CN113444885B - Method for preferentially extracting metal lithium from waste ternary lithium ion battery and simultaneously obtaining battery-grade metal salt - Google Patents

Method for preferentially extracting metal lithium from waste ternary lithium ion battery and simultaneously obtaining battery-grade metal salt Download PDF

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CN113444885B
CN113444885B CN202110631918.6A CN202110631918A CN113444885B CN 113444885 B CN113444885 B CN 113444885B CN 202110631918 A CN202110631918 A CN 202110631918A CN 113444885 B CN113444885 B CN 113444885B
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extraction
battery
grade
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sulfate
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CN113444885A (en
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郑华均
潘曜灵
郑灵霞
赵浙菲
甄爱钢
孔繁振
凌怊
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Zhejiang Tianneng New Material Co ltd
Zhejiang University of Technology ZJUT
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Zhejiang Tianneng New Material Co ltd
Zhejiang University of Technology ZJUT
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/10—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/10—Sulfates
    • 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
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • 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
    • 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
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • 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
    • 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
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Abstract

The invention provides a method for preferentially extracting metal lithium from waste ternary lithium ion batteries and simultaneously obtaining battery-grade metal salt, which comprises the steps of roasting and reducing black powder of the waste batteries in a clean and single hydrogen atmosphere, then leaching with pure water to achieve the aim of preferentially extracting metal lithium resources, effectively improving the recovery rate of metal lithium, avoiding generation of harmful and toxic waste flue gas such as carbon dioxide, sulfur dioxide and the like in the recovery process, and being clean and environment-friendly in the recovery process; and moreover, by adopting a countercurrent extraction method of nickel soap organic extraction-sulfuric acid back extraction, other metal impurities are prevented from entering a solution in the extraction process, the purity of metal salt is greatly improved, and battery-grade cobalt sulfate, nickel sulfate and manganese sulfate are obtained.

Description

Method for preferentially extracting metal lithium from waste ternary lithium ion battery and simultaneously obtaining battery-grade metal salt
Technical Field
The invention belongs to the field of solid waste recovery and treatment, and particularly relates to a method for recovering high-purity metal resources from waste ternary lithium ion batteries in an environment-friendly, efficient and low-cost manner.
Background
Since the 90 s of the last century, with the innovation of positive electrode materials, negative electrode materials and electrolytes, lithium ion batteries have been commercialized and rapidly widely used in many fields. Particularly, the popularization of new energy automobiles leads the demand of lithium ion batteries to be rapidly increased, and the annual average growth rate reaches 9.4 percent. The metal resources for manufacturing the lithium ion battery, in particular to the metal supply and demand gap which is scarce by mineral resources such as lithium, cobalt and the like, is enlarged. Therefore, how to recover metal resources from waste lithium ion batteries and reuse the metal resources for manufacturing the lithium ion batteries is an important way for promoting the sustainable development of the lithium ion battery industry.
At present, the recovery of waste lithium ion batteries generally comprises the steps of firstly extracting metal resources such as nickel, cobalt, manganese and the like from black powder containing the metal resources by adopting a wet leaching and extraction technology, then finally extracting lithium metal resources in a carbonate precipitation mode, and leading the metal lithium resources to pass through the long process flow, so that the loss of the metal lithium resources in the recovery process is inevitably caused, and the recovery rate of lithium is obviously reduced; on the other hand, because a large amount of lithium ions exist in the processes of leaching, extraction and back extraction, the purity of nickel and cobalt salts obtained by extraction cannot reach the battery grade standard, and the nickel and cobalt salts are difficult to return to the remanufacturing of the lithium ion battery. Therefore, it is necessary to develop a method for preferentially extracting lithium and simultaneously recovering a battery-grade metal salt.
Chinese patent CN106129511A discloses a method for comprehensively recovering valuable metals from waste lithium ion battery materials, which mainly mixes the positive electrode material of the waste lithium ion battery with a reducing agent, carries out reduction roasting treatment at the temperature of 500-750 ℃,the roasted product is firstly CO 2 Immersing in carbonized water to obtain aqueous solution of lithium bicarbonate for preparing Li 2 CO 3 And (5) producing the product. Although the method realizes the preferential extraction of lithium metal, the Li is obtained because the anode material of the waste lithium ion battery inevitably contains impurities of other elements such as aluminum and the like 2 CO 3 The product is crude lithium carbonate, and a solid reducing agent is introduced, so that the leaching residue amount is increased.
The chinese patent application No. cn202010724526.X discloses a method for preparing lithium carbonate by using waste lithium ion batteries and battery-grade lithium carbonate, which comprises the steps of reducing and roasting powder of the waste lithium ion batteries by using natural gas, adding water for leaching and filtering, and then sequentially precipitating by using sulfuric acid and sodium carbonate to obtain lithium carbonate. Although the aim of preferentially extracting lithium is fulfilled, the lithium is roasted in the natural gas atmosphere, a large amount of carbon dioxide is generated in the roasting process, the incompletely-reacted natural gas can be directly discharged to the air after being treated, the graphite carbon in the black powder of the waste battery is not fully utilized, and the environment is not protected; in addition, there is no clear scheme for the subsequent purification of manganese, nickel and cobalt.
Chinese patent application CN 109935922A discloses a method for recovering valuable metals from waste lithium ion battery materials, which comprises the steps of mixing a waste lithium ion battery anode material with low-valent sulfates such as sulfur and sulfide, carrying out vulcanization roasting treatment at the temperature of 300-900 ℃, leaching roasted products by water to obtain a lithium salt aqueous solution, further preparing a lithium carbonate product, leaching water leaching residues by adopting oxidation acid leaching or direct acid leaching to leach valuable elements such as nickel, cobalt, manganese and the like, and purifying and extracting leachate to obtain corresponding cobalt salts, nickel salts and the like. The method has the problems that sulfide is adopted for roasting, and the roasted flue gas contains a large amount of toxic and harmful gases such as sulfur dioxide or sulfur trioxide and the like, and needs further purification treatment; meanwhile, the recovery rate of the lithium salt is low finally, and the purity of other metals such as nickel-cobalt-manganese salt solution cannot reach the battery grade standard, so that the lithium salt is difficult to be directly used for remanufacturing the ternary lithium ion battery anode material.
Disclosure of Invention
The invention aims to provide a clean, low-carbon emission and high-recovery-rate recovery method for preferentially extracting metal lithium resources from waste ternary lithium ion batteries, and the recovered manganese sulfate, cobalt sulfate and nickel sulfate metal salts reach the battery-level standard established by technical innovation strategy alliance of the recovery environmental protection industry, and can be directly recycled for remanufacturing lithium ion batteries.
The innovation of the invention is mainly as follows:
firstly, the metal lithium resource can be extracted with low cost and priority by adopting low-temperature roasting in a hydrogen atmosphere, the recovery rate of the lithium resource is improved, and the influence of the recovery process on the environment is reduced;
second is R 2 the-Ni structure is a soap-converting organic extractant, and a countercurrent extraction method is adopted to clarify the order of extracting metal resources, so that high-purity manganese sulfate and battery-grade cobalt sulfate and nickel sulfate are obtained.
The technical scheme of the invention is as follows:
a method for preferentially extracting metallic lithium from a waste ternary lithium ion battery and simultaneously obtaining battery-grade metal salt, comprising the following steps:
step 1: calcination with hydrogen
The waste ternary lithium ion battery is subjected to overdischarge, disassembly and crushing, screening, carbonization furnace roasting and multistage sorting to obtain black powder containing lithium, manganese, nickel and cobalt metal resources and graphite carbon, and the black powder is subjected to reduction roasting for 2-4 hours at 500-700 ℃ under the hydrogen atmosphere of 0.02-0.2 MPa to obtain reduced powder;
step 2: preferential extraction of lithium
Adding the reduced powder obtained in the step 1 into pure water, uniformly dispersing, performing filter pressing to obtain filter residue and filtrate, and performing reduced pressure concentration and crystallization on the filtrate to obtain lithium hydroxide monohydrate;
the mass ratio of the reduction powder to the pure water is 1:3 to 5;
the treatment effects of the steps 1-2 are as follows: the black powder is roasted, so that the metal lithium resource exists in the form of lithium oxide, and the pure water is added for dissolving to obtain lithium hydroxide, wherein the recovery rate of the lithium resource reaches over 96 percent; meanwhile, reducing the metal manganese, cobalt and nickel into divalent metal ions for subsequent recovery;
and step 3: sulfuric acid leaching
Dissolving the filter residue obtained in the step 2 by using sulfuric acid to obtain a leaching solution, and controlling the pH value of the leaching solution to be 1.5-2;
the concentration of the sulfuric acid is 98wt%, and the mass ratio of the filter residue to the sulfuric acid is 1:5 to 6;
and 4, step 4: p204 extraction of impurities
Mixing the leachate obtained in the step 3 with a soap-conversion organic extractant P204, and controlling the volume ratio of an organic phase to a water phase to be 2-4: 1 (preferably 3);
260# solvent oil is added into the soap-conversion organic extractant P204, and the volume of the P204 accounts for 20-30%;
the extraction stage number is 8-10 stages during extraction, and the pH of the water phase at the outlet of the extraction section is controlled to be 2.5-2.8;
washing the extracted organic phase by 0.5mol/L sulfuric acid for 12-13 grades; then carrying out back extraction on the loaded organic P204 by using 2.0mol/L sulfuric acid, wherein the number of back extraction stage stages is 6, so as to obtain a mixed solution of aluminum sulfate, calcium sulfate, copper sulfate, zinc sulfate and manganese sulfate; the no-load organic is recycled after 3-level reverse iron and 2-level water washing;
the treatment effect of the step 4 is as follows: in the extraction process, the impurities of calcium, aluminum, copper and zinc ions in the water phase are all extracted into the organic phase, so that the metal impurities are removed, and the subsequent processes are ensured to obtain battery-grade manganese sulfate, cobalt sulfate and nickel sulfate;
and 5: extraction of high purity manganese salt
Mixing the raffinate obtained in the step 4 with a soap-conversion organic extractant P204, and controlling the volume ratio of an organic phase to a water phase to be 2-4: 1 (preferably 3;
260# solvent oil is added into the soap-conversion organic extractant P204, and the volume of the P204 accounts for 20-30%;
the extraction stage number is 9-10 stages during extraction, and the pH of the water phase at the outlet of the extraction section is controlled to be 2.5-3.3;
washing the extracted organic phase by 0.5mol/L sulfuric acid, and washing for 12-13 levels; then carrying out back extraction on the loaded organic P204 by using 2.2-2.3 mol/L sulfuric acid, wherein the number of the back extraction stages is 6, so as to obtain a high-purity manganese sulfate solution, and standing, deoiling, fine filtering, evaporating and crystallizing the high-purity manganese sulfate solution to obtain battery-grade manganese sulfate; the no-load organic is recycled after being subjected to 3-level reverse iron and 2-level water washing;
the processing effect of the step 5 is as follows: through the back extraction process, manganese ions completely enter a water phase, so that a high-purity manganese sulfate solution is obtained, and the purity of a product can reach more than 99% after an evaporation crystallization process;
step 6: cobalt salt for extracting battery grade standard
Mixing the raffinate obtained in the step 5 with a soap-converting organic extractant P507, and controlling the volume ratio of an organic phase to a water phase to be 2-4: 1 (preferably 3;
260# solvent oil is added into the soap-conversion organic extractant P507, and the volume of the P507 accounts for 20-30%;
the extraction stage number is 10-11 stages during extraction, and the pH of the water phase at the outlet of the extraction section is controlled to be 4.0-4.5;
washing the extracted organic phase with 0.5mol/L sulfuric acid for 14-15 stages; then, carrying out back extraction on the loaded organic P507 by using 2.4mol/L sulfuric acid, wherein the number of the back extraction stage is 6, so as to obtain a high-purity cobalt sulfate solution, and standing, deoiling, fine filtering, evaporating and crystallizing the high-purity cobalt sulfate solution to obtain battery-grade cobalt sulfate; the no-load organic is recycled after 3-level reverse iron and 2-level water washing;
the processing effect of the step 6 is as follows: in the extraction process, cobalt ions in the water phase are all extracted into an organic phase; in the back extraction process, cobalt ions are completely dissolved back into a water phase, so that a high-purity cobalt sulfate solution is obtained; the battery-grade cobalt sulfate is obtained after the high-purity cobalt sulfate solution is subjected to subsequent treatment, and the mass fraction of metal cobalt in the product can reach more than 20.5%;
and 7: extraction of battery grade standard nickel salts
And (3) mixing the raffinate obtained in the step (6) with a soap-converting organic extractant Cyanex272, and controlling the volume ratio of an organic phase to a water phase to be 2-4: 1 (preferably 3;
260# solvent oil is added into a soap-converting organic extractant Cyanex272, and the volume of the Cyanex272 accounts for 20-30%;
the extraction stage number is 8-9 stages during extraction, and the pH of the water phase at the outlet of the extraction section is controlled to be 5.0-5.5;
washing the extracted organic phase by 0.5mol/L sulfuric acid, and washing for 6 grades; then carrying out back extraction on the loaded organic Cyanex272 by using 2mol/L sulfuric acid, wherein the number of back extraction stages is 6; the no-load organic is recycled after 3-level reverse iron and 2-level water washing;
the processing effect of the step 7 is as follows: in the extraction process, magnesium ions in the water phase are all extracted to an organic phase to obtain a high-purity nickel sulfate solution, the high-purity nickel sulfate solution is subjected to subsequent treatment to obtain battery-grade nickel sulfate, and the mass fraction of metal nickel in the product can reach more than 22.1%.
The structure of the soap-converting organic extractant used in the steps 4, 5, 6 and 7 of the invention is R 2 Ni, the method adopted is to saponify the organic extractant with liquid alkali and then to convert the nickel sulfate into soap. The saponification grade number of P204 is 2 grades, and the soap conversion grade number of nickel sulfate is 6 grades; the saponification grade of P507 is 2 grades, and the soap conversion grade of nickel sulfate is 6 grades; CY-272 saponification grade is 3 grades, and nickel sulfate is converted into soap grade 6. Extraction with a soap-converting organic extractant avoids mixing metallic Na ions into the aqueous phase.
The method for preferentially extracting the metal lithium from the black powder of the waste ternary lithium ion battery and simultaneously obtaining the high-purity metal manganese, cobalt and nickel salts has the beneficial effects that:
firstly, waste battery black powder is roasted and reduced in a clean and single hydrogen atmosphere, and then pure water is adopted for leaching, so that the aim of preferentially extracting metal lithium resources is achieved, the recovery rate of metal lithium is effectively improved, harmful and toxic waste flue gas such as carbon dioxide and sulfur dioxide is avoided in the recovery process, and the recovery process is clean and environment-friendly;
and secondly, a countercurrent extraction method of nickel soap organic extraction-sulfuric acid back extraction is adopted, other metal impurities are prevented from entering a solution in the extraction process, the purity of metal salt is greatly improved, and the battery-grade sulfate is obtained through subsequent processes of standing, oil removal, fine filtration and the like, so that the method is simple and the recovery cost is low.
Drawings
FIG. 1: the invention relates to a process flow chart.
Detailed Description
The invention is further described below by means of specific examples, without the scope of protection of the invention being limited thereto.
Example 1
Step 1: the black powder of the waste battery is obtained by overdischarging, disassembling and crushing, screening, roasting in a carbonization furnace and multi-stage sorting the waste ternary lithium ion battery. The contents of metal nickel, cobalt, manganese and lithium in the black powder of the waste battery are respectively 32.73,7.50, 16.99 and 6.54 percent, and impurities such as aluminum, calcium, magnesium, copper and the like also exist in the black powder.
And (3) roasting the black powder for 2.8 hours at 550 ℃ under the hydrogen atmosphere, and controlling the pressure of hydrogen in the rotary kiln to be 0.02MPa to obtain the reduced powder.
Step 2: and (3) adding the reduced powder obtained in the step (1) into pure water, fully stirring, and carrying out filter pressing to obtain filter residue and a lithium hydroxide solution, wherein 92% of metal lithium is leached into the solution.
And step 3: and (3) dissolving the filter residue obtained in the step (2) by using sulfuric acid with the concentration of 98 percent to obtain a leaching solution with the pH value of 1.5.
And 4, step 4: fully mixing the leachate obtained in the step 3 with a nickel soap organic extractant P204, mixing the organic extractant P204 with No. 260 solvent oil in a proportion of 25%, controlling the extraction stage number to be 9 stages, controlling the volume ratio of an organic phase to a water phase to be 3, controlling the pH value of the water phase at the outlet of the extraction stage to be 2.8, and carrying out countercurrent extraction on the organic phase and the water phase. Washing the organic phase obtained after extraction with 0.5mol/L sulfuric acid, wherein the washing stage number is 13 stages, and then back-extracting the loaded organic P204 with 2.0mol/L sulfuric acid to obtain a mixed solution of manganese sulfate, calcium sulfate, copper sulfate, zinc sulfate and aluminum sulfate, wherein the back-extraction stage number is 6 stages. And the unloaded organic is recycled after being subjected to 3-level reverse iron and 2-level water washing.
And 5: fully mixing the raffinate obtained in the step 4 with a nickel soap organic extractant P204, mixing the organic extractant P204 with No. 260 solvent oil in a ratio of 25%, controlling the extraction stage number to be 9 stages, controlling the volume ratio of an organic phase to an aqueous phase to be 3, controlling the pH value of the aqueous phase at the outlet of the extraction stage to be 2.8, and performing countercurrent extraction on the organic phase and the aqueous phase. Washing the organic phase obtained after extraction with 0.5mol/L sulfuric acid, wherein the washing stage number is 13 stages, and then back-extracting the loaded organic P204 with 2.2mol/L sulfuric acid to obtain a manganese sulfate solution, wherein the back-extraction stage number is 6 stages. And the unloaded organic matters are recycled after grade 3 iron-reversing and grade 2 water washing. Standing the manganese sulfate solution, removing oil, finely filtering, and evaporating and crystallizing to obtain the battery-grade manganese sulfate. The manganese content in the obtained manganese sulfate is 32.3 percent, and the contents of impurities such as cobalt, nickel, magnesium and calcium are respectively 0.0032 percent, 0.0041 percent, 0.0054 percent and 0.0088 percent, which reach the HG/T4823-2015 standard.
Step 6: mixing the raffinate in the step 5 with a nickel soap organic extractant P507, mixing the organic extractant with No. 260 solvent oil in an amount of 25 percent of the P507, controlling the extraction stage number to be 11 stages, controlling the volume ratio of an organic phase to a water phase to be 3, controlling the pH value of the water phase at the outlet of the extraction stage to be 4.0, and performing countercurrent extraction on the organic phase and the water phase. Washing the extracted organic phase by using 0.5mol/L sulfuric acid, wherein the washing grade is 15 grades, and then back-extracting the loaded organic P507 by using 2.4mol/L sulfuric acid to obtain a cobalt sulfate solution, wherein the back-extraction grade is 7 grades. And the unloaded organic is recycled after being subjected to 3-level reverse iron and 2-level water washing. The cobalt sulfate solution is stood, degreased and finely filtered to obtain battery-grade cobalt sulfate solution, wherein the cobalt in the chemical components is 115.72g/L, the contents of impurities such as manganese, nickel, magnesium and calcium are respectively 0.0058, 0.0145, 0.0023 and 0.0022g/L, and the standard of T/ATCRR10-2020 is reached.
And 7: mixing the raffinate obtained in the step 6 with a soap-converting organic extractant Cyanex272, mixing the organic extractant with No. 260 solvent oil by 25 percent of CY-272, controlling the extraction stage number to be 9 stages, controlling the volume ratio of an organic phase to an aqueous phase to be 3, controlling the pH value of the aqueous phase at the outlet of the extraction stage to be 5.2, and performing countercurrent extraction on the organic phase and the aqueous phase. And (3) standing, deoiling and finely filtering the raffinate, and then evaporating to obtain a battery-grade nickel sulfate solution. The nickel content in the obtained nickel sulfate is 120.98g/L, the contents of impurities of manganese, cobalt, magnesium and calcium are respectively 0.86 ppm, 17.65 ppm, 2.31 ppm and 1.10ppm, and the standard of T/ATCRR 12-2020 is reached.
Loading an organic extractant, washing by 7 stages, performing back extraction on 2mol/L sulfuric acid to obtain a magnesium sulfate solution, wherein the number of the back extraction stages is 6, and performing back iron removal by 3 stages and washing by 2 stages of water to recycle the organic extractant.
Example 2
Step 1: the black powder of the waste battery is obtained by overdischarging, disassembling and crushing, screening, roasting in a carbonization furnace and multi-stage sorting the waste ternary lithium ion battery. The contents of metal nickel, cobalt, manganese and lithium in the black powder of the waste battery are respectively 32.73,7.50, 16.99 and 6.54 percent, and impurities such as aluminum, calcium, magnesium, copper and the like also exist in the black powder.
And (3) roasting the black powder for 3 hours at 570 ℃ under the hydrogen atmosphere, and controlling the pressure of hydrogen in the rotary kiln to be 0.03MPa to obtain the reduced powder.
And 2, step: and (3) adding the reduced powder obtained in the step (1) into pure water, fully stirring, and carrying out filter pressing to obtain filter residue and a lithium hydroxide solution, wherein 94% of metal lithium is leached into the solution.
And step 3: and (3) dissolving the filter residue obtained in the step (2) by using sulfuric acid with the concentration of 98 percent to obtain a leaching solution with the pH value of 1.7.
And 4, step 4: fully mixing the leachate obtained in the step 3 with a nickel soap organic extractant P204, mixing the organic extractant P204 with No. 260 solvent oil in a ratio of 25%, controlling the extraction stage number to be 10 stages, controlling the volume ratio of an organic phase to a water phase to be 3, controlling the pH value of the water phase at the outlet of the extraction stage to be 2.7, and performing countercurrent extraction on the organic phase and the water phase. Washing the organic phase obtained after extraction with 0.5mol/L sulfuric acid, wherein the washing stage number is 13, and then carrying out back extraction on the loaded organic P204 with 2.0mol/L sulfuric acid to obtain a mixed solution of manganese sulfate, calcium sulfate, copper sulfate, zinc sulfate and aluminum sulfate, wherein the back extraction stage number is 6. And the unloaded organic is recycled after being subjected to 3-level reverse iron and 2-level water washing.
And 5: fully mixing the raffinate obtained in the step 4 with a nickel soap organic extractant P204, mixing the organic extractant P204 with No. 260 solvent oil in a ratio of 25%, controlling the extraction stage number to be 9 stages, controlling the volume ratio of an organic phase to an aqueous phase to be 3, controlling the pH value of the aqueous phase at the outlet of the extraction stage to be 2.9, and performing countercurrent extraction on the organic phase and the aqueous phase. Washing the organic phase obtained after extraction with 0.5mol/L sulfuric acid, wherein the washing grade is 12 grades, and then back-extracting the loaded organic P204 with 2.2mol/L sulfuric acid to obtain a manganese sulfate solution, wherein the back-extraction grade is 6 grades. And the unloaded organic is recycled after being subjected to 3-level reverse iron and 2-level water washing. Standing the manganese sulfate solution, removing oil, finely filtering, and evaporating and crystallizing to obtain the battery-grade manganese sulfate. The manganese content in the obtained manganese sulfate is 32.8 percent, and the contents of impurities such as cobalt, nickel, magnesium and calcium are respectively 0.0042 percent, 0.0039 percent, 0.0074 percent and 0.0079 percent, which reach the HG/T4823-2015 standard.
And 6: mixing the raffinate in the step 5 with a nickel soap organic extracting agent P507, mixing the organic extracting agent with No. 260 solvent oil according to 25 percent of the proportion of P507, controlling the extraction stage number to be 11 stages, controlling the volume ratio of an organic phase to an aqueous phase to be 3, controlling the pH value of the aqueous phase at the outlet of the extraction section to be 4.2, and performing countercurrent extraction on the organic phase and the aqueous phase. Washing the extracted organic phase with 0.5mol/L sulfuric acid, wherein the washing grade is 14 grades, and then back-extracting the loaded organic P507 with 2.4mol/L sulfuric acid to obtain a cobalt sulfate solution, wherein the back-extraction grade is 6 grades. And the unloaded organic is recycled after being subjected to 3-level reverse iron and 2-level water washing. The battery grade cobalt sulfate solution is obtained after standing, oil removal and fine filtration of the cobalt sulfate solution, wherein the cobalt content in the chemical components is 117.43g/L, the contents of impurities such as manganese, nickel, magnesium and calcium are respectively 0.0050, 0.0054, 0.0015 and 0.0015g/L, and the standard of T/ATCRR10-2020 is reached.
And 7: and (3) mixing the raffinate obtained in the step (6) with a soap-converting organic extractant Cyanex272, mixing the organic extractant with No. 260 solvent oil in an amount of 25% of CY-272, controlling the extraction stage number to be 10 stages, controlling the volume ratio of an organic phase to an aqueous phase to be 3, controlling the pH value of the aqueous phase at the outlet of the extraction stage to be 5.1, and performing countercurrent extraction on the organic phase and the aqueous phase. And (3) standing, deoiling and finely filtering the raffinate, and then evaporating to obtain a battery-grade nickel sulfate solution. The nickel content in the obtained nickel sulfate is 119.39g/L, the contents of impurities of manganese, cobalt, magnesium and calcium are respectively 1.35 ppm, 12.69 ppm, 0.27 ppm and 0.64ppm, and the standard of T/ATCRR 12-2020 is reached.
Loading an organic extractant, washing 7 grades, performing 2mol/L sulfuric acid back extraction to obtain a magnesium sulfate solution, wherein the number of back extraction stages is 6 grades, and performing 3-grade iron back washing and 2-grade water washing on the magnesium sulfate solution to recycle the organic extractant.

Claims (10)

1. A method for preferentially extracting metallic lithium from a waste ternary lithium ion battery and simultaneously obtaining battery-grade metal salt is characterized by comprising the following steps:
step 1: calcination with hydrogen
The waste ternary lithium ion battery is subjected to over-discharge, disassembly and crushing, screening, carbonization furnace roasting and multi-stage sorting to obtain black powder containing lithium, manganese, nickel and cobalt metal resources and graphite carbon, and the black powder is subjected to reduction roasting for 2-4 hours at 500-700 ℃ under the hydrogen atmosphere of 0.02-0.2 MPa to obtain reduced powder;
step 2: preferential extraction of lithium
Adding the reduced powder obtained in the step 1 into pure water, uniformly dispersing, performing filter pressing to obtain filter residue and filtrate, and performing reduced pressure concentration and crystallization on the filtrate to obtain lithium hydroxide monohydrate;
and 3, step 3: leaching extract impurities
Dissolving the filter residue obtained in the step 2 by using 98wt% of sulfuric acid to obtain a leaching solution; mixing the leachate with a soap-conversion organic extractant P204, extracting impurity metal calcium, copper, zinc and aluminum ions into an organic phase by adopting a counter-current extraction method to remove, and collecting raffinate;
and 4, step 4: extraction of manganese, cobalt and nickel
And (3) extracting the metal resources in the raffinate in the step (3) by adopting a soap-conversion organic extractant and a countercurrent extraction method according to the order of manganese, cobalt and nickel to respectively obtain high-purity manganese sulfate, battery-grade cobalt sulfate and nickel sulfate.
2. The method for preferentially extracting metallic lithium and simultaneously obtaining battery-grade metal salt from the waste ternary lithium ion battery as claimed in claim 1 is characterized in that the method for extracting manganese, cobalt and nickel comprises the following steps:
step a: extraction of high purity manganese salt
Mixing raffinate collected after leaching and extracting impurities with a soap-transfer organic extractant P204, and controlling the volume ratio of an organic phase to a water phase to be 2-4: 1, extracting by adopting a countercurrent extraction method, and collecting raffinate;
washing the extracted organic phase with 0.5mol/L sulfuric acid, performing back extraction with 2.2-2.3 mol/L sulfuric acid to obtain a manganese sulfate solution, and standing, removing oil, performing fine filtration and evaporative crystallization to obtain high-purity manganese sulfate;
step b: cobalt salt for extracting battery grade standard
Mixing the raffinate obtained in the step a with a soap-converting organic extractant P507, and controlling the volume ratio of an organic phase to a water phase to be 2-4: 1, extracting by adopting a countercurrent extraction method, and collecting raffinate;
washing the extracted organic phase with 0.5mol/L sulfuric acid, then performing back extraction with 2.4mol/L sulfuric acid to obtain a cobalt sulfate solution, and standing, removing oil, performing fine filtration and evaporative crystallization to obtain battery-grade cobalt sulfate;
step c: extraction of battery grade standard nickel salts
And c, mixing the raffinate obtained in the step b with a soap-converting organic extractant Cyanex272, and controlling the volume ratio of an organic phase to a water phase to be 2-4: 1, extracting by adopting a counter-current extraction method, collecting raffinate, standing the raffinate, removing oil, finely filtering, evaporating and crystallizing to obtain the battery-grade nickel sulfate.
3. The method for preferentially extracting metallic lithium from waste ternary lithium ion batteries and simultaneously obtaining battery-grade metal salts as claimed in claim 2, wherein in the step a, 260# solvent oil is added into the soap-converting organic extractant P204, and the volume of the P204 accounts for 20-30%.
4. The method for preferentially extracting metallic lithium and simultaneously obtaining battery-grade metal salt from waste ternary lithium ion batteries according to claim 2, wherein in the step a: the extraction stage number is 9-10 stages during extraction, and the pH of the water phase at the outlet of the extraction section is controlled to be 2.5-3.3; washing the extracted organic phase by 0.5mol/L sulfuric acid, and washing for 12-13 levels; then carrying out back extraction on the loaded organic P204 by using 2.2-2.3 mol/L sulfuric acid, wherein the number of the back extraction stages is 6, so as to obtain a manganese sulfate solution, and standing, deoiling, fine filtering, evaporating and crystallizing the manganese sulfate solution to obtain high-purity manganese sulfate; the no-load organic is recycled after 3-level reverse iron and 2-level water washing.
5. The method for preferentially extracting the metallic lithium from the waste ternary lithium ion batteries and simultaneously obtaining the battery-grade metal salt as claimed in claim 2, wherein in the step b, 260# solvent oil is added into the soap-conversion organic extractant P507, and the volume of the P507 accounts for 20-30%.
6. The method for preferentially extracting metallic lithium and simultaneously obtaining battery-grade metal salt from waste ternary lithium ion batteries according to claim 2, wherein in the step b: the extraction stage number is 10-11 stages during extraction, and the pH of the water phase at the outlet of the extraction section is controlled to be 4.0-4.5; washing the extracted organic phase with 0.5mol/L sulfuric acid for 14-15 stages; then, carrying out back extraction on the loaded organic P507 by using 2.4mol/L sulfuric acid, wherein the number of the back extraction stage is 6, so as to obtain a cobalt sulfate solution, and standing, deoiling, fine filtering, evaporating and crystallizing the cobalt sulfate solution to obtain battery-grade cobalt sulfate; the no-load organic matter is recycled after 3-level reverse iron and 2-level water washing.
7. The method for preferentially extracting the metallic lithium from the waste ternary lithium ion batteries and simultaneously obtaining the battery-grade metal salt according to claim 2, wherein in the step c, 260# solvent oil is added into a soap-converting organic extractant Cyanex272, and the volume ratio of the Cyanex272 is 20-30%.
8. The method for preferentially extracting metallic lithium and simultaneously obtaining battery-grade metal salts from waste ternary lithium ion batteries according to claim 2, wherein in the step c: the extraction stage number is 8-9 stages during extraction, and the pH of the water phase at the outlet of the extraction section is controlled to be 5.0-5.5; washing the extracted organic phase by 0.5mol/L sulfuric acid, and washing for 6 grades; then carrying out back extraction on the loaded organic Cyanex272 by using 2mol/L sulfuric acid, wherein the number of the back extraction stages is 6; the no-load organic is recycled after 3-level reverse iron and 2-level water washing.
9. The method for preferentially extracting metallic lithium from waste ternary lithium ion batteries and simultaneously obtaining battery-grade metal salts as claimed in claim 1, wherein in step 3, 260# solvent oil is added into a soap-converting organic extractant P204, and the volume of P204 accounts for 20-30%.
10. The method for preferentially extracting metallic lithium and simultaneously obtaining battery-grade metal salt from waste ternary lithium ion batteries according to claim 1, wherein in the step 3: the extraction stage number is 8-10 stages during extraction, and the pH of the water phase at the outlet of the extraction section is controlled to be 2.5-2.8; washing the extracted organic phase by 0.5mol/L sulfuric acid, and washing for 12-13 levels; then, carrying out back extraction on the loaded organic P204 by using 2.0mol/L sulfuric acid, wherein the number of the back extraction stage is 6, and obtaining a mixed solution of aluminum sulfate, calcium sulfate, copper sulfate and zinc sulfate; the no-load organic is recycled after 3-level reverse iron and 2-level water washing.
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