute nickel sulfamate solution with a nickel content of 20-30 g / L to the sodium soap organic solution, and the volume ratio (L / L) of the sodium soap organic solution to the dilute nickel sulfamate solution is 5-10:1. Perform 5-10 extractions at 25-30°C to convert the sodium soap organic solution into nickel soap organic solution, thus obtaining a nickel soap organic solution.

[0018] ⑶Nickel soap organic washing sodium: The nickel soap organic solution is subjected to 5-10 extractions at 25-30°C using an aminosulfonic acid solution with a hydrogen ion concentration of 0.5-1g / L. The volume ratio (L / L) of the nickel soap organic solution to the aminosulfonic acid solution is 5-10:1. After the sodium washing is completed, the pre-liquid and the sodium washing solution are obtained respectively.

[0019] The sodium content of the sodium washing solution is less than 10 mg / L, and the nickel content is 20-30 g / L. The sodium washing solution is returned to step (2) for repeated use.

[0020] ⑷ Extraction and impurity removal: The nickel sulfamate solution with a nickel content of 180-200 g / L, a Ca ion content of 20-50 mg / L, and a pH value of 4.0-4.5 is extracted with the fore-liquid. The extraction conditions are a temperature of 25-30°C, 5-10 extraction stages, and a volume ratio (L / L) of the nickel sulfamate solution to the fore-liquid of 1:1-2. After the extraction, a raffinate solution with a nickel content of more than 170 g / L, a Ca ion content of less than 4 mg / L, and a pH value of more than 3.5 is obtained.

[0021] ⑸ Extraction agent backwash: Add saturated aminosulfonic acid solution to the organic solution extracted in step (4), perform backwashing at 25-30°C, and the volume ratio (L / L) of organic solution to aminosulfonic acid solution is 1-2:1. Backwashing is completed when the organic solution is clear and transparent. The organic solution after backwashing is returned to step (1) to react with sodium hydroxide solution for sodium soap reaction, so as to achieve repeated use.

[0022] Example 1 A method for removing Ca ions from a nickel sulfamate solution based on an extraction method comprises the following steps: ⑴Preparation of sodium soap organic solution: 8400mL of light white oil and 600mL of diluted P204 were used to obtain a pre-saponification solution with a hydrogen ion concentration of 0.20g / L. 150mL of 32% sodium hydroxide solution was added to the pre-saponification solution to carry out a sodium soap reaction at 25°C to obtain a sodium soap organic solution with a hydrogen ion concentration of 0.038g / L, and a saponification rate of 81%.

[0023] (2) Preparation of nickel soap organic solution: Add dilute nickel sulfamate solution with a nickel content of 26.6 g / L to the sodium soap organic solution, and the volume ratio (L / L) of the sodium soap organic solution to the dilute nickel sulfamate solution is 10:1. Perform 5-stage extraction at 25°C to convert the sodium soap organic solution into nickel soap organic solution to obtain the nickel soap organic solution.

[0024] ⑶Nickel soap organic washing sodium: The nickel soap organic solution was subjected to five-stage extraction and sodium washing at 25°C using an aminosulfonic acid solution with a hydrogen ion concentration of 0.5 g / L. The volume ratio (L / L) of the nickel soap organic solution to the aminosulfonic acid solution was 10:1. After the sodium washing was completed, the pre-liquid and the sodium washing solution were obtained respectively.

[0025] The front liquid is the nickel soap organic solution after the sodium washing is finished, which is used as the organic phase for subsequent extraction of calcium ions in the nickel sulfamate solution. The sodium content of the sodium washing solution is 7 mg / L, and the nickel content is 24.3 g / L. The sodium washing solution is returned to step (2) for repeated use.

[0026] ⑷ Extraction and impurity removal: The fore-liquid was used to extract the nickel sulfamate solution with a nickel content of 185.3 g / L, a Ca ion content of 40.6 mg / L, and a pH value of 4.0. The extraction conditions were a temperature of 25°C, a level of extraction of 5, and a volume ratio (L / L) of the nickel sulfamate solution to the fore-liquid of 1:1. After the extraction, a raffinate solution with a nickel content of 176.4 g / L, a Ca ion content of 3.4 mg / L, and a pH value of 3.7 was obtained.

[0027] ⑸ Extraction agent backwash: Add saturated aminosulfonic acid solution to the organic solution extracted in step (4), and perform backwashing at 25° C. The volume ratio (L / L) of the organic solution to the aminosulfonic acid solution is 1:1. The backwashing is completed when the organic solution is clear and transparent. The organic solution after backwashing is returned to step (1) to react with sodium hydroxide solution for sodium soap reaction, and is reused.

[0028] Example 2 A method for removing Ca ions from a nickel sulfamate solution based on an extraction method comprises the following steps: ⑴Preparation of sodium soap organic solution: 8400mL of light white oil and 600mL of diluted P204 were used to obtain a pre-saponification solution with a hydrogen ion concentration of 0.20g / L. 150mL of 32% sodium hydroxide solution was added to the pre-saponification solution to carry out a sodium soap reaction at 28°C to obtain a sodium soap organic solution with a hydrogen ion concentration of 0.038g / L, and a saponification rate of 81%.

[0029] (2) Preparation of nickel soap organic solution: Add dilute nickel sulfamate solution with a nickel content of 24.5 g / L to the sodium soap organic solution, and the volume ratio (L / L) of the sodium soap organic solution to the dilute nickel sulfamate solution is 10:1. Perform 5-stage extraction at 28°C to convert the sodium soap organic solution into nickel soap organic solution to obtain the nickel soap organic solution.

[0030] ⑶Nickel soap organic washing sodium: The nickel soap organic solution was subjected to eight-stage extraction and sodium washing at 28°C using an aminosulfonic acid solution with a hydrogen ion concentration of 0.54 g / L. The volume ratio (L / L) of the nickel soap organic solution to the aminosulfonic acid solution was 10:1. After the sodium washing was completed, the pre-liquid and the sodium washing solution were obtained respectively.

[0031] The front liquid is the nickel soap organic solution after the sodium washing is finished, which is used as the organic phase for subsequent extraction of calcium ions in the nickel sulfamate solution. The sodium content of the sodium washing solution is 9 mg / L, and the nickel content is 22.6 g / L. The sodium washing solution is returned to step (2) for repeated use.

[0032] ⑷ Extraction and impurity removal: The fore-liquid was used to extract the nickel sulfamate solution with a nickel content of 192.7 g / L, a Ca ion content of 36.5 mg / L, and a pH value of 4.3. The extraction conditions were a temperature of 28°C, a level of extraction of 5, and a volume ratio (L / L) of the nickel sulfamate solution to the fore-liquid of 1:1. After the extraction, a raffinate solution with a nickel content of 182.6 g / L, a Ca ion content of 3.1 mg / L, and a pH value of 3.6 was obtained.

[0033] ⑸ Extraction agent backwash: Add saturated aminosulfonic acid solution to the organic solution extracted in step (4), and perform backwashing at 28° C. The volume ratio (L / L) of the organic solution to the aminosulfonic acid solution is 1:1. The backwashing is completed when the organic solution becomes clear and transparent. The organic solution after backwashing is returned to step (1) to perform sodium soap reaction with sodium hydroxide solution for repeated use.

[0034] Example 3 A method for removing Ca ions from a nickel sulfamate solution based on an extraction method comprises the following steps: ⑴Preparation of sodium soap organic solution: 8400mL of light white oil and 600mL of diluted P204 were used to obtain a pre-saponification solution with a hydrogen ion concentration of 0.20g / L. 160mL of 32% sodium hydroxide solution was added to the pre-saponification solution to carry out a sodium soap reaction at 30°C to obtain a 0.025g / L sodium soap organic solution with a hydrogen ion concentration of 0.038g / L, and a saponification rate of 87.5%.

[0035] (2) Preparation of nickel soap organic solution: Add dilute nickel sulfamate solution with a nickel content of 26.7 g / L to the sodium soap organic solution, and the volume ratio (L / L) of the sodium soap organic solution to the dilute nickel sulfamate solution is 5:1. Perform 5-stage extraction at 30°C to convert the sodium soap organic solution into nickel soap organic solution to obtain a nickel soap organic solution.

[0036] ⑶Nickel soap organic washing sodium: The nickel soap organic solution was subjected to 10-stage extraction and sodium washing at 30°C using an aminosulfonic acid solution with a hydrogen ion concentration of 1.0 g / L. The volume ratio (L / L) of the nickel soap organic solution to the aminosulfonic acid solution was 5:1. After the sodium washing was completed, the pre-liquid and the sodium washing solution were obtained respectively.

[0037] The front liquid is the nickel soap organic solution after the sodium washing is finished, which is used as the organic phase for subsequent extraction of calcium ions in the nickel sulfamate solution. The sodium content of the sodium washing solution is 6 mg / L, and the nickel content is 23.3 g / L. The sodium washing solution is returned to step (2) for repeated use.

[0038] ⑷ Extraction and impurity removal: The pre-liquid was used to extract the nickel sulfamate solution with a nickel content of 188.6 g / L, a Ca ion content of 30.5 mg / L, and a pH value of 4.5. The extraction conditions were a temperature of 30°C, a level of extraction of 5, and a volume ratio (L / L) of the nickel sulfamate solution to the pre-liquid of 1:2. After the extraction, a raffinate solution with a nickel content of 179.6 g / L, a Ca ion content of 2.9 mg / L, and a pH value of 3.8 was obtained.

[0039] ⑸ Extraction agent backwash: Add saturated aminosulfonic acid solution to the organic solution extracted in step (4), and perform backwashing at 30° C. The volume ratio (L / L) of the organic solution to the aminosulfonic acid solution is 2:1. The backwashing is completed when the organic solution is clear and transparent. The organic solution after backwashing is returned to step (1) to react with sodium hydroxide solution for sodium soap reaction, and is reused.

Claims

1. A method for removing Ca ions from a nickel sulfamate solution based on an extraction method, comprising the following steps: ⑴Preparation of sodium soap organic solution: P204 is diluted with light white oil to obtain a pre-saponification solution with a hydrogen ion concentration of 0.2 g / L, a sodium hydroxide solution with a mass concentration of 32% is added to the pre-saponification solution, and a sodium soap reaction is carried out at 25-30°C to obtain a sodium soap organic solution with a hydrogen ion concentration of 0.02-0.04 g / L; (2) Preparation of nickel soap organic solution: Adding a dilute nickel sulfamate solution having a nickel content of 20 to 30 g / L to the sodium soap organic solution, performing 5 to 10 extraction steps at 25 to 30° C. to convert the sodium soap organic solution into nickel soap organic solution, thereby obtaining a nickel soap organic solution; ⑶Nickel soap organic washing sodium: Using an aminosulfonic acid solution with a hydrogen ion concentration of 0.5-1 g / L to extract and wash the nickel soap organic solution at 25-30° C. for 5-10 steps to obtain a pre-liquid and a sodium washing solution, respectively; the sodium washing solution is returned to step (2) for repeated use; ⑷ Extraction and impurity removal: The fore-liquid is used to extract a nickel sulfamate solution having a nickel content of 180-200 g / L, a Ca ion content of 20-50 mg / L, and a pH value of 4.0-4.5, to obtain a raffinate solution having a nickel content of greater than 170 g / L, a Ca ion content of less than 4 mg / L, and a pH value of greater than 3.5; ⑸ Extraction agent backwash: A saturated aminosulfonic acid solution is added to the organic solution after extraction in step (4) for backwashing, and the organic solution after backwashing is returned to step (1) for sodium soap reaction with sodium hydroxide solution to achieve repeated use.

2. A method for removing Ca ions from a nickel sulfamate solution based on an extraction method as claimed in claim 1, characterized in that: In the step (1), the pH of the solution before saponification is 0.2, the saponification rate is 80-90%, and the pH of the solution after saponification is 0.02-0.

04.

3. A method for removing Ca ions from a nickel sulfamate solution based on an extraction method as claimed in claim 1, characterized in that: In the step (2), the volume ratio of the sodium soap organic solution to the dilute nickel sulfamate solution is 5-10:

1.

4. A method for removing Ca ions from a nickel sulfamate solution based on an extraction method as claimed in claim 1, characterized in that: In the step (3), the volume ratio of the nickel soap organic solution to the aminosulfonic acid solution is 5-10:

1.

5. A method for removing Ca ions from a nickel sulfamate solution based on an extraction method as claimed in claim 1, characterized in that: The sodium content of the sodium washing solution in step (3) is less than 10 mg / L, and the nickel content is 20-30 g / L.

6. A method for removing Ca ions from a nickel sulfamate solution based on an extraction method as claimed in claim 1, characterized in that: The extraction conditions in step (4) are that the temperature is 25-30° C., the extraction level is 5-10, and the volume ratio of the nickel sulfamate solution to the pre-liquid is 1:1-2.

7. The method for removing Ca ions from a nickel sulfamate solution based on an extraction method as claimed in claim 1, characterized in that: In the step (5), the backwashing temperature is 25-30° C., the volume ratio of the organic solution to the aminosulfonic acid solution is 1-2:1, and the washing is performed until the organic solution is clear and transparent.