CN114752782A - Process suitable for refining and impurity removing of low-calcium magnesium crude nickel sulfate - Google Patents
Process suitable for refining and impurity removing of low-calcium magnesium crude nickel sulfate Download PDFInfo
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- CN114752782A CN114752782A CN202210464813.0A CN202210464813A CN114752782A CN 114752782 A CN114752782 A CN 114752782A CN 202210464813 A CN202210464813 A CN 202210464813A CN 114752782 A CN114752782 A CN 114752782A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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Abstract
The invention discloses a process suitable for refining and impurity removal of low-calcium magnesium crude nickel sulfate, which is characterized in that the refining and impurity removal is carried out by adopting the processes of copper removal by vulcanization, iron removal by oxidative hydrolysis and further extraction and separation by C272, the treatment level is reduced, the traditional nickel sulfate refining process is greatly shortened, and the removal of impurities such as copper, iron, lead, zinc and the like can be effectively realized.
Description
Technical Field
The invention relates to the technical field of metal smelting, in particular to a process suitable for refining and impurity removal of low-calcium magnesium crude nickel sulfate.
Background
The crude nickel sulfate is a byproduct of a plurality of copper smelting enterprises, usually, after copper is removed and arsenic is removed in a copper electrolysis liquid purification process, evaporation crystallization, freezing crystallization or a combined process mode of the two are adopted for recycling, the content of impurities such as copper, iron, lead, zinc, sulfuric acid and the like which are usually carried in the crude nickel sulfate product generated by pressure filtration is high, and due to the special production process of the copper smelting enterprises, the content of calcium and magnesium is extremely low, the crude nickel sulfate belongs to low-calcium-magnesium crude nickel sulfate, and the content of calcium and magnesium in the crude nickel sulfate reaches the quality requirement of battery-grade nickel sulfate.
The crude nickel sulfate has low nickel content and low nickel valuation coefficient, so that the market sale price is not high, the general crude nickel sulfate sale valuation coefficient is only about 75-80%, the reduction loss is large, the production and operation benefits of enterprises are not facilitated, and the refined nickel sulfate produced by refining and purification can be directly used as a product for industries such as batteries and the like.
At present, the purification method of crude nickel sulfate mainly comprises the following steps: chemical precipitation, solvent extraction, ion exchange, and combined chemical precipitation and solvent extraction purification. Wherein:
(1) chemical precipitation method: namely, the method comprises the steps of sulfuration precipitation, oxidative hydrolysis precipitation and fluorination precipitation, and has the defects of low impurity removal rate, large loss of nickel and high reagent consumption.
(2) Solvent extraction method: the method is a traditional nickel sulfate refining process, and has the defects of long process, multiple stages, large occupied area and high investment cost.
(3) Ion exchange method: namely, cation or anion exchange resin is adopted to absorb and remove impurities, and the method has the defects of strict requirements on raw material components, small application range and easy blockage of the resin.
Therefore, the process which has the advantages of short process flow, low investment and low operation cost and is suitable for refining and purifying the crude nickel sulfate of the copper smelting enterprises is found, and the process has a remarkable effect on improving the production and operation benefits of the copper smelting enterprises.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a process suitable for refining and impurity removal of low-calcium magnesium crude nickel sulfate.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process suitable for refining and removing impurities from low-calcium magnesium crude nickel sulfate comprises the following specific steps:
s1, dissolving: dissolving the crude nickel sulfate with pure water or distilled water;
s2, removing copper through vulcanization: carrying out copper deposition on the solution obtained in the step S1 by using hydrogen sulfide gas, filtering after the reaction is finished, and carrying out hydrolysis and iron removal on the filtrate in a step S3;
s3, hydrolysis and iron removal: adjusting the pH of the filtrate obtained in the step S2 to 4-4.5, adding hydrogen peroxide, filtering after the reaction is finished, and extracting and back-extracting the obtained filtrate in the step S4;
s4, extraction and back extraction: adjusting the pH of the filtrate obtained in the step S3 to 4.4-4.5, and then performing extraction and back extraction; the organic phase used for extraction was C272;
s5, oil removal: carrying out oil separation on the raffinate obtained in the step S4 by adopting a four-section oil separation groove, wherein the oil content of liquid water is less than 5ppm after the oil separation;
and S6, sequentially carrying out triple-effect vacuum evaporation, cooling crystallization and centrifugal separation on the raffinate obtained after oil separation in the step S5, and finally obtaining a solid, namely a refined nickel sulfate finished product.
Further, in step S1, the dissolution temperature is 40-50 ℃, and the concentration of nickel in the solution is controlled to be 60-80 g/L.
Further, in step S2, the adding amount of hydrogen sulfide gas is 2-4 times of the theoretical amount of copper deposition, the pH value is kept to be less than 2, the copper deposition reaction temperature is 70-90 ℃, and the reaction time is 0.5-3 h.
Further, in step S2, the main component of the filter residue is copper sulfide, and the filter residue is returned to the flash smelting system for recovery.
Further, in step S2, hydrogen sulfide gas is generated by gas-liquid sulfurization of sodium hydrosulfide.
Further, in step S3, adjusting the pH of the filtrate obtained in step S2 with a NaOH solution with the mass concentration of 1% -10% at the temperature of 60-80 ℃; the mass concentration of hydrogen peroxide is 27.5 percent, and the molar ratio of Fe to hydrogen peroxide is 1: 2; the reaction time is 20-30 min.
Further, in step S4, adjusting the pH of the filtrate obtained in step S3 with a NaOH solution with a mass concentration of 1% to 10%; in the extraction, the volume concentration of C272 is 15%, the saponification rate is 65%, the extraction ratio O/A is 1-1.6:1, and the temperature is normal temperature; the back extraction is carried out by adopting sulfuric acid, the concentration of the sulfuric acid is 160-.
Further, in step S4, 3-5 stages of extraction and stripping are performed.
The invention has the beneficial effects that: the invention adopts the processes of copper sulfide removal, oxidative hydrolysis iron removal and C272 further extraction separation impurity removal to carry out refining impurity removal, reduces the treatment stages, greatly shortens the traditional nickel sulfate refining process, and can effectively realize the removal of impurities such as copper, iron, lead, zinc and the like.
Drawings
FIG. 1 is a flow chart of the process of example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, and it should be noted that the present embodiment is based on the technical solution, and the detailed implementation and the specific operation process are provided, but the protection scope of the present invention is not limited to the present embodiment.
The embodiment provides a process suitable for refining and impurity removing of low-calcium magnesium crude nickel sulfate, as shown in fig. 1, the specific process is as follows:
s1, dissolving: dissolving the crude nickel sulfate with pure water or distilled water at 40-50 deg.C, and controlling the concentration of nickel in the solution to 60-80 g/L;
s2, copper sulfide removal: carrying out copper deposition on the solution obtained in the step S1 by utilizing hydrogen sulfide gas generated by gas-liquid vulcanization of sodium hydrosulfide, wherein the addition amount of the hydrogen sulfide gas is 2-4 times of the theoretical amount of the deposited copper, the pH value is kept to be less than 2, the reaction temperature of copper deposition is 70-90 ℃, the reaction time is 0.5-3h, then filtering is carried out, the filtrate enters the step S3 for hydrolysis and iron removal, and the filter residue is mainly copper sulfide and can be returned to a smelting flash system for recovery; lead in the crude nickel sulfate is removed in small quantities during sulfidisation, mainly in subsequent extraction.
S3, hydrolysis and iron removal: adjusting the pH of the filtrate obtained in the step S2 to 4-4.5 by using a NaOH solution with the mass concentration of 1-10% at the temperature of 60-80 ℃, adding hydrogen peroxide with the mass concentration of 27.5%, wherein the molar ratio of Fe to hydrogen peroxide is 1:2, reacting for 20-30min, filtering, and extracting and back-extracting the obtained filtrate in the step S4. The iron-removing slag mainly contains ferric hydroxide and can be used as a precipitator for wastewater treatment to participate in the wastewater treatment.
S4, extraction and back extraction: adjusting the pH of the filtrate obtained in the step S3 to 4.4-4.5 by using a NaOH solution with the mass concentration of 1-10%, and then performing extraction and back extraction; in the extraction, the organic phase is C272 with the volume concentration of 15%, the saponification rate is 65%, the extraction phase ratio O/A is 1-1.6:1, and the temperature is normal temperature; the back extraction is carried out by adopting sulfuric acid, the concentration of the sulfuric acid is 160-. 3-5 levels of extraction and back extraction are carried out. The zinc and most of the lead in the crude nickel sulphate is removed in the extraction. The strip liquor obtained in the step can also participate in the wastewater treatment.
S5, oil removal: and (4) carrying out oil separation on the raffinate obtained in the step S4 by adopting a four-section oil separation groove, wherein the oil content of liquid water is less than 5ppm after the oil separation.
And S6, sequentially carrying out triple-effect vacuum evaporation, cooling crystallization and centrifugal separation on the raffinate obtained after oil separation in the step S5, and finally obtaining a solid, namely a refined nickel sulfate finished product. The finished product of the refined nickel sulfate can reach the standard of battery-grade nickel sulfate. It should be noted that the primary centrifugal mother liquor can be recycled, and the hydrolysis deferrization step or the triple-effect vacuum evaporation step is determined according to the impurity content, when the impurity content is low, the triple-effect vacuum evaporation is performed, and when the impurity content is high, the hydrolysis deferrization process is performed to remove impurities.
Various corresponding changes and modifications can be made by those skilled in the art based on the above technical solutions and concepts, and all such changes and modifications should be included in the protection scope of the present invention.
Claims (8)
1. A process suitable for refining and impurity removing of low-calcium magnesium crude nickel sulfate is characterized by comprising the following specific steps:
s1, dissolving: dissolving the crude nickel sulfate with pure water or distilled water;
s2, copper sulfide removal: carrying out copper deposition on the solution obtained in the step S1 by using hydrogen sulfide gas, filtering after the reaction is finished, and carrying out hydrolysis and iron removal on the filtrate in a step S3;
s3, hydrolysis and iron removal: adjusting the pH of the filtrate obtained in the step S2 to 4-4.5, adding hydrogen peroxide, filtering after the reaction is finished, and extracting and back-extracting the obtained filtrate in the step S4;
s4, extraction and back extraction: adjusting the pH of the filtrate obtained in the step S3 to 4.4-4.5, and then performing extraction and back extraction; the organic phase used for extraction was C272;
s5, oil separation: adopting a four-section oil separation groove to separate oil from the raffinate obtained in the step S4, wherein the oil content of liquid water is less than 5ppm after oil separation;
and S6, sequentially carrying out triple-effect vacuum evaporation, cooling crystallization and centrifugal separation on the raffinate obtained after oil separation in the step S5, and finally obtaining a solid, namely a refined nickel sulfate finished product.
2. The process according to claim 1, wherein in step S1, the dissolution temperature is 40-50 ℃, and the concentration of nickel in the solution is controlled to be 60-80 g/L.
3. The process of claim 1, wherein in step S2, the hydrogen sulfide gas is added in an amount of 2-4 times the theoretical amount of copper deposition while maintaining the pH <2, the copper deposition reaction temperature is 70-90 ℃, and the reaction time is 0.5-3 h.
4. The process as claimed in claim 1, wherein in step S2, the main component of the filter residue is copper sulfide, and the filter residue is returned to the flash smelting system for recovery.
5. The process of claim 1, wherein in step S2, the hydrogen sulfide gas is generated by gas-liquid sulfurization of sodium hydrosulfide.
6. The process according to claim 1, wherein in step S3, the pH of the filtrate obtained in step S2 is adjusted with a 1% -10% NaOH solution at 60 ℃ -80 ℃ by mass concentration; the mass concentration of hydrogen peroxide is 27.5 percent, and the molar ratio of Fe to hydrogen peroxide is 1: 2; the reaction time is 20-30 min.
7. The process as claimed in claim 1, wherein in step S4, the pH of the filtrate obtained in step S3 is adjusted with a 1% -10% NaOH solution by mass concentration; in the extraction, the volume concentration of C272 is 15%, the saponification rate is 65%, the extraction ratio of O/A is 1-1.6:1, and the temperature is normal temperature; the back extraction is carried out by adopting sulfuric acid, the concentration of the sulfuric acid is 160-.
8. The process of claim 1, wherein in step S4, 3-5 stages of extraction and stripping are performed.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210464813.0A CN114752782A (en) | 2022-04-29 | 2022-04-29 | Process suitable for refining and impurity removing of low-calcium magnesium crude nickel sulfate |
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| CN202210464813.0A CN114752782A (en) | 2022-04-29 | 2022-04-29 | Process suitable for refining and impurity removing of low-calcium magnesium crude nickel sulfate |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA989493B (en) * | 1997-10-24 | 1999-04-21 | Dynatec Corp | Process for upgrading copper sulphide residues containing nickel and iron |
| CN101209853A (en) * | 2007-12-25 | 2008-07-02 | 金川集团有限公司 | Method for preparing cupric sulfate from spongy copper and copper-containing acid pickle |
| CN108117105A (en) * | 2017-12-29 | 2018-06-05 | 江西瑞林稀贵金属科技有限公司 | A kind of process for purification of Copper making by-product crude nickle sulphate |
| CN109897955A (en) * | 2019-04-17 | 2019-06-18 | 江西铜业股份有限公司 | A kind of method of nickel sulfate solution deep purifying |
| CN112481501A (en) * | 2020-11-12 | 2021-03-12 | 阳谷祥光铜业有限公司 | Method for preparing nickel powder by using decoppering final solution |
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2022
- 2022-04-29 CN CN202210464813.0A patent/CN114752782A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA989493B (en) * | 1997-10-24 | 1999-04-21 | Dynatec Corp | Process for upgrading copper sulphide residues containing nickel and iron |
| CN101209853A (en) * | 2007-12-25 | 2008-07-02 | 金川集团有限公司 | Method for preparing cupric sulfate from spongy copper and copper-containing acid pickle |
| CN108117105A (en) * | 2017-12-29 | 2018-06-05 | 江西瑞林稀贵金属科技有限公司 | A kind of process for purification of Copper making by-product crude nickle sulphate |
| CN109897955A (en) * | 2019-04-17 | 2019-06-18 | 江西铜业股份有限公司 | A kind of method of nickel sulfate solution deep purifying |
| CN112481501A (en) * | 2020-11-12 | 2021-03-12 | 阳谷祥光铜业有限公司 | Method for preparing nickel powder by using decoppering final solution |
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