Method for recovering metal from waste nickel cobalt lithium manganate battery material

Abstract

The invention relates to a method for recovering metal from a waste nickel cobalt lithium manganate battery material, and belongs to the technical field of metal separation and enrichment, and the raw materials for recovering metal from the waste nickel cobalt lithium manganate battery material comprise coke, an ion battery ternary precursor material, deionized water, hydrogen peroxide, sulfuric acid, sodium carbonate, nickel carbonate and the like. The thought of synchronous extraction of nickel, cobalt and manganese in the waste lithium ion battery, directional purification of impurity elements and short-process direct preparation of the nickel-cobalt-manganese ternary material is innovatively provided, and a theoretical basis and a technical prototype are provided for green recovery and value-added utilization of nickel, cobalt and manganese in the waste lithium ion battery. The ternary precursor material of the lithium ion battery is used as functional orientation, selective precipitation and low-separation-ratio extraction separation of the waste lithium ion battery leachate are carried out, and the environmental load is minimized.

Description

Technical Field

[0001] The invention belongs to the technical field of separation and enrichment of metals, and in particular relates to a method for recovering metals from waste nickel-cobalt-manganese-oxide lithium battery materials. Background Art

[0002] With the popularity of electric vehicles and portable electronic devices, the use of lithium-ion batteries has increased dramatically, resulting in an increase in the generation of waste lithium-ion batteries. Waste nickel-cobalt-manganese oxide batteries, as one of the important types, mainly contain valuable metal components such as nickel, cobalt, and manganese. These metals have important economic and environmental value in the manufacture and recycling of batteries. Therefore, the development of effective recycling technology is of great significance to achieve sustainable utilization of resources and reduce environmental pollution.

[0003] At present, the commonly used treatment methods for waste nickel-cobalt-manganese-oxide lithium batteries mainly include physical methods, chemical methods and thermal treatment methods. Among them, physical methods such as crushing and screening can initially separate the metal components in the battery, but their recovery rate is relatively low and impurities cannot be removed. Chemical methods extract metals through acid leaching and other means, but this method usually has a long process, high cost and serious environmental pollution. In addition, the thermal treatment method produces harmful gases during the roasting process, which burdens the environment.

[0004] The existing technology generally has the following shortcomings when processing waste lithium-ion batteries: first, the processing process is complicated, which leads to increased time and cost; second, it causes pollution to the environment, especially in the metal extraction process, which easily produces waste liquid and harmful gases; third, it is difficult to effectively remove impurity elements, affecting the purity and market value of the final product.

[0005] In response to the above problems, the present invention innovatively proposes a method for recovering metals from waste nickel-cobalt-manganese-oxide lithium battery materials. This method emphasizes the simultaneous extraction of nickel, cobalt, and manganese and the directional purification of impurity elements, simplifies the traditional processing flow, and reduces the impact on the environment. By using lithium-ion battery ternary precursor materials as a functional guide, selective precipitation and low separation ratio extraction separation of waste lithium-ion battery leachate are carried out to minimize the environmental load. This method not only improves the metal recovery rate, but also provides a theoretical basis and technical prototype for the green recycling and value-added utilization of waste lithium-ion batteries, and has broad application prospects. Summary of the invention

[0006] The purpose of the present invention is to provide a method for recovering metals from waste nickel-cobalt-manganese-oxide lithium battery materials, especially by combining traditional metallurgical methods with terminal product manufacturing processes, through short-process, low-cost, refined processing, directly preparing high-value-added products with specific structures and functions, studying the recovery of metals such as nickel, cobalt, and manganese from waste batteries, and producing products such as nickel sulfate, cobalt sulfate, and manganese sulfate, which not only solves the problem of insufficient resources and meets the needs of power battery production, but also solves the problem of environmental pollution caused by waste batteries, and is of great significance to promoting the sustainable development of my country's new energy industry chain and environmental protection.

[0007] The specific technical solutions are as follows:

[0008] A method for recovering metals from waste nickel cobalt manganese oxide battery materials, characterized in that, in parts by weight, the raw materials of the method for recovering metals from waste nickel cobalt manganese oxide battery materials are composed of: 50-100 parts of coke, 100-200 parts of ternary precursor materials for ion batteries, 500-1000 parts of deionized water, 10-30 parts of hydrogen peroxide, 20-35 parts of sulfuric acid, 3-10 parts of sodium carbonate, 2-5 parts of nickel carbonate, 0.025-0.1 parts of modified polystyrene, 10-60 parts of ethanol, and 2-4 parts of polyvinyl alcohol. The specific steps of recovering metals from waste nickel cobalt manganese oxide battery materials are as follows:

[0009] S1: Add coke and ternary precursor materials of ion batteries in proportion to a multifunctional reactor, stir at a rate of 1300-1500 r / min, and mix and stir at 10-30° C. for 30-120 minutes;

[0010] S2: After stirring, placing the mixture in a muffle furnace, setting the roasting temperature to 400-600° C., and the roasting time to 10-240 minutes, to obtain a roasted material;

[0011] S3: adding the calcined material to a ball mill at a ratio of 1:1.5 to 1:2 and mixing with a steel ball milling medium, grinding at a speed of 200 to 250 rpm for 20 to 60 minutes, and then soaking in water for 40 to 120 minutes;

[0012] S4: The calcined material after water immersion is passed through a vibrating screen at a vibration frequency of 600 to 1200 rpm, with an amplitude of 2 to 4 mm, and sieved for 10 to 30 minutes, and the sieved calcined material is filtered using a pressure filter, with a filtration pressure of 0.5 to 1.0 MPa and a filtration speed of 5 to 10 L / min to obtain a lithium-containing aqueous solution and nickel-cobalt-manganese slag;

[0013] S5: The nickel-cobalt-manganese slag in step S is poured into a leaching tank at a liquid-to-solid ratio of 4 to 12, and stirred at a stirring speed of 1500 to 1800 r / min, and mixed and stirred at 10 to 30° C. for 60 to 120 minutes;

[0014] S6: adding sulfuric acid and hydrogen peroxide in proportion to the leaching tank in step S5, stirring and leaching, controlling the leaching temperature at 45°C to 85°C, the leaching time at 30 to 150 minutes, setting the stirring speed at 1500 to 1800 r / min, and mixing and stirring at 10 to 30°C for 60 to 120 minutes;

[0015] S7: The leachate obtained in step S6 is subjected to filter pressing at a filtration pressure of 0.4-0.8 MPa. The filter residue obtained after the filter pressing is pumped into a slag washing tank for slag washing. The filter residue obtained after the slag washing is used as scrap residue, and the slag washing water is pumped into the leaching tank in step S5 as bottom water;

[0016] S8: The leachate obtained by the filter press in step S7 is subjected to directional precipitation and impurity removal, sodium carbonate and nickel carbonate are added to the iron removal tank in proportion to remove iron and aluminum and filter press, the filtration pressure is 0.4-0.8MPa, and iron-aluminum slag and iron-aluminum-removed liquid are obtained after filter press, and the iron-aluminum slag is washed with 5-10 parts of sulfuric acid and 500-600 parts of deionized water. The iron slag obtained by filter press after washing can be scrapped, and the washing water is pumped into the leaching tank in step S5 as bottom water;

[0017] S9: The iron and aluminum removal solution in step S8 is subjected to extraction and impurity removal technology to obtain copper, manganese, zinc solution and nickel, cobalt, manganese stripping solution products.

[0018] In some of the embodiments, the method further comprises treating the calcined material in step S2 under a nitrogen atmosphere at a calcination temperature of 400-600° C. for 20-40 minutes to prevent metal oxidation and improve the recovery rate of nickel, cobalt and manganese.

[0019] In some of the embodiments, in step S3, polyvinyl alcohol is added in a concentration of 2% to 4% by mass during the water immersion process to enhance the hydrophilicity between particles and improve the dissolution rate of metal.

[0020] In some of the embodiments, in step S4, during the screening process, an ultrasonic vibrating screen is used for screening at a frequency of 20 to 40 kHz for 20 to 60 minutes to improve separation efficiency and reduce particle adhesion.

[0021] In some of the embodiments, in step S7, during the residue washing process, deionized water is used for three rinses, and the amount of water used each time is 2 to 5 times the weight of the residue to ensure that residual impurities are removed.

[0022] In some of the embodiments, in step S8, modified polystyrene is used as a precipitant to improve the selectivity of iron and aluminum removal, the reaction temperature is 40-60° C., and the treatment time is 30-90 minutes.

[0023] In some of the embodiments, in step S9, 10% to 12% of an organic solvent ethanol is added for extraction to improve the separation efficiency of copper, manganese and zinc, and the reaction time is 120 minutes.

[0024] This reaction has the following advantages:

[0025] (1) Yield improvement: By optimizing the roasting temperature and time, controlling the pH value of the leaching solution and the reaction temperature, the recovery rates of nickel, cobalt and manganese can be significantly improved, ensuring maximum extraction of valuable metal components.

[0026] (2) Environmentally friendly: This method adopts low separation ratio extraction separation technology, which reduces the risk of environmental pollution, reduces the emission of waste liquid and harmful gases, and achieves green recycling.

[0027] (3) Cost reduction: Combined with selective precipitation technology, it reduces the demand for expensive chemical reagents, reduces overall production costs, and improves economic benefits.

[0028] (4) Multi-metal recovery: This reaction can achieve the simultaneous extraction of nickel, cobalt and manganese, while purifying the impurity elements in a targeted manner, making the final product purer and more competitive in the market. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 Schematic diagram of the process of recovering metals from waste nickel-cobalt-manganese-oxide lithium battery materials DETAILED DESCRIPTION

[0030] The following will combine the technical process steps, specific implementation conditions and materials in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0031] Example 1

[0032] like Figure 1As shown, coke and ternary precursor materials for ion batteries are added in proportion to a multifunctional reactor, the stirring rate is 1300r / min, the mixture is stirred at 15°C for 40 minutes, and after stirring, it is placed in a muffle furnace, the roasting temperature is set to 400°C, the roasting time is 100 minutes, and roasting is performed to obtain a roasted material, the roasted material is treated in a nitrogen atmosphere, the roasting temperature is 400°C, the treatment time is 20 minutes, the treated material is mixed with a steel ball mill at a ratio of 1:1.5, added to a ball mill, ground at a speed of 200rpm for 20 minutes, and then immersed in water for 40 minutes, 2% mass concentration of polyvinyl alcohol is added to the aqueous solution to obtain the calcined material after water immersion, and set aside.

[0033] Table 1 Ratio of raw materials required for calcination and water immersion of ternary precursor materials for ion batteries in Example 1

[0034] Coke 50 servings Ternary precursor materials for ion batteries 100 copies Polyvinyl alcohol 2 servings

[0035] Example 2

[0036] like Figure 1 As shown, coke and ternary precursor materials for ion batteries are added in proportion to a multifunctional reactor, the stirring rate is 1500r / min, the mixture is stirred at 30°C for 120 minutes, and after stirring, it is placed in a muffle furnace, the roasting temperature is set to 600°C, the roasting time is 200 minutes, and roasting is performed to obtain a roasted material, the roasted material is treated in a nitrogen atmosphere, the roasting temperature is 500°C, the treatment time is 30 minutes, the treated material is mixed with a steel ball mill at a ratio of 1:2 and added to a ball mill, ground at a speed of 240rpm for 50 minutes, and then immersed in water for 80 minutes, 4% mass concentration of polyvinyl alcohol is added to the aqueous solution to obtain the leached roasted material for standby use.

[0037] Table 2 Ratio of raw materials required for calcination and water immersion of ternary precursor materials for ion batteries in Example 2

[0038] Coke 50 servings Ternary precursor materials for ion batteries 100 copies Polyvinyl alcohol 4 servings

[0039] Example 3

[0040] like Figure 1 As shown, the calcined material after water immersion in Example 1 was passed through a vibrating screen at a vibration frequency of 600 rpm, the amplitude was controlled to be 2 mm, and sieving was performed for 10 minutes. The sifted calcined material was filtered using a pressure filter, the filtration pressure was set to 0.5 MPa, and the filtration speed was set to 5 L / min to obtain a lithium-containing aqueous solution and nickel-cobalt-manganese slag; set aside.

[0041] Example 4

[0042] like Figure 1As shown, the calcined material after water immersion in Example 2 was sieved by an ultrasonic vibrating screen at a frequency of 40 kHz for 60 minutes, and the sieved calcined material was filtered using a pressure filter, the filtration pressure was set to 1.0 MPa, and the filtration speed was set to 10 L / min to obtain a lithium-containing aqueous solution and nickel-cobalt-manganese slag; set aside.

[0043] Example 5

[0044] like Figure 1 As shown, the nickel-cobalt-manganese slag in Example 3 is poured into a leaching tank at a liquid-to-solid ratio of 6, stirred, and the stirring speed is set to 1500r / min, and mixed and stirred for 60 minutes at 10°C; sulfuric acid and hydrogen peroxide are added to the leaching tank in step S5 in proportion, stirred and leached, the leaching temperature is controlled at 45°C, the leaching time is 60 minutes, the stirring speed is set to 1500r / min, and mixed and stirred for 60 minutes at 10°C; the obtained leachate is filtered, and the filtration pressure is 0.4MPa. The filter residue obtained after the filter pressure is poured into a slag washing tank for slag washing. During the slag washing process, deionized water is used for three rinses, and the amount of water used each time is twice the weight of the filter residue. The filter residue obtained after slag washing is used as scrap residue, and the slag washing water is poured into the leaching tank in step S5 as bottom water for standby use.

[0045] Table 3 Example 5 Raw material ratio required for leaching nickel-cobalt-manganese slag

[0046] sulfuric acid 5 servings Hydrogen Peroxide 15 servings Deionized water 300 copies

[0047] Example 6

[0048] like Figure 1 As shown, the nickel-cobalt-manganese slag in Example 4 is poured into a leaching tank at a liquid-to-solid ratio of 10, stirred, and the stirring speed is set to 1800 r / min, and mixed and stirred for 100 minutes at 30°C; sulfuric acid and hydrogen peroxide are added to the leaching tank in step S5 in proportion, stirred and leached, the leaching temperature is controlled at 65°C, the leaching time is 120 minutes, the stirring speed is set to 1600 r / min, and mixed and stirred for 100 minutes at 30°C; the obtained leachate is filtered at a filtration pressure of 0.8 MPa, and the filter residue obtained after the filter pressure is poured into a slag washing tank for slag washing. During the slag washing process, deionized water is used for three rinses, and the amount of water used each time is 5 times the weight of the filter residue. The filter residue obtained after slag washing is used as scrap residue, and the slag washing water is poured into the leaching tank in step S5 as bottom water for standby use.

[0049] Table 4 Example 5 Raw material ratio required for leaching nickel-cobalt-manganese slag

[0050] sulfuric acid 3 servings Hydrogen Peroxide 15 servings Deionized water 700 copies

[0051] Example 7

[0052] like Figure 1 As shown, the leachate obtained by filter pressing in Example 5 is subjected to directional precipitation and impurity removal, sodium carbonate and nickel carbonate are added to the iron removal tank in proportion to remove iron and aluminum and filter pressing is performed, the filtration pressure is 0.4 MPa, and iron-aluminum slag and iron-aluminum-removed liquid are obtained after filter pressing. The iron-aluminum slag is washed with sulfuric acid and deionized water, and the iron slag obtained by filter pressing after slag washing can be scrapped, and the slag washing water is pumped into the intermediate leaching tank as bottom water; the iron-aluminum-removed liquid is extracted and impurities are removed by adding 10% organic solvent ethanol to obtain copper, manganese, zinc solution and nickel, cobalt, manganese stripping liquid products.

[0053] Table 5 Ratio of raw materials required for impurity removal of leachate in Example 7

[0054]

[0055]

[0056] According to "YS / T 798-2012 Nickel Cobalt Manganese Oxide Lithium", the metal ion concentration was determined using inductively coupled plasma emission spectroscopy to determine the content of each element in the nickel cobalt manganese stripping solution. The test results showed that it met the national standards.

[0057] Table 6 Detection composition table of nickel-cobalt-manganese stripping solution prepared in Example 7

[0058] project content Nickel (Ni)w% 19.246 Cobalt (Co) w% 17.615 Manganese (Mn) w% 21.365 Copper (Cu) w% 7.549 Sodium(Na)w% 0.0176 Magnesium (Mg) w% 0.0107 Calcium (Ca) w% 0.0086 Iron (Fe) w% 0.0027 Zinc (Zn) w% 0.0013 Copper (Cu) w% 0.0032

[0059] Example 8

[0060] like Figure 1 As shown, the leachate obtained by pressure filtration in Example 6 is subjected to directional precipitation and impurity removal, sodium carbonate and nickel carbonate are added to the iron removal tank in proportion, and modified polystyrene is used as a precipitant to improve the selectivity of iron and aluminum removal, the reaction temperature is 60°C, and the treatment time is 90 minutes. Pressure filtration is also performed, and the filtration pressure is 0.8MPa. After pressure filtration, iron-aluminum slag and iron-aluminum-removed liquid are obtained. The iron-aluminum slag is washed with sulfuric acid and deionized water. The iron slag obtained by pressure filtration after washing can be scrapped, and the slag washing water is pumped into the leaching tank in step S5 as bottom water; the iron-aluminum-removed liquid is extracted and impurities are removed by adding 12% organic solvent ethanol to obtain copper, manganese, zinc solution and nickel, cobalt, manganese stripping liquid products.

[0061] Table 7 Ratio of raw materials required for impurity removal of leachate in Example 8

[0062]

[0063]

[0064] According to "YS / T 798-2012 Nickel Cobalt Manganese Oxide Lithium", the metal ion concentration was determined using inductively coupled plasma emission spectroscopy to determine the content of each element in the nickel cobalt manganese stripping solution. The test results showed that it met the national standards.

[0065] Table 8 Detection composition table of nickel-cobalt-manganese stripping solution prepared in Example 8

[0066] project content Nickel (Ni)w% 21.726 Cobalt (Co) w% 18.975 Manganese (Mn) w% 13.426 Copper (Cu) w% 7.537 Sodium(Na)w% 0.0278 Magnesium (Mg) w% 0.0113 Calcium (Ca) w% 0.0045 Iron (Fe) w% 0.0032 Zinc (Zn) w% 0.0004 Copper (Cu) w% 0.0019

[0067] Technical personnel should note that: Although the present invention has been described according to the above specific implementation methods, the inventive concept of the present invention is not limited to this invention, and any modification using the inventive concept will be included in the scope of protection of this patent.

Claims

1. A method for recovering metals from waste nickel-cobalt-manganese-oxide lithium battery materials, characterized in that: The raw material composition of the method for recovering metals from waste nickel cobalt manganese oxide battery materials is as follows: 50-100 parts of coke, 100-200 parts of ternary precursor materials for ion batteries, 500-1000 parts of deionized water, 10-30 parts of hydrogen peroxide, 20-35 parts of sulfuric acid, 3-10 parts of sodium carbonate, 2-5 parts of nickel carbonate, 0.025-0.1 parts of modified polystyrene, 10-60 parts of ethanol, and 2-4 parts of polyvinyl alcohol. The specific steps of recovering metals from waste nickel cobalt manganese oxide battery materials are as follows: S1: Add coke and ternary precursor materials of ion batteries in proportion to a multifunctional reactor, stir at a rate of 1300-1500 r / min, and mix and stir at 10-30° C. for 30-120 minutes; S2: After stirring, placing the mixture in a muffle furnace, setting the roasting temperature to 400-600° C., and the roasting time to 10-240 minutes, to obtain a roasted material; S3: adding the calcined material to a ball mill at a ratio of 1:1.5 to 1:2 and mixing with a steel ball milling medium, grinding at a speed of 200 to 250 rpm for 20 to 60 minutes, and then soaking in water for 40 to 120 minutes; S4: The calcined material after water immersion is passed through a vibrating screen at a vibration frequency of 600 to 1200 rpm, with an amplitude of 2 to 4 mm, and sieved for 10 to 30 minutes, and the sieved calcined material is filtered using a pressure filter, with a filtration pressure of 0.5 to 1.0 MPa and a filtration speed of 5 to 10 L / min to obtain a lithium-containing aqueous solution and nickel-cobalt-manganese slag; S5: The nickel-cobalt-manganese slag in step S is poured into a leaching tank at a liquid-to-solid ratio of 4 to 12, and stirred at a stirring speed of 1500 to 1800 r / min, and mixed and stirred at 10 to 30° C. for 60 to 120 minutes; S6: adding sulfuric acid and hydrogen peroxide in proportion to the leaching tank in step S5, stirring and leaching, controlling the leaching temperature at 45°C to 85°C, the leaching time at 30 to 150 minutes, setting the stirring speed at 1500 to 1800 r / min, and mixing and stirring at 10 to 30°C for 60 to 120 minutes; S7: The leachate obtained in step S6 is subjected to filter pressing at a filtration pressure of 0.4-0.8 MPa. The filter residue obtained after the filter pressing is pumped into a slag washing tank for slag washing. The filter residue obtained after the slag washing is used as scrap residue, and the slag washing water is pumped into the leaching tank in step S5 as bottom water; S8: The leachate obtained by the filter press in step S7 is subjected to directional precipitation and impurity removal, sodium carbonate and nickel carbonate are added to the iron removal tank in proportion to remove iron and aluminum and filter press, the filtration pressure is 0.4-0.8MPa, and iron-aluminum slag and iron-aluminum-removed liquid are obtained after filter press, and the iron-aluminum slag is washed with 5-10 parts of sulfuric acid and 500-600 parts of deionized water. The iron slag obtained by filter press after washing can be scrapped, and the washing water is pumped into the leaching tank in step S5 as bottom water; S9: The iron and aluminum removal solution in step S8 is subjected to extraction and impurity removal technology to obtain copper, manganese, zinc solution and nickel, cobalt, manganese stripping solution products.

2. A method for recovering metals from waste nickel-cobalt-manganese-oxide lithium battery materials as claimed in claim 1, characterized in that: The method further comprises in step S2 treating the calcined material under a nitrogen atmosphere at a calcination temperature of 400-600° C. for 20-40 minutes to prevent metal oxidation and improve the recovery rate of nickel, cobalt and manganese.

3. A method for recovering metals from waste nickel-cobalt-manganese-oxide lithium battery materials as claimed in claim 1, characterized in that: In step S3, polyvinyl alcohol with a mass concentration of 2% to 4% is added during the water immersion process to enhance the hydrophilicity between particles and improve the dissolution rate of metal.

4. A method for recovering metals from waste nickel-cobalt-manganese-oxide lithium battery materials as claimed in claim 1, characterized in that: In step S4, during the screening process, an ultrasonic vibrating screen is used for screening at a frequency of 20 to 40 kHz for 20 to 60 minutes to improve separation efficiency and reduce particle adhesion.

5. A method for recovering metals from waste nickel-cobalt-manganese-oxide lithium battery materials as claimed in claim 1, characterized in that: In step S7, during the residue washing process, deionized water is used for three rinses, and the amount of water used each time is 2 to 5 times the weight of the filter residue to ensure that residual impurities are removed.

6. A method for recovering metals from waste nickel-cobalt-manganese-oxide lithium battery materials as claimed in claim 1, characterized in that: In step S8, modified polystyrene is used as a precipitant to improve the selectivity of iron and aluminum removal, the reaction temperature is 40 to 60°C, and the treatment time is 30 to 90 minutes.

7. A method for recovering metals from waste nickel-cobalt-manganese-oxide lithium battery materials as claimed in claim 1, characterized in that: In step S9, 10% to 12% of an organic solvent ethanol is added for extraction to improve the separation efficiency of copper, manganese and zinc. The reaction time is 120 minutes.

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