CN116334393A - Method for preparing battery grade pure nickel sulfate solution from battery waste - Google Patents
Method for preparing battery grade pure nickel sulfate solution from battery waste Download PDFInfo
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- CN116334393A CN116334393A CN202310151033.5A CN202310151033A CN116334393A CN 116334393 A CN116334393 A CN 116334393A CN 202310151033 A CN202310151033 A CN 202310151033A CN 116334393 A CN116334393 A CN 116334393A
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- Prior art keywords
- battery
- nickel sulfate
- sulfate solution
- waste
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B15/00—Other processes for the manufacture of iron from iron compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0086—Treating solutions by physical methods
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- C—CHEMISTRY; METALLURGY
- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for preparing battery grade pure nickel sulfate solution from battery waste, which selects an organic extractant, adopts 1N sulfuric acid to control the PH value of materials in the extraction process according to the extraction rules of the extractant under different PH values, and the obtained raffinate is the battery grade nickel sulfate solution which can reach the industry standard, namely, the nickel element in the battery waste can be recovered through one extraction process, the battery grade nickel sulfate solution can be directly obtained, the process is greatly simplified, and the cost reduction and the synergy are realized; and the extracted organic extract is subjected to acid back extraction to respectively obtain cobalt magnesium back extraction liquid, copper manganese calcium back extraction liquid and iron back extraction liquid, so that other metal elements can be recovered, and the iron back extraction liquid can also be used for recycling the organic extractant, thereby achieving the purposes of further reducing cost and enhancing efficiency.
Description
Technical Field
The invention relates to the technical field of recycling of waste battery materials, in particular to a method for preparing battery grade pure nickel sulfate solution from battery waste.
Background
Along with the continuous development of the electric vehicle industry, the requirements of ternary lithium battery cells are continuously increased, and meanwhile, ternary lithium battery waste is also continuously increased, and nickel metal contained in waste battery materials is also used as a preparation raw material of the cells, so that the nickel metal is extracted and recovered from the waste batteries in the prior art. However, most of the current processes have complicated steps and poor recovery efficiency of raw materials, and after nickel is recovered, procedures are needed to prepare the nickel into the battery grade pure nickel sulfate meeting the standard.
Disclosure of Invention
Therefore, based on the background, the invention improves the prior art, and provides a method for preparing the battery grade pure nickel sulfate solution from the battery waste, which can not only efficiently extract nickel element through a one-time extraction process, but also directly obtain the battery grade pure nickel sulfate solution meeting the standard, thereby greatly shortening the process, reducing the energy consumption and reducing the cost.
A method for preparing battery grade pure nickel sulfate from battery waste, which comprises the following steps:
s1: preparation of battery waste liquid
Crushing the waste batteries, sieving, adding the crushed waste batteries into sulfuric acid for acid dissolution, and filtering to remove insoluble impurities;
s2: extraction separation
Adding an organic extractant into the sulfuric acid feed liquid of the waste battery, and controlling the PH value in the extraction process to obtain an organic extract and raffinate;
s3: separation of cobalt and magnesium elements
Carrying out back extraction on the organic extract liquid obtained in the step S1 by adopting sulfuric acid solution to obtain cobalt magnesium back extraction liquid;
s4: separating copper, manganese and calcium elements
Carrying out back extraction on the organic extract in the step S3 by adopting hydrochloric acid to obtain copper-manganese-calcium back extraction liquid;
s5: separation of elemental iron
Carrying out back extraction on the organic extract in the step S4 by adopting hydrochloric acid to obtain iron back extract;
s6: organic extractant recovery
And (3) adding water into the organic extract obtained in the step (S5) for washing, and separating to obtain the organic extract which is the recovered organic extractant.
Further, the organic extractant in step S2 is P-507 extractant.
Further, in the step S2, the PH value of the extraction process is controlled by adopting 1N sulfuric acid;
the pH value of the extraction process is controlled to be 4-5.
Further, the concentration of the sulfuric acid solution in step S2 is 2N.
Further, the concentration of hydrochloric acid in step S5 is 3N.
Further, the concentration of hydrochloric acid in step S5 is 6N.
The beneficial effects achieved by adopting the invention are as follows:
according to the invention, an organic extractant is selected, and according to the extraction rules of the extractant under different pH values, the pH value of materials in the extraction process is controlled by adopting 1N sulfuric acid, and the obtained raffinate is battery grade nickel sulfate liquid which can reach the industry standard, namely, through one extraction process, not only nickel element in battery waste can be recovered, but also battery grade nickel sulfate liquid can be directly obtained, the process is greatly simplified, and the cost reduction and synergy are realized;
and the extracted organic extract is subjected to acid back extraction to respectively obtain cobalt magnesium back extraction liquid, copper manganese calcium back extraction liquid and iron back extraction liquid, so that other metal elements can be recovered, and the iron back extraction liquid can also be used for recycling the organic extractant, thereby achieving the purposes of further reducing cost and enhancing efficiency.
Detailed Description
Reference now will be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the scope or spirit of the invention. For example, features illustrated or described as part of one embodiment can be used on another embodiment to yield still a further embodiment.
Accordingly, it is intended that the present invention cover such modifications and variations as fall within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention will be disclosed in or be apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention. The invention is further illustrated below with reference to examples.
A method for preparing battery grade pure nickel sulfate from battery waste, which comprises the following steps:
s1: preparation of battery waste liquid
Crushing the waste batteries, sieving, adding the crushed waste batteries into sulfuric acid for acid dissolution, and filtering to remove insoluble impurities;
s2: extraction separation
Adding an organic extractant into the sulfuric acid feed liquid of the waste battery, and controlling the PH value in the extraction process to obtain an organic extract and raffinate;
the organic extractant in the step adopts a P-507 extractant, the P-507 extractant has different extraction rates of cobalt, magnesium, copper, manganese, calcium and other metal elements at different pH values, and the higher the pH value is, the higher the extraction rate of nickel is, so in order to reduce the extraction rate of nickel in the extraction process, the pH value of materials in the extraction process needs to be adjusted.
S3: separation of cobalt and magnesium elements
Carrying out back extraction on the organic extract liquid obtained in the step S1 by adopting sulfuric acid solution to obtain cobalt magnesium back extraction liquid;
s4: separating copper, manganese and calcium elements
Carrying out back extraction on the organic extract in the step S3 by adopting hydrochloric acid to obtain copper-manganese-calcium back extraction liquid;
s5: separation of elemental iron
Carrying out back extraction on the organic extract in the step S4 by adopting hydrochloric acid to obtain iron back extract;
s6: organic extractant recovery
And (3) adding water into the organic extract obtained in the step (S5) for washing, and separating to obtain the organic extract which is the recovered organic extractant.
Example 1: s1: preparation of battery waste liquid
Crushing the waste batteries, sieving, adding the crushed waste batteries into sulfuric acid for acid dissolution, and filtering to remove insoluble impurities;
s2: extraction separation
Adding a P-507 extractant into the sulfuric acid feed liquid of the waste battery, and controlling the PH value in the extraction process to obtain an organic extract and raffinate;
preferably, the PH value in the extraction process can be controlled to be 4-5, so that the extraction rate of metals such as copper, manganese, calcium, cobalt and the like in the P-507 extractant is higher, and the extraction rate of nickel is lower.
In the specific implementation, the magnesium content in the raffinate after the extraction by the P-507 extractant is less than or equal to 1mg/l, and after the detection according to the industry standard of the battery grade nickel sulfate solution with the standard number of T/ATCRR 122020S3, the standard is completely met, namely the battery grade nickel sulfate solution meeting the industry standard can be prepared by one-step extraction of the step.
S3: separation of cobalt and magnesium elements
Carrying out back extraction on the organic extract liquid obtained in the step S1 by adopting a 2N sulfuric acid solution to obtain cobalt magnesium back extraction liquid;
the nickel in the cobalt-magnesium back extraction liquid is less than or equal to 1 g/liter.
S4: separating copper, manganese and calcium elements
Performing back extraction on the organic extract in the step S3 by adopting 3N hydrochloric acid to obtain copper-manganese-calcium back extract;
in the step, hydrochloric acid is adopted to replace sulfuric acid to strip copper, manganese and calcium elements, so that the increase of three-phase slag caused by precipitation can be prevented.
S5: separation of elemental iron
Performing back extraction on the organic extract in the step S4 by adopting 6N hydrochloric acid to obtain an iron back extract difficult to back extract;
s6: organic extractant recovery
And (3) adding water into the organic extract obtained in the step (S5) for washing, and separating to obtain the organic extract which is the recovered organic extractant.
The organic extractant recovered in this step can be directly applied to step S2 for extraction.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
Claims (6)
1. The method for preparing the battery grade pure nickel sulfate solution from the battery waste is characterized by comprising the following steps:
s1: preparation of battery waste liquid
Crushing the waste batteries, sieving, adding the crushed waste batteries into sulfuric acid for acid dissolution, and filtering to remove insoluble impurities;
s2: extraction separation
Adding an organic extractant into the sulfuric acid feed liquid of the waste battery, and controlling the PH value in the extraction process to obtain an organic extract and raffinate;
s3: separation of cobalt and magnesium elements
Carrying out back extraction on the organic extract liquid obtained in the step S1 by adopting sulfuric acid solution to obtain cobalt magnesium back extraction liquid;
s4: separating copper, manganese and calcium elements
Carrying out back extraction on the organic extract in the step S3 by adopting hydrochloric acid to obtain copper-manganese-calcium back extraction liquid;
s5: separation of elemental iron
Carrying out back extraction on the organic extract in the step S4 by adopting hydrochloric acid to obtain iron back extract;
s6: organic extractant recovery
And (3) adding water into the organic extract obtained in the step (S5) for washing, and separating to obtain the organic extract which is the recovered organic extractant.
2. The method for preparing battery grade pure nickel sulfate solution from battery waste according to claim 1, wherein the organic extractant in step S2 is P-507 extractant.
3. The method for preparing battery grade pure nickel sulfate solution from battery waste according to claim 2, wherein in step S2, the PH value of the extraction process is controlled by 1N sulfuric acid;
the pH value of the extraction process is controlled to be 4-5.
4. The method for preparing battery grade pure nickel sulfate solution from battery waste according to claim 1, wherein the concentration of sulfuric acid solution in step S2 is 2N.
5. The method for preparing battery grade pure nickel sulfate solution from battery waste according to claim 1, wherein the concentration of hydrochloric acid in step S5 is 3N.
6. The method for preparing battery grade pure nickel sulfate solution from battery waste according to claim 1, wherein the concentration of hydrochloric acid in step S5 is 6N.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310151033.5A CN116334393A (en) | 2023-02-22 | 2023-02-22 | Method for preparing battery grade pure nickel sulfate solution from battery waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310151033.5A CN116334393A (en) | 2023-02-22 | 2023-02-22 | Method for preparing battery grade pure nickel sulfate solution from battery waste |
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| Publication Number | Publication Date |
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| CN116334393A true CN116334393A (en) | 2023-06-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202310151033.5A Pending CN116334393A (en) | 2023-02-22 | 2023-02-22 | Method for preparing battery grade pure nickel sulfate solution from battery waste |
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| CN (1) | CN116334393A (en) |
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2023
- 2023-02-22 CN CN202310151033.5A patent/CN116334393A/en active Pending
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