Method for recovering nickel, cobalt, manganese and lithium

Abstract

The invention provides a method for recovering nickel, cobalt, manganese and lithium. The recycling method comprises the following steps that S1, lithium battery recycled materials are sequentially subjected to disassembling, crushing, heat treatment and demagnetization, and black powder is obtained; s2, decomposing the black powder by adopting an acidophilic bacteria solution, and removing a copper element and an aluminum element to obtain a decomposed product; s3, acid leaching is conducted on the decomposer, and a leaching solution is obtained; s4, performing fractional extraction on the leachate to obtain raffinate, a manganese salt solution, a cobalt salt solution and a nickel salt solution; s5, performing evaporative crystallization on the raffinate to obtain a lithium salt solution; and S6, the manganese salt solution, the cobalt salt solution, the nickel salt solution and the lithium salt solution are subjected to co-precipitation independently, and a manganese salt solid, a cobalt salt solid, a nickel salt solid and a lithium salt solid are obtained. By adopting the recovery method provided by the invention, the recovery purity and yield of nickel, cobalt, manganese and lithium can be improved.

Description

Technical Field

[0001] The present application relates to the technical field of metal recovery, and in particular to a method for recovering nickel, cobalt, manganese and lithium. Background Art

[0002] With the advancement of technology and the vigorous promotion of national policies, consumer electronic products are constantly being updated, new energy vehicles, energy storage batteries, etc. are becoming increasingly popular, and the demand for lithium-ion batteries is growing rapidly. In this context, lithium-ion battery manufacturers are constantly expanding their production capacity. As lithium batteries gradually enter the scrap stage, the demand for lithium battery recycling is growing rapidly. At this stage, with the continuous rise in the price of upstream lithium battery materials and the increasing shortage of upstream metal resources, the economic benefits of lithium battery material recycling will become more prominent. The metal elements in lithium batteries have economic value and can be recycled, becoming one of the important sources of raw materials for lithium-ion battery production. The recycling of lithium batteries can effectively reduce battery costs.

[0003] The traditional preparation method of recycled materials has low recycling efficiency and high environmental pollution, which makes it difficult to meet the current recycling requirements. The recycling of metal elements in lithium-ion batteries is limited by the variety of recycling sources, resource shortages, and complex recycling and purification processes, making it difficult for recycled materials to meet market demand. At the same time, the choice of recycling process has a great impact on the purity of recycled materials and environmental pollution. Therefore, choosing appropriate recycling sources and processes has become an important way to improve the purity of recycled materials, but the current traditional recycling process has not yet achieved the expected results. Summary of the invention

[0004] The main purpose of the present application is to provide a method for recovering nickel, cobalt, manganese and lithium to solve the problem of low recovery rate in the prior art for recovering nickel, cobalt, manganese and lithium.

[0005] In order to achieve the above-mentioned purpose, according to one aspect of the present application, a method for recovering nickel, cobalt, manganese and lithium is provided, and the recovery method comprises the following steps: step S1, disassembling, crushing, heat treating and demagnetizing the lithium battery recovery material in sequence to obtain black powder; step S2, decomposing the black powder with an acidophilic bacteria solution to remove copper and aluminum elements to obtain a decomposition product; step S3, acid leaching the decomposition product to obtain a leachate; step S4, graded extraction of the leachate to obtain a raffinate, a manganese salt solution, a cobalt salt solution and a nickel salt solution; step S5, evaporating and crystallizing the raffinate to obtain a lithium salt solution; step S6, independently co-precipitating the manganese salt solution, the cobalt salt solution, the nickel salt solution and the lithium salt solution to obtain a manganese salt solid, a cobalt salt solid, a nickel salt solid and a lithium salt solid.

[0006] Furthermore, in the above step S2, the OD600 of the acidophilic bacteria liquid is 0.6-1; and / or the ratio of the mass of the black powder to the volume of the acidophilic bacteria liquid is 1:10-20.

[0007] Furthermore, in the above step S2, the acidophilic bacteria liquid and the black powder are mixed to obtain a mixed liquid; the pH value of the mixed liquid is adjusted to 1 to 3, and then decomposed; further, the decomposition time is 3 to 7 days; and / or the decomposition temperature is 30 to 50°C.

[0008] Further, the above-mentioned acidophilic bacterial solution is A. monosulfide oxidizing bacterial solution, Acb. disulfide oxidizing bacterial solution or a mixed bacterial solution of A. monosulfide oxidizing bacterial solution and Acb. disulfide oxidizing bacterial solution; further, the mixed bacterial solution is formed by mixing A. monosulfide oxidizing bacterial solution with an OD600 of 0.6 to 1 and Acb. disulfide oxidizing bacterial solution with an OD600 of 0.6 to 1, and the volume ratio of A. monosulfide oxidizing bacterial solution and Acb. disulfide oxidizing bacterial solution is 1:0.5 to 2.

[0009] Furthermore, the above-mentioned step S4 includes: step S41, mixing the leachate with the first extractant to obtain a first mixed solution, adjusting the pH value of the first mixed solution to 2-3, and then performing a first extraction and a first stripping in sequence to obtain a first raffinate and a manganese salt solution; step S42, mixing the first raffinate with the second extractant to obtain a second mixed solution, adjusting the pH value of the second mixed solution to 4-5, and then performing a second extraction and a second stripping in sequence to obtain a second raffinate and a cobalt salt solution; step S43, mixing the second raffinate with the third extractant to obtain a third mixed solution, adjusting the pH value of the third mixed solution to 7-8, and then performing a third extraction and a third stripping in sequence to obtain a raffinate and a nickel salt solution.

[0010] Furthermore, the volume ratio of the above-mentioned leaching solution to the first extractant is 1:0.1~1; and / or, the volume ratio of the first raffinate to the second extractant is 1:0.1~1; and / or, the volume ratio of the second raffinate to the third extractant is 1:0.1~1; further, the concentrations of the first extractant, the second extractant and the third extractant are each independently 0.2~1 mol / L; and / or, the temperatures of the first extraction, the second extraction and the third extraction are each independently 25~50°C; further, the first extractant is P204 extractant and / or A308 extractant; and / or, the second extractant is P507 extractant and / or A308 extractant; and / or, the third extractant is C272 extractant and / or A308 extractant.

[0011] Furthermore, in the above step S1, the heat treatment temperature is 300-800°C; and / or, the heat treatment time is 1-8 hours; and / or, the median particle size of the black powder is 5-30 μm.

[0012] Furthermore, in the above step S3, the decomposition product is pickled with acid; further, the mass ratio of the acid to the decomposition product is 1:1-10; and / or the acid pickling temperature is 20-50°C; and / or the acid pickling time is 1-6h; further, the acid is sulfuric acid and / or hydrochloric acid.

[0013] Furthermore, in the above step S5, the temperature of evaporation crystallization is 80-150° C.; and / or the time of evaporation crystallization is 1-6 hours.

[0014] Furthermore, the coprecipitation temperature is 20-30°C; and / or the coprecipitation time is 1-6h; further, the precipitant used in the coprecipitation is selected from any one or more of NH4HCO3, NaHCO3, Na2CO3 and NaOH.

[0015] Applying the technical solution of the present application, in step S1, the lithium battery recycling material is disassembled and crushed in turn, which helps to separate the material containing the recycling element, remove the organic components in the material by heat treatment, and remove the magnetic impurities such as Fe in the material by demagnetization. In step S2, the black powder is decomposed by acidophilic bacteria liquid, which helps to remove the copper and aluminum elements in the black powder, thereby helping to improve the purity and yield of the recovered metal. In step S3, the decomposed product is acid-leached, and the manganese, cobalt, nickel and lithium in the decomposed product are dissolved to obtain a leachate. In step S4, the manganese, cobalt, nickel and lithium in the leachate are effectively separated by graded extraction. The present application effectively recovers nickel, cobalt, manganese and lithium from lithium battery recycling materials by adopting a composite recovery process combining physical recovery, biological recovery and wet recovery, especially using acidophilic bacteria for biological recovery, so that the purification of metal elements is more efficient, and at the same time, different metals can be selectively separated by graded extraction. Therefore, the recovery method of the present application helps to improve the purity and yield of nickel, cobalt, manganese and lithium recovery. At the same time, the recovery method of the present application has good process stability and low environmental pollution, and can simplify the production process according to demand, thereby reducing raw material and production costs. DETAILED DESCRIPTION

[0016] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present application will be described in detail below in conjunction with the embodiments.

[0017] As analyzed in the background technology of this application, the recovery of nickel, cobalt, manganese and lithium in the prior art has the problem of low recovery rate. In order to solve this problem, this application provides a method for recovering nickel, cobalt, manganese and lithium.

[0018] In a typical embodiment of the present application, a method for recovering nickel, cobalt, manganese and lithium is provided, and the recovery method comprises the following steps: step S1, disassembling, crushing, heat treating and demagnetizing the lithium battery recovery material in sequence to obtain black powder; step S2, decomposing the black powder with an acidophilic bacteria solution to remove copper and aluminum elements to obtain a decomposition product; step S3, acid leaching the decomposition product to obtain a leachate; step S4, graded extraction of the leachate to obtain a raffinate, a manganese salt solution, a cobalt salt solution and a nickel salt solution; step S5, evaporating and crystallizing the raffinate to obtain a lithium salt solution; step S6, independently co-precipitating the manganese salt solution, the cobalt salt solution, the nickel salt solution and the lithium salt solution to obtain a manganese salt solid, a cobalt salt solid, a nickel salt solid and a lithium salt solid.

[0019] In step S1, the lithium battery recycling material is disassembled and crushed in turn, which helps to separate the materials containing recycling elements, remove the organic components in the material by heat treatment, and remove magnetic impurities such as Fe in the material by demagnetization. In step S2, the black powder is decomposed by acidophilic bacteria liquid, which helps to remove the copper and aluminum elements in the black powder, thereby helping to improve the purity and yield of the recovered metal. In step S3, the decomposed product is acid-leached, and the manganese, cobalt, nickel and lithium in the decomposed product are dissolved to obtain a leachate. In step S4, the manganese, cobalt, nickel and lithium in the leachate are effectively separated by graded extraction. The present application effectively recovers nickel, cobalt, manganese and lithium from lithium battery recycling materials by adopting a composite recovery process combining physical recovery, biological recovery and wet recovery, especially using acidophilic bacteria for biological recovery, so that the purification of metal elements is more efficient, and at the same time, different metals can be selectively separated by graded extraction. Therefore, the recovery method of the present application helps to improve the purity and yield of nickel, cobalt, manganese and lithium recovery. At the same time, the recovery method of the present application has good process stability and low environmental pollution, and can simplify the production process according to demand, thereby reducing raw material and production costs.

[0020] The above-mentioned lithium battery recycled materials come from lithium battery positive electrode precursor recycled materials, lithium battery positive electrode material recycled materials, lithium battery positive electrode slurry recycled materials, lithium battery pole piece recycled materials and waste lithium battery recycled materials.

[0021] In one embodiment of the present application, in the above step S2, the OD600 of the acidophilic bacteria liquid is 0.6-1; and / or the ratio of the mass of the black powder to the volume of the acidophilic bacteria liquid is 1:10-20.

[0022] A higher bacterial solution concentration can increase the dissolution rate of copper and aluminum elements, because more microbial cells can participate in the oxidation-reduction process of metals, thereby increasing the release of copper and aluminum elements. However, too high a bacterial solution concentration may lead to insufficient oxygen supply in the bioreactor, affecting the growth and activity of microorganisms, and may also increase the processing cost. Therefore, controlling the concentration of the acidophilic solution within the above range helps to improve the removal efficiency of copper and aluminum elements. Controlling the ratio of the mass of black powder to the volume of the acidophilic solution within the above range helps to ensure sufficient contact between the acidophilic bacteria and the black powder, thereby helping to further improve the removal rate of copper and aluminum elements.

[0023] The OD600 of the acidophilic bacteria solution may be 0.6, 0.7, 0.8, 0.9 or 1. The ratio of the mass of the black powder to the volume of the acidophilic bacteria solution may be 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19 or 1:20.

[0024] In one embodiment of the present application, in the above step S2, the acidophilic bacteria liquid and the black powder are mixed to obtain a mixed liquid; the pH value of the mixed liquid is adjusted to 1 to 3, and then decomposition is carried out; in one embodiment of the present application, the decomposition time is 3 to 7 days; and / or the decomposition temperature is 30 to 50°C.

[0025] Acidophilic bacteria have higher activity in an acidic environment. Controlling the pH value of the mixed solution within the above range helps to control the acidophilic bacteria to selectively dissolve copper and aluminum, thereby helping to improve the recovery rate of recovered metals. Controlling the decomposition time and temperature within the above range helps to improve the redox ability of acidophilic bacteria to copper and aluminum, thereby helping to further improve the purity of recovered metals.

[0026] The decomposition time may be 3 days, 4 days, 5 days, 6 days or 7 days. The decomposition temperature may be 30°C, 35°C, 40°C, 45°C or 50°C.

[0027] In one embodiment of the present application, the regulator for adjusting the pH value of the above-mentioned mixed solution is an acid; in one embodiment of the present application, the acid is hydrochloric acid and / or sulfuric acid.

[0028] In one embodiment of the present application, the above-mentioned acidophilic bacterial liquid is A. monosulfide oxidizing bacterial liquid, Acb. disulfide oxidizing bacterial liquid or a mixed bacterial liquid of A. monosulfide oxidizing bacterial liquid and Acb. disulfide oxidizing bacterial liquid; in one embodiment of the present application, the mixed bacterial liquid is formed by mixing A. monosulfide oxidizing bacterial liquid with an OD600 of 0.6 to 1 and Acb. disulfide oxidizing bacterial liquid with an OD600 of 0.6 to 1, and the volume ratio of A. monosulfide oxidizing bacterial liquid to Acb. disulfide oxidizing bacterial liquid is 1:0.5 to 2.

[0029] A. monosulfide oxidizing bacteria liquid and Acb. disulfide oxidizing bacteria liquid act together on refined black powder, which helps to improve the synergistic effect between the two, and biocatalytically oxidize the copper and aluminum elements in the black powder. A. monosulfide oxidizing bacteria and Acb. disulfide oxidizing bacteria combine with copper ions and aluminum ions after catalytic oxidation to form organic covalent compounds, which helps to further improve the removal effect of copper and aluminum, thereby helping to improve the recovery purity and recovery efficiency of the recycled material.

[0030] The volume ratio of the above-mentioned A. monosulfide oxidizing bacteria solution and Acb. disulfide oxidizing bacteria solution may be 1:0.5, 1:1, 1:1.5 or 1:2.

[0031] In one embodiment of the present application, the acidophilic bacteria is placed in a FeS medium for expansion culture for 21 days at a temperature of 30° C. and a rotation speed of 150 rpm to obtain an acidophilic bacteria solution. In one embodiment of the present application, the acidophilic bacteria is A. monosulfur oxidizing bacteria or Acb. disulfur oxidizing bacteria, A. monosulfur oxidizing bacteria is purchased from Shanghai Baozang Biotechnology Center, model SHMCCD71747, and Acb. disulfur oxidizing bacteria is purchased from Wuhan Ruichen Standard Material Technology Co., Ltd., model SHMCC S71747.

[0032] In one embodiment of the present application, the above-mentioned step S4 includes: step S41, mixing the leachate with the first extractant to obtain a first mixed solution, adjusting the pH value of the first mixed solution to 2-3, and then performing a first extraction and a first stripping in sequence to obtain a first raffinate and a manganese salt solution; step S42, mixing the first raffinate with the second extractant to obtain a second mixed solution, adjusting the pH value of the second mixed solution to 4-5, and then performing a second extraction and a second stripping in sequence to obtain a second raffinate and a cobalt salt solution; step S43, mixing the second raffinate with the third extractant to obtain a third mixed solution, adjusting the pH value of the third mixed solution to 7-8, and then performing a third extraction and a third stripping in sequence to obtain a raffinate and a nickel salt solution.

[0033] By adjusting the pH value at different stages, the solubility of metal ions and the selectivity of the extractant can be controlled. At a pH of 2 to 3, manganese salts can be effectively extracted, while at a higher pH of 4 to 5, cobalt salts are extracted, and at an even higher pH of 7 to 8, nickel salts are suitable for extraction. This technical strategy of adjusting the pH value step by step helps to achieve the sequential separation of manganese, cobalt, and nickel metals, thereby helping to improve the purity and efficiency of metal recovery.

[0034] Including but not limited to, the stripping agent used in the first stripping, the stripping agent used in the second stripping and the stripping agent used in the third stripping are all sulfuric acid.

[0035] In one embodiment of the present application, the pH regulator in the above extraction is 1-2 mol / L NaOH or KOH.

[0036] In one embodiment of the present application, the volume ratio of the above-mentioned leachate to the first extractant is 1:0.1~1; and / or, the volume ratio of the first raffinate to the second extractant is 1:0.1~1; and / or, the volume ratio of the second raffinate to the third extractant is 1:0.1~1; in one embodiment of the present application, the concentrations of the first extractant, the second extractant and the third extractant are each independently 0.2~1 mol / L; and / or, the temperatures of the first extraction, the second extraction and the third extraction are each independently 25~50°C; in one embodiment of the present application, the first extractant is P204 extractant and / or A308 extractant; and / or, the second extractant is P507 extractant and / or A308 extractant; and / or, the third extractant is C272 extractant and / or A308 extractant.

[0037] Controlling the volume ratio of the leaching solution to the first extractant, the volume ratio of the first raffinate to the second extractant, and the volume ratio of the second raffinate to the third extractant within the above ranges helps to improve the metal extraction rate. The concentration of the extractant affects the distribution coefficient of the metal ions between the extractant and the aqueous phase. Controlling the concentrations of the first extractant, the second extractant, and the third extractant within the above ranges helps to improve the selectivity of metal separation, thereby helping to improve the yield and purity of the recovered metal. Controlling the temperatures of the first extraction, the second extraction, and the third extraction within the above ranges helps to improve the extraction efficiency. Controlling the types of the first extractant, the second extractant, and the third extractant within the above ranges helps to further improve the selectivity of metal separation.

[0038] In one embodiment of the present application, in the above step S1, the heat treatment temperature is 300-800°C; and / or, the heat treatment time is 1-8 hours; and / or, the median particle size of the black powder is 5-30 μm.

[0039] A lower temperature for heat treatment may not be enough to completely decompose organic matter, resulting in organic residues in subsequent treatment that may interfere with metal recovery. A too high temperature for heat treatment may cause oxidation loss of metals, especially lithium, resulting in a decrease in recovery rate. Controlling the temperature of heat treatment within the above range helps to reduce metal loss while removing organic matter, thereby helping to improve metal recovery efficiency and purity. Controlling the time of heat treatment within the above range helps to reduce energy consumption while removing organic matter. Smaller black powder particle size helps to increase the contact area between metal and treatment reagent, which is beneficial to the dissolution of metal and the separation of impurities. However, too small a particle size may cause dust problems during the treatment process, increase recovery costs, and too fine powder may be more difficult to separate in subsequent physical sorting. Controlling the median particle size of black powder within the above range helps to balance metal recovery efficiency and operational convenience, reduce energy consumption, and reduce production costs.

[0040] In one embodiment of the present application, in the above step S3, the decomposition product is acid-leached with acid; in one embodiment of the present application, the mass ratio of the acid to the decomposition product is 1:1-10; and / or the acid leaching temperature is 20-50°C; and / or the acid leaching time is 1-6h; in one embodiment of the present application, the acid is sulfuric acid and / or hydrochloric acid.

[0041] Manganese, cobalt, nickel and lithium in the decomposition product are dissolved by acid leaching. Controlling the mass ratio of acid to decomposition product within the above range helps to improve the efficiency of metal dissolution. Lower acid leaching temperature can reduce energy consumption, but may prolong the time required for metal dissolution. Higher acid leaching temperature can accelerate metal dissolution, but it should be noted that too high temperature may cause excessive volatilization of acid and metal oxidation, affecting the purity and efficiency of metal recovery. Controlling the acid leaching temperature within the above range helps to control energy consumption and reduce metal loss while improving metal dissolution efficiency. Controlling the acid leaching time within the above range helps to improve metal dissolution efficiency.

[0042] In one embodiment of the present application, in the above step S5, the temperature of evaporation crystallization is 80-150° C.; and / or the time of evaporation crystallization is 1-6 hours.

[0043] The lithium salt solution is enriched by evaporation and crystallization, and the temperature and time of the evaporation and crystallization are controlled within the above range, which helps to further improve the purity and yield of metallic lithium.

[0044] In one embodiment of the present application, the co-precipitation temperature is 20-30°C; and / or the co-precipitation time is 1-6h; in one embodiment of the present application, the precipitant used in the co-precipitation is selected from any one or more of NH4HCO3, NaHCO3, Na2CO3 and NaOH.

[0045] Nickel, cobalt, manganese and lithium are separated from the solution by coprecipitation to form a precipitate, and the obtained precipitate can be used as a raw material for preparing positive electrode materials. Controlling the temperature and time of coprecipitation within the above range helps to improve the efficiency of coprecipitation.

[0046] The beneficial effects of the present application will be further illustrated below in conjunction with embodiments.

[0047] Example 1

[0048] S1: 1000g of 18650 ternary lithium battery waste batteries are used as raw materials, and crude black powder is obtained after disassembly, discharge, crushing and eddy current separation.

[0049] S2: The crude black powder is heat-treated at 500° C. for 3 h to remove organic components and obtain a heat-treated product.

[0050] S3: The heat-treated product is subjected to demagnetization treatment, and then subjected to secondary crushing and fine grinding to obtain black powder, the median particle size of which is 20 μm.

[0051] S4: A. monosulfur oxidizing bacteria of Shanghai Baozang Biotechnology Center, model SHMCC D71747, was expanded and cultured in FeS medium for 21 days at a temperature of 30°C and a rotation speed of 150rpm to obtain A. monosulfur oxidizing bacteria liquid. The OD600 of the A. monosulfur oxidizing bacteria liquid was 0.6. After mixing the black powder with the A. monosulfur oxidizing bacteria liquid, an appropriate amount of sulfuric acid was added to adjust the pH to 1 for decomposition. The ratio of the mass of the black powder to the volume of the A. monosulfur oxidizing bacteria liquid was 1:10. The decomposition time was 3 days and the decomposition temperature was 30°C to obtain a decomposition product.

[0052] S5: The decomposition product is pickled and leached with 98% concentrated sulfuric acid, the mass ratio of 98% concentrated sulfuric acid to the decomposition product is 1:1, the acid leaching temperature is 20° C., the acid leaching time is 6 hours, and a leachate is obtained.

[0053] S6: P204 extractant is added to the leachate, and the pH is adjusted to 2 with 1mol / L NaOH. The concentration of P204 extractant is 1mol / L, the extraction temperature is 25°C, the volume ratio of leachate to P204 extractant is 1:0.1, and then sulfuric acid is used as a stripping agent for stripping and separation to obtain a first raffinate and a MnSO4 solution; P507 extractant is added to the first raffinate, and the pH is adjusted to 4 with 1mol / L NaOH. The concentration of P507 extractant is 1mol / L, and the extraction temperature is The temperature is 25℃, the volume ratio of the first raffinate to the P507 extractant is 1:0.1, and then the stripping agent sulfuric acid is used for stripping and separation to obtain the second raffinate and CoSO4 solution; the C272 extractant is added to the second raffinate, and the pH is adjusted to 7 with 1mol / L NaOH. The concentration of the C272 extractant is 1mol / L, the extraction temperature is 25℃, the volume ratio of the second raffinate to the C272 extractant is 1:0.1, and then the stripping agent sulfuric acid is used for stripping and separation to obtain the raffinate and NiSO4 solution.

[0054] S7: The raffinate is evaporated and crystallized at a temperature of 80° C. for 6 hours to obtain a Li2SO4 solution.

[0055] S8: The obtained MnSO4 solution, CoSO4 solution, NiSO4 solution and Li2SO4 solution are subjected to co-precipitation reaction independently, the precipitant is NH4HCO3, the co-precipitation temperature is 20°C, the co-precipitation time is 6 hours, and the obtained precipitate is filtered, washed and dried to obtain manganese carbonate, cobalt carbonate, nickel carbonate and lithium carbonate.

[0056] Example 2

[0057] The difference from Example 1 is that the OD600 of A. monosulfide oxidizing bacteria solution is 1, the ratio of the mass of black powder to the volume of A. monosulfide oxidizing bacteria solution is 1:20, and manganese carbonate, cobalt carbonate, nickel carbonate and lithium carbonate are finally obtained.

[0058] Example 3

[0059] The difference from Example 1 is that the OD600 of A. monosulfide oxidizing bacteria solution is 2, the ratio of the mass of black powder to the volume of A. monosulfide oxidizing bacteria solution is 1:40, and manganese carbonate, cobalt carbonate, nickel carbonate and lithium carbonate are finally obtained.

[0060] Example 4

[0061] The difference from Example 1 is that after the black powder is mixed with the A. monosulfur oxidizing bacteria solution, an appropriate amount of sulfuric acid is added to adjust the pH to 3 for decomposition. The decomposition time is 7 days and the decomposition temperature is 50° C., and manganese carbonate, cobalt carbonate, nickel carbonate and lithium carbonate are finally obtained.

[0062] Example 5

[0063] The difference from Example 1 is that after the black powder is mixed with the A. monosulfur oxidizing bacteria solution, an appropriate amount of sulfuric acid is added to adjust the pH to 4 for decomposition. The decomposition time is 1 day and the decomposition temperature is 20° C., and manganese carbonate, cobalt carbonate, nickel carbonate and lithium carbonate are finally obtained.

[0064] Example 6

[0065] The difference from Example 1 is that A. monosulfide oxidizing bacteria of Shanghai Baozang Biotechnology Center, model SHMCC D71747, is expanded and cultured in FeS medium for 21 days at a temperature of 30° C. and a rotation speed of 150 rpm to obtain A. monosulfide oxidizing bacteria liquid, and the OD600 of the A. monosulfide oxidizing bacteria liquid is 0.6; Acb. disulfide oxidizing bacteria of Wuhan Ruichen Standard Material Technology Co., Ltd., model SHMCC S71747, is expanded and cultured in FeS medium for 21 days at a temperature of 30° C. and a rotation speed of 150 rpm to obtain Acb. disulfide oxidizing bacteria liquid, and the OD600 of the Acb. disulfide oxidizing bacteria liquid is 0.6; A. monosulfide oxidizing bacteria liquid and Acb. disulfide oxidizing bacteria liquid are mixed at a volume ratio of 1:0.5 to obtain a mixed bacterial liquid, and the black powder is decomposed by the mixed bacterial liquid to finally obtain manganese carbonate, cobalt carbonate, nickel carbonate and lithium carbonate.

[0066] Example 7

[0067] The difference from Example 1 is that A. monosulfide oxidizing bacteria of Shanghai Baozang Biotechnology Center, model SHMCC D71747, was expanded and cultured in FeS medium for 21 days at a temperature of 30° C. and a rotation speed of 150 rpm to obtain A. monosulfide oxidizing bacteria liquid, and the OD600 of the A. monosulfide oxidizing bacteria liquid was 0.6; Acb. disulfide oxidizing bacteria of Wuhan Ruichen Standard Material Technology Co., Ltd., model SHMCC S71747, was expanded and cultured in FeS medium for 21 days at a temperature of 30° C. and a rotation speed of 150 rpm to obtain Acb. disulfide oxidizing bacteria liquid, and the OD600 of the Acb. disulfide oxidizing bacteria liquid was 0.6; the A. monosulfide oxidizing bacteria liquid and the Acb. disulfide oxidizing bacteria liquid were mixed in a volume ratio of 1:2 to obtain a mixed bacterial liquid, and the black powder was decomposed using the mixed bacterial liquid to finally obtain manganese carbonate, cobalt carbonate, nickel carbonate and lithium carbonate.

[0068] Example 8

[0069] The difference from Example 1 is that P204 extractant is added to the leachate, the pH is adjusted to 3 with 1 mol / L NaOH, the concentration of P204 extractant is 1 mol / L, the extraction temperature is 25°C, the volume ratio of the leachate to the P204 extractant is 1:0.1, and then sulfuric acid is used as a stripping agent for stripping and separation to obtain a first raffinate and a MnSO4 solution; P507 extractant is added to the first raffinate, the pH is adjusted to 5 with 1 mol / L NaOH, the concentration of P507 extractant is 1 mol / L, the extraction temperature is 25°C, and the first The volume ratio of the raffinate to the P507 extractant is 1:0.1, and then the stripping agent sulfuric acid is used for stripping and separation to obtain a second raffinate and a CoSO4 solution; then the C272 extractant is added to the second raffinate, and the pH is adjusted to 8 with 1 mol / L NaOH, the concentration of the C272 extractant is 1 mol / L, the extraction temperature is 25°C, the volume ratio of the second raffinate to the C272 extractant is 1:0.1, and then the stripping agent sulfuric acid is used for stripping and separation to obtain a raffinate and a NiSO4 solution, and finally manganese carbonate, cobalt carbonate, nickel carbonate and lithium carbonate are obtained.

[0070] Example 9

[0071] The difference from Example 1 is that P204 extractant is added to the leachate, the pH is adjusted to 4 with 1 mol / L NaOH, the concentration of P204 extractant is 1 mol / L, the extraction temperature is 25°C, the volume ratio of the leachate to the P204 extractant is 1:0.1, and then sulfuric acid is used as a stripping agent for stripping and separation to obtain a first raffinate and a MnSO4 solution; P507 extractant is added to the first raffinate, the pH is adjusted to 6 with 1 mol / L NaOH, the concentration of P507 extractant is 1 mol / L, the extraction temperature is 25°C, and the first The volume ratio of the raffinate to the P507 extractant is 1:0.1, and then the stripping agent sulfuric acid is used for stripping and separation to obtain a second raffinate and a CoSO4 solution; then the C272 extractant is added to the second raffinate, and the pH is adjusted to 9 with 1 mol / L NaOH, the concentration of the C272 extractant is 1 mol / L, the extraction temperature is 25°C, the volume ratio of the second raffinate to the C272 extractant is 1:0.1, and then the stripping agent sulfuric acid is used for stripping and separation to obtain a raffinate and a NiSO4 solution, and finally manganese carbonate, cobalt carbonate, nickel carbonate and lithium carbonate are obtained.

[0072] Example 10

[0073] The difference from Example 1 is that P204 extractant is added to the leachate, the pH is adjusted to 2 with 1 mol / L NaOH, the concentration of P204 extractant is 1 mol / L, the extraction temperature is 50°C, the volume ratio of the leachate to the P204 extractant is 1:1, and then sulfuric acid is used as a stripping agent for stripping and separation to obtain a first raffinate and a MnSO4 solution; P507 extractant is added to the first raffinate, the pH is adjusted to 4 with 1 mol / L NaOH, the concentration of P507 extractant is 1 mol / L, the extraction temperature is 50°C, and the first raffinate is added with 1 mol / L NaOH. The volume ratio of the first raffinate to the P507 extractant is 1:1, and then the stripping agent sulfuric acid is used for stripping and separation to obtain a second raffinate and a CoSO4 solution; then the C272 extractant is added to the second raffinate, and the pH is adjusted to 7 with 1 mol / L NaOH, the concentration of the C272 extractant is 1 mol / L, the extraction temperature is 50°C, the volume ratio of the second raffinate to the C272 extractant is 1:1, and then the stripping agent sulfuric acid is used for stripping and separation to obtain a raffinate and a NiSO4 solution, and finally manganese carbonate, cobalt carbonate, nickel carbonate and lithium carbonate are obtained.

[0074] Embodiment 11

[0075] The difference from Example 1 is that P204 extractant is added to the leachate, the pH is adjusted to 2 with 1 mol / L NaOH, the concentration of P204 extractant is 1 mol / L, the extraction temperature is 55°C, the volume ratio of the leachate to the P204 extractant is 1:2, and then sulfuric acid is used as a stripping agent for stripping and separation to obtain a first raffinate and a MnSO4 solution; P507 extractant is added to the first raffinate, the pH is adjusted to 4 with 1 mol / L NaOH, the concentration of P507 extractant is 1 mol / L, the extraction temperature is 55°C, and the first The volume ratio of the first raffinate to the P507 extractant is 1:2, and then the stripping agent sulfuric acid is used for stripping and separation to obtain a second raffinate and a CoSO4 solution; then the C272 extractant is added to the second raffinate, and the pH is adjusted to 7 with 1 mol / L NaOH, the concentration of the C272 extractant is 1 mol / L, the extraction temperature is 55°C, the volume ratio of the second raffinate to the C272 extractant is 1:2, and then the stripping agent sulfuric acid is used for stripping and separation to obtain a raffinate and a NiSO4 solution, and finally manganese carbonate, cobalt carbonate, nickel carbonate and lithium carbonate are obtained.

[0076] Example 12

[0077] The difference from Example 1 is that the heat treatment temperature is 300° C., the heat treatment time is 8 h, the median particle size of the black powder is 5 μm, and manganese carbonate, cobalt carbonate, nickel carbonate and lithium carbonate are finally obtained.

[0078] Example 13

[0079] The difference from Example 1 is that the heat treatment temperature is 800° C., the heat treatment time is 1 h, the median particle size of the black powder is 30 μm, and manganese carbonate, cobalt carbonate, nickel carbonate and lithium carbonate are finally obtained.

[0080] Embodiment 14

[0081] The difference from Example 1 is that the heat treatment temperature is 900° C., the heat treatment time is 0.5 h, the median particle size of the black powder is 40 μm, and manganese carbonate, cobalt carbonate, nickel carbonate and lithium carbonate are finally obtained.

[0082] Embodiment 15

[0083] The difference from Example 1 is that the mass ratio of 98% acid to decomposition product is 1:10, the acid leaching temperature is 50° C., the acid leaching time is 1 h, and manganese carbonate, cobalt carbonate, nickel carbonate and lithium carbonate are finally obtained.

[0084] Example 16

[0085] The difference from Example 1 is that the mass ratio of 98% acid to decomposition product is 1:20, the acid leaching temperature is 60° C., the acid leaching time is 0.5 h, and manganese carbonate, cobalt carbonate, nickel carbonate and lithium carbonate are finally obtained.

[0086] Comparative Example 1

[0087] The difference from Example 1 is that the use of A. monosulfur oxidizing bacteria liquid to decompose the black powder is eliminated, and manganese carbonate, cobalt carbonate, nickel carbonate and lithium carbonate are finally obtained.

[0088] The manganese carbonate, cobalt carbonate, nickel carbonate and lithium carbonate prepared in the examples and comparative examples were tested for the recovery rates of manganese, cobalt, nickel and lithium and the purity of manganese carbonate, cobalt carbonate, nickel carbonate and lithium carbonate. The test results are shown in Table 1.

[0089] Table 1

[0090]

[0091] From the above description, it can be seen that the above embodiments of the present application achieve the following technical effects:

[0092] In step S1, the lithium battery recycling material is disassembled and crushed in turn, which helps to separate the materials containing recycling elements, remove the organic components in the material by heat treatment, and remove magnetic impurities such as Fe in the material by demagnetization. In step S2, the black powder is decomposed by acidophilic bacteria liquid, which helps to remove the copper and aluminum elements in the black powder, thereby helping to improve the purity and yield of the recovered metal. In step S3, the decomposed product is acid-leached, and the manganese, cobalt, nickel and lithium in the decomposed product are dissolved to obtain a leachate. In step S4, the manganese, cobalt, nickel and lithium in the leachate are effectively separated by graded extraction. The present application effectively recovers nickel, cobalt, manganese and lithium from lithium battery recycling materials by adopting a composite recovery process combining physical recovery, biological recovery and wet recovery, especially using acidophilic bacteria for biological recovery, so that the purification of metal elements is more efficient, and at the same time, different metals can be selectively separated by graded extraction. Therefore, the recovery method of the present application helps to improve the purity and yield of nickel, cobalt, manganese and lithium recovery. At the same time, the recovery method of the present application has good process stability and low environmental pollution, and can simplify the production process according to demand, thereby reducing raw material and production costs.

[0093] The above are only embodiments of the present application and are not intended to limit the present application. For those skilled in the art, the present application may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for recovering nickel, cobalt, manganese and lithium, characterized in that: The recovery method comprises the following steps: Step S1, disassembling, crushing, heat treating and demagnetizing the lithium battery recycling material in sequence to obtain black powder; Step S2, using an acidophilic bacteria liquid to decompose the black powder to remove copper and aluminum elements to obtain a decomposed product; Step S3, acid leaching the decomposed product to obtain a leachate; Step S4, performing graded extraction on the leachate to obtain a raffinate, a manganese salt solution, a cobalt salt solution and a nickel salt solution; Step S5, evaporating and crystallizing the raffinate to obtain a lithium salt solution; Step S6, independently co-precipitating the manganese salt solution, the cobalt salt solution, the nickel salt solution and the lithium salt solution to obtain a manganese salt solid, a cobalt salt solid, a nickel salt solid and a lithium salt solid.

2. The recycling method according to claim 1, characterized in that: In the step S2, the OD600 of the acidophilic bacteria liquid is 0.6-1; and / or the ratio of the mass of the black powder to the volume of the acidophilic bacteria liquid is 1:10-20.

3. The recovery method according to claim 1 or 2, characterized in that: In the step S2, the acidophilic bacteria liquid and the black powder are mixed to obtain a mixed liquid; the pH value of the mixed liquid is adjusted to 1-3, and then the decomposition is performed; preferably, the decomposition time is 3-7 days; and / or the decomposition temperature is 30-50°C.

4. The recovery method according to any one of claims 1 to 3, characterized in that: The acidophilic bacterial solution is A. monosulfide oxidizing bacterial solution, Acb. disulfide oxidizing bacterial solution or a mixed bacterial solution of A. monosulfide oxidizing bacterial solution and Acb. disulfide oxidizing bacterial solution; preferably, the mixed bacterial solution is formed by mixing the A. monosulfide oxidizing bacterial solution with an OD600 of 0.6 to 1 and the Acb. disulfide oxidizing bacterial solution with an OD600 of 0.6 to 1, and the volume ratio of the A. monosulfide oxidizing bacterial solution to the Acb. disulfide oxidizing bacterial solution is 1:0.5 to 2.

5. The recovery method according to any one of claims 1 to 4, characterized in that: The step S4 comprises: Step S41, mixing the leachate with a first extractant to obtain a first mixed solution, adjusting the pH value of the first mixed solution to 2-3, and then sequentially performing a first extraction and a first stripping to obtain a first raffinate and the manganese salt solution; Step S42, mixing the first raffinate with a second extractant to obtain a second mixed solution, adjusting the pH value of the second mixed solution to 4-5, and then sequentially performing a second extraction and a second stripping to obtain a second raffinate and the cobalt salt solution; Step S43, mixing the second raffinate with a third extractant to obtain a third mixed solution, adjusting the pH value of the third mixed solution to 7-8, and then sequentially performing a third extraction and a third stripping to obtain the raffinate and the nickel salt solution.

6. The recycling method according to claim 5, characterized in that: The volume ratio of the leachate to the first extractant is 1:0.1-1; and / or the volume ratio of the first raffinate to the second extractant is 1:0.1-1; and / or the volume ratio of the second raffinate to the third extractant is 1:0.1-1; Preferably, the concentrations of the first extractant, the second extractant and the third extractant are each independently 0.2 to 1 mol / L; and / or the temperatures of the first extraction, the second extraction and the third extraction are each independently 25 to 50° C.; Preferably, the first extractant is P204 extractant and / or A308 extractant; and / or, the second extractant is P507 extractant and / or A308 extractant; And / or, the third extractant is C272 extractant and / or A308 extractant.

7. The recovery method according to any one of claims 1 to 6, characterized in that: In the step S1, the temperature of the heat treatment is 300-800° C.; and / or, the time of the heat treatment is 1-8 hours; and / or, the median particle size of the black powder is 5-30 μm.

8. The recovery method according to any one of claims 1 to 7, characterized in that: In the step S3, the decomposition product is acid-leached with an acid; preferably, the mass ratio of the acid to the decomposition product is 1:1-10; and / or the temperature of the acid leaching is 20-50°C; and / or the time of the acid leaching is 1-6 hours; preferably, the acid is sulfuric acid and / or hydrochloric acid.

9. The recovery method according to any one of claims 1 to 8, characterized in that: In the step S5, the temperature of the evaporation crystallization is 80 to 150° C.; and / or the time of the evaporation crystallization is 1 to 6 hours.

10. The recovery method according to any one of claims 1 to 9, characterized in that: The coprecipitation temperature is 20-30° C.; and / or the coprecipitation time is 1-6 h; preferably, the precipitant used in the coprecipitation is selected from any one or more of NH 4 HCO 3 , NaHCO 3 , Na 2 CO 3 and NaOH.

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