CN115571925B - Method for recycling and preparing lithium carbonate and ternary precursor from waste lithium batteries - Google Patents
Method for recycling and preparing lithium carbonate and ternary precursor from waste lithium batteries Download PDFInfo
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- CN115571925B CN115571925B CN202210946041.4A CN202210946041A CN115571925B CN 115571925 B CN115571925 B CN 115571925B CN 202210946041 A CN202210946041 A CN 202210946041A CN 115571925 B CN115571925 B CN 115571925B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 55
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 52
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 38
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 38
- 239000002243 precursor Substances 0.000 title claims abstract description 35
- 239000002699 waste material Substances 0.000 title claims abstract description 30
- 238000004064 recycling Methods 0.000 title claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 104
- 238000002386 leaching Methods 0.000 claims abstract description 89
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 49
- 239000002184 metal Substances 0.000 claims abstract description 49
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 39
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 37
- 238000000975 co-precipitation Methods 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 17
- 239000000706 filtrate Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 69
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 238000000926 separation method Methods 0.000 claims description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 238000001556 precipitation Methods 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 19
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 16
- 229910017052 cobalt Inorganic materials 0.000 claims description 16
- 239000010941 cobalt Chemical class 0.000 claims description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 16
- 239000011572 manganese Substances 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 239000002893 slag Substances 0.000 claims description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229910052748 manganese Chemical class 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 12
- 239000010405 anode material Substances 0.000 claims description 11
- 238000004537 pulping Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000003518 caustics Substances 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 6
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002912 waste gas Substances 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 22
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 19
- 238000013329 compounding Methods 0.000 abstract description 7
- 239000010926 waste battery Substances 0.000 abstract description 4
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000003638 chemical reducing agent Substances 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229940073644 nickel Drugs 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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 discloses a method for recycling and preparing lithium carbonate and ternary precursors from waste lithium batteries, which comprises the following steps: (1) sulfur dioxide primary acid leaching; (2) secondary ammonia leaching of an ammonia water-ammonium salt system; (3) mixing and compounding the leaching solution to adjust the metal proportion; (4) preparing cobalt nickel manganese coprecipitate by a coprecipitation method; (5) ammonia absorption and reuse ammonia leaching; (6) Washing and drying the cobalt nickel manganese coprecipitate to prepare a cobalt nickel manganese ternary precursor material; and (7) precipitating lithium from the lithium-containing filtrate to prepare lithium carbonate. According to the invention, a two-stage leaching process is adopted, valuable elements in the waste lithium batteries are leached out efficiently, the leaching rate of the waste lithium batteries is further improved by an ammonia leaching process of an ammonia water-ammonium salt system, the recovery and recycling of the ammonia water are realized while the ternary precursor is recovered through coprecipitation, and lithium carbonate can be recovered from the separated lithium-containing filtrate. The process has low recovery cost and high recovery product value, and is suitable for popularization and application in the waste battery recovery industry.
Description
Technical Field
The invention relates to the technical field of waste battery material recovery and recycling, in particular to a method for preparing lithium carbonate and ternary precursors by recycling waste lithium batteries.
Background
With the development of the power automobile industry, the output and the demand of the lithium ion battery are improved year by year, and as the effective service life of the lithium ion battery is 5-8 years, the scrapping amount of the power battery is also increased year by year, and 35 ten thousand tons of waste lithium ion batteries are expected to be generated in 2025 years. The waste lithium ion battery contains organic substances and heavy metals, if the waste lithium ion battery is directly discharged, the environment pollution is caused, the human health is endangered, and in addition, the waste lithium ion battery contains Li, ni, co, mn, cu and other valuable metals, and the price of the metals is relatively high, so that the waste lithium ion battery is efficiently and environmentally recycled, the environmental pressure can be solved, and considerable economic benefits can be brought.
The recovery process of the nickel-cobalt-manganese ternary lithium battery is mainly divided into a fire process and a wet process, wherein the fire process generally carries out high-temperature smelting on the waste lithium ion battery directly to generate a metal alloy, and valuable metals such as the IEM in the beauty of Belgium, germany and the like are extracted from the alloy. The wet process includes the first disassembling and sorting waste battery, leaching the obtained positive electrode waste with sulfuric acid, adding reductant to obtain nickel, cobalt and manganese sulfate product. The traditional wet process has the defects that the acid leaching process needs to be added with a reducing agent, the cost is high, the process flow of the extraction and separation of nickel, cobalt and manganese is long, and the operation is complex. In addition, the concentration of Li in raffinate after nickel, cobalt and manganese are extracted is lower, so that the recovery rate of the Li is reduced.
In recent years, a method for recovering valuable metals in a lithium ion battery by a combined process of a pyrogenic process and a wet process has been attracting more attention, for example, patent CN106129511a is to mix a lithium ion battery anode material with a solid carbon reducing agent such as brown coal and the like, perform reduction roasting, introduce carbon dioxide into a roasting product to perform water leaching to obtain a lithium bicarbonate solution, evaporate and crystallize to obtain a lithium carbonate product, and extract and purify water leaching residues after acid leaching or ammonia leaching to recover nickel, cobalt and manganese. The method takes solid carbon sources such as lignite and the like as a reducing agent, the using amount of the reducing agent is large, and impurities in the reducing agent can influence the quality of nickel, cobalt and manganese products and graphite.
In the aspect of nickel-cobalt-manganese recovery, an extraction method and a coprecipitation method are mainly adopted for separation and recovery at present. The patent CN107267759A lithium battery anode material is subjected to acid leaching treatment, and after impurity removal, the nickel cobalt manganese is subjected to multistage extraction by using an alkali saponified P507 extractant, so as to obtain nickel cobalt manganese strip liquor and lithium-containing raffinate. However, when P507 is adopted for extraction, lithium is also extracted into an organic phase, and enters a stripping solution during back extraction, so that the quality of a nickel cobalt manganese precursor is affected, and the recovery rate of lithium is also greatly reduced.
In view of the foregoing, there is a need to develop efficient and economical methods for recovering waste ternary lithium ion batteries to prepare lithium carbonate and ternary precursors.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing lithium carbonate and ternary precursor by recycling waste lithium batteries.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
according to one aspect of the invention, the invention discloses a method for recycling and preparing lithium carbonate and ternary precursors from waste lithium batteries, which comprises the following processing steps:
(1) Sulfur dioxide primary acid leaching: pulping anode material powder to obtain slurry, introducing sulfur dioxide gas into the slurry for primary acid leaching, and carrying out solid-liquid separation to obtain a metal salt solution and acid leaching residues;
(2) Secondary ammonia leaching: introducing sulfur dioxide in the step (1) into ammonia water, reacting to obtain an ammonium sulfite solution, pulping the acid leaching slag obtained in the step (1), adding the ammonia water and the ammonium sulfite solution into the slurry for secondary ammonia leaching reaction, and carrying out solid-liquid separation to obtain ammonia leaching slag and ammonia leaching liquid, wherein the ammonia leaching liquid enters the next step for use;
(3) And (3) compounding and adjusting: carrying out precipitation impurity removal treatment on the metal salt solution obtained in the step (1), mixing the metal salt clear solution obtained after solid-liquid separation with the ammonia immersion liquid obtained in the step (2) to obtain a mixed solution, detecting the content of each metal in the mixed solution, and adding metal salt into the mixed solution to carry out compound adjustment to obtain a ternary compound solution;
(4) Co-precipitation: adding caustic alkali into the ternary complex liquid obtained in the step (3) under the condition of heating and stirring to perform coprecipitation reaction, absorbing the obtained ammonia gas to obtain ammonia water, and repeating the step (2), wherein the ammonia water is recycled;
(5) Preparing a ternary precursor material: after the coprecipitation reaction in the step (4) is finished, carrying out solid-liquid separation to obtain cobalt nickel manganese coprecipitate and lithium-containing filtrate, and washing and drying the cobalt nickel manganese coprecipitate to obtain a ternary precursor material;
(6) And (3) recovering lithium carbonate: and (3) carrying out carbonation method lithium precipitation reaction on the lithium-containing filtrate obtained in the step (5), and then carrying out solid-liquid separation, washing and drying to obtain a lithium carbonate product.
Preferably, the liquid-solid ratio of the slurry in the step (1) is 3:1-30:1, the sulfur dioxide gas is generated by an industrial sulfur dioxide waste gas or a sulfur dioxide generator, the pH value of the acid leaching reaction is controlled to be less than 4, the reaction temperature is 30-90 ℃, and the reaction time is 10-120min.
Preferably, the aqueous ammonia in step (2): sulfur dioxide (molar ratio) is more than or equal to 2:1, the concentration of the ammonium sulfite solution is 0.5-2mol/L, the concentration of the ammonia water is 2-5mol/L, and the ammonia leaching reaction temperature is controlled to be 30-90 ℃.
Preferably, in the step (3), the deep impurity removal adopts sodium sulfide two-stage precipitation to remove impurity copper in the metal salt solution, and the pH value of the reaction is controlled to be 2-3.
Preferably, in the step (3), the Li in the mixed solution is adjusted by compounding: (ni+co+mn) =1 to 1.15:1.
preferably, the metal salt in the step (3) is an inorganic metal salt of nickel, cobalt, manganese.
Preferably, the heating temperature of the coprecipitation reaction in the step (4) is 40-80 ℃, the pH value of the reaction is adjusted to 10-12 by ammonia water, and the reaction time is 0.5-6 h.
Preferably, the carbonation process in step (6) is a carbon dioxide precipitation process or a carbonate precipitation process.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
1. the invention adopts SO produced by industrial production 2 The waste gas is used as reactants of the acid leaching agent and the ammonia leaching agent, so that the purpose of treating waste by waste is achieved, and the cost of an auxiliary medicament in the production and recovery process is greatly reduced.
2. The invention adopts a process of combining primary acid leaching and secondary ammonia leaching, wherein the primary weak acid leaching converts part of metal into metal sulfate, the secondary ammonia leaching adopts an ammonia-ammonium salt leaching system, the rest metal is further leached, cobalt and lithium can be selectively leached preferentially under the leaching system, the leaching rate of cobalt and lithium can reach more than 99 percent, and the leaching rate of nickel and manganese can reach more than 97 percent. The ammonium salt in the ammonia leaching system is ammonium sulfite, which is a reducing agent, and the reducing agent is not needed to be added in the reaction process, so that the dual-function effect of reducing and coordinating metal is achieved, and the consumption cost of the reducing agent is reduced.
3. The cobalt-nickel-manganese in the anode material is recovered by adopting a coprecipitation method, and lithium exists in the solution, so that the separation of the cobalt-nickel-manganese ternary material and the lithium is realized. The ammonia generated in the system can be further recovered to obtain ammonia water by adding caustic alkali coprecipitation, and the ammonia water can be used for ammonia leaching agent preparation and ammonia leaching reaction, so that recovery and internal circulation of process products are realized, and the process production cost is reduced.
4. The ternary precursor material and lithium carbonate are obtained through recycling, the production cost is low, the product performance is good, the recycling product value is high, and the method is suitable for popularization and application in the waste battery recycling industry.
Brief description of the drawings
FIG. 1 is a flow chart of a method for recycling and preparing lithium carbonate and ternary precursor from waste lithium batteries according to the invention;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail by referring to preferred embodiments. It should be noted, however, that many of the details set forth in the description are merely provided to provide a thorough understanding of one or more aspects of the invention, and that these aspects of the invention may be practiced without these specific details.
Example 1
As shown in fig. 1, the method for preparing lithium carbonate and ternary precursor by recycling waste lithium batteries comprises the following operation steps:
(1) Sulfur dioxide primary acid leaching: pulping anode material powder (nickel-cobalt-manganese ternary lithium battery anode material) to obtain slurry, controlling the liquid-solid ratio of the slurry to be 10:1, introducing industrial sulfur dioxide waste gas into the slurry to carry out primary acid leaching, controlling the pH value of acid leaching reaction to be 4, controlling the reaction temperature to be 30 ℃, and controlling the reaction time to be 10min, and obtaining metal salt solution and acid leaching slag after solid-liquid separation;
(2) Secondary ammonia leaching: introducing sulfur dioxide in the step (1) into ammonia water, and introducing the ammonia water: sulfur dioxide (molar ratio) =2:1, reacting to obtain ammonium sulfite solution, pulping the acid leaching slag obtained in the step (1), adding ammonia water and the ammonium sulfite solution into the solution to perform secondary ammonia leaching reaction, wherein the concentration of the ammonium sulfite is 0.5mol/L, the concentration of the ammonia water is 2mol/L, controlling the ammonia leaching reaction temperature to be 50 ℃, obtaining ammonia leaching slag and ammonia leaching liquid after solid-liquid separation, and allowing the ammonia leaching liquid to enter the next step for use;
(3) And (3) compounding and adjusting: removing impurity copper in the metal salt solution obtained in the step (1) through sodium sulfide two-stage precipitation, controlling the reaction pH value to be 3, mixing the metal salt clear solution obtained after solid-liquid separation with the ammonia immersion liquid obtained in the step (2) to obtain mixed liquid, detecting the content of each metal in the mixed liquid, adding inorganic metal salts of nickel, cobalt and manganese into the mixed liquid for compound adjustment, and adjusting Li in the mixed liquid: (ni+co+mn) =1: 1, obtaining ternary compound liquid;
(4) Co-precipitation: adding caustic alkali into the ternary compound solution obtained in the step (3) under the condition of heating and stirring for coprecipitation reaction, controlling the heating temperature to be 40 ℃, adjusting the reaction pH value to be 10 by ammonia water, and absorbing ammonia gas obtained by the coprecipitation reaction for 0.5h to obtain ammonia water, and repeating the step (2), wherein the ammonia water is recycled;
(5) Preparing a ternary precursor material: after the coprecipitation reaction in the step (4), carrying out solid-liquid separation to obtain cobalt-nickel-manganese coprecipitate and lithium-containing filtrate, and washing and drying the cobalt-nickel-manganese coprecipitate to obtain a ternary precursor material;
(6) And (3) recovering lithium carbonate: introducing CO into the lithium-containing filtrate obtained in the step (5) 2 And carrying out lithium precipitation reaction, and then carrying out solid-liquid separation, washing and drying to obtain a lithium carbonate product.
Example 2
As shown in fig. 1, the method for preparing lithium carbonate and ternary precursor by recycling waste lithium batteries comprises the following operation steps:
(1) Sulfur dioxide primary acid leaching: and (3) pulping the anode material powder to obtain slurry, controlling the liquid-solid ratio of the slurry to be 3:1, introducing industrial sulfur dioxide waste gas into the slurry to carry out primary acid leaching, controlling the pH value of the acid leaching reaction to be 3.5, controlling the reaction temperature to be 80 ℃, and controlling the reaction time to be 30min, and obtaining the metal salt solution and acid leaching slag after solid-liquid separation.
(2) Secondary ammonia leaching: introducing sulfur dioxide in the step (1) into ammonia water, wherein the ammonia water is prepared by the following steps: and (3) reacting to obtain ammonium sulfite, pulping the acid leaching slag obtained in the step (1), adding ammonia water and ammonium sulfite into the slurry to perform secondary ammonia leaching reaction, wherein the concentration of the ammonium sulfite is 1mol/L, the concentration of the ammonia water is 3mol/L, the ammonia leaching reaction temperature is controlled to be 30 ℃, and obtaining ammonia leaching slag and ammonia leaching liquid after solid-liquid separation, wherein the ammonia leaching liquid enters the next step for use.
(3) And (3) compounding and adjusting: removing impurity copper in the metal salt solution obtained in the step (1) through sodium sulfide two-stage precipitation, controlling the reaction pH value to be 2.5, mixing the metal salt clear solution obtained after solid-liquid separation with the ammonia immersion liquid obtained in the step (2) to obtain mixed liquid, detecting the content of each metal in the mixed liquid, adding inorganic metal salts of nickel, cobalt and manganese into the mixed liquid for compound adjustment, and adjusting Li in the mixed liquid: (ni+co+mn) =1.05: 1, obtaining ternary compound liquid;
(4) Co-precipitation: adding caustic alkali into the ternary complex liquid obtained in the step (3) under the condition of heating and stirring for coprecipitation reaction, controlling the heating temperature to be 60 ℃, adjusting the reaction pH value to be 12 by ammonia water, reacting for 2 hours, absorbing ammonia gas obtained by the coprecipitation reaction to obtain ammonia water, and repeating the step (2), wherein the ammonia water is recycled;
(5) Preparing a ternary precursor material: after the coprecipitation reaction in the step (4), carrying out solid-liquid separation to obtain cobalt-nickel-manganese coprecipitate and lithium-containing filtrate, and washing and drying the cobalt-nickel-manganese coprecipitate to obtain a ternary precursor material;
(6) And (3) recovering lithium carbonate: adding sodium carbonate into the lithium-containing filtrate obtained in the step (5) to carry out lithium precipitation reaction, and then carrying out solid-liquid separation, washing and drying to obtain a lithium carbonate product.
Example 3
As shown in fig. 1, the method for preparing lithium carbonate and ternary precursor by recycling waste lithium batteries comprises the following operation steps:
(1) Sulfur dioxide primary acid leaching: and (3) pulping the anode material powder to obtain slurry, wherein the liquid-solid ratio of the slurry is controlled to be 30:1, introducing sulfur dioxide waste gas into the slurry to carry out primary acid leaching, controlling the pH value of the acid leaching reaction to be 3, reacting at 90 ℃ for 120min, and carrying out solid-liquid separation to obtain a metal salt solution and acid leaching residues.
(2) Secondary ammonia leaching: introducing sulfur dioxide in the step (1) into ammonia water, wherein the ammonia water is prepared by the following steps: and (3) reacting to obtain ammonium sulfite, pulping the acid leaching slag obtained in the step (1), adding ammonia water and ammonium sulfite into the acid leaching slag to perform secondary ammonia leaching reaction, wherein the concentration of the ammonium sulfite is 2mol/L, the concentration of the ammonia water is 5mol/L, the ammonia leaching reaction temperature is controlled to be 90 ℃, and obtaining ammonia leaching slag and ammonia leaching liquid after solid-liquid separation, wherein the ammonia leaching liquid enters the next step for use.
(3) And (3) compounding and adjusting: removing impurity copper in the metal salt solution obtained in the step (1) through sodium sulfide two-stage precipitation, controlling the reaction pH value to be 2, mixing the metal salt clear solution obtained after solid-liquid separation with the ammonia immersion liquid obtained in the step (2) to obtain mixed liquid, detecting the content of each metal in the mixed liquid, adding inorganic metal salts of nickel, cobalt and manganese into the mixed liquid for compound adjustment, and adjusting Li in the mixed liquid: (ni+co+mn) =1.15: 1, obtaining ternary compound liquid;
(4) Co-precipitation: adding caustic alkali into the ternary complex liquid obtained in the step (3) under the condition of heating and stirring for coprecipitation reaction, controlling the heating temperature to be 80 ℃, adjusting the reaction pH value to be 11 by ammonia water, and absorbing ammonia gas obtained by the coprecipitation reaction for 6 hours to obtain ammonia water, and repeating the step (2), wherein the ammonia water is recycled;
(5) Preparing a ternary precursor material: after the coprecipitation reaction in the step (4), carrying out solid-liquid separation to obtain cobalt-nickel-manganese coprecipitate and lithium-containing filtrate, and washing and drying the cobalt-nickel-manganese coprecipitate to obtain a ternary precursor material;
(6) And (3) recovering lithium carbonate: adding sodium carbonate into the lithium-containing filtrate obtained in the step (5) to carry out lithium precipitation reaction, and then carrying out solid-liquid separation, washing and drying to obtain a lithium carbonate product.
Comparative example
The method for preparing lithium carbonate and ternary precursor by recycling waste lithium batteries by sulfuric acid leaching method comprises the following operation steps:
(1) Sulfuric acid pickling: the method comprises the steps of pulping anode material powder to obtain slurry, controlling the liquid-solid ratio of the slurry to be 10:1, adding 1mol/L sulfuric acid into the slurry to perform primary acid leaching, controlling the pH value of acid leaching reaction to be 1, controlling the reaction temperature to be 80 ℃, controlling the reaction time to be 60min, and obtaining metal salt solution and acid leaching slag after solid-liquid separation.
(2) And (3) compounding and adjusting: removing impurity copper in the metal salt solution obtained in the step (1) through sodium sulfide two-stage precipitation, controlling the reaction pH value to be 3, obtaining metal salt clear liquid after solid-liquid separation, detecting the content of each metal in the metal salt clear liquid, adding inorganic metal salts of nickel, cobalt and manganese into the metal salt clear liquid for compound adjustment, and adjusting Li in the metal salt clear liquid: (ni+co+mn) =1: 1, obtaining ternary compound liquid;
(3) Co-precipitation: adding caustic alkali into the ternary complex liquid obtained in the step (3) to carry out coprecipitation reaction, and regulating the pH value of the reaction to 11 by ammonia water, wherein the reaction time is 1h;
(4) Preparing a ternary precursor material: after the coprecipitation reaction in the step (4), carrying out solid-liquid separation to obtain cobalt-nickel-manganese coprecipitate and lithium-containing filtrate, and washing and drying the cobalt-nickel-manganese coprecipitate to obtain a ternary precursor material;
(5) And (3) recovering lithium carbonate: adding sodium carbonate into the lithium-containing filtrate obtained in the step (5) to carry out lithium precipitation reaction, and then carrying out solid-liquid separation, washing and drying to obtain a lithium carbonate product.
The applicant respectively adopts the methods of examples 1-3 and comparative example to recycle the same batch of waste ternary lithium battery anode materials, performs purity detection on each component of the obtained ternary precursor materials and lithium carbonate products, calculates the purity of the products and the recovery rate of cobalt, nickel, manganese and lithium, and the results are shown in table 1.
Table 1 product purity and recovery index obtained for each example
| Project | Example 1 | Example 2 | Example 3 | Comparative example |
| Cobalt recovery/% | 91.7 | 95.6 | 99.5 | 91.2 |
| Nickel recovery/% | 93.5 | 95.9 | 99.5 | 91.6 |
| Manganese recovery/% | 91.4 | 94.6 | 98.3 | 89.1 |
| Lithium recovery/% | 91.5 | 97.6 | 97.9 | 89.5 |
| Lithium carbonate purity/% | 92.5 | 95.2 | 99.5 | 90.8 |
The result shows that the method has nickel and cobalt recovery rate up to 99%, manganese and lithium recovery rate up to 97%, lithium carbonate purity up to 99.5%, and is superior to metal recovery rate and lithium carbonate purity obtained by sulfuric acid leaching recovery. .
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications could be made by those skilled in the art without departing from the principles of the present invention, which modifications would also be considered to be within the scope of the invention.
Claims (6)
1. The method for preparing the lithium carbonate and the ternary precursor by recycling the waste lithium batteries is characterized by comprising the following processing steps:
step (1) sulfur dioxide primary acid leaching: pulping anode material powder to obtain slurry, introducing sulfur dioxide gas into the slurry for primary acid leaching, and carrying out solid-liquid separation to obtain a metal salt solution and acid leaching residues; the liquid-solid ratio of the slurry is 3:1-30:1, the sulfur dioxide gas is generated by an industrial sulfur dioxide waste gas or sulfur dioxide generator, the pH value of the acid leaching reaction is controlled to be less than 4, the reaction temperature is 30-90 ℃, and the reaction time is 10-120min;
step (2) secondary ammonia leaching: introducing sulfur dioxide in the step (1) into ammonia water, reacting to obtain an ammonium sulfite solution, pulping the acid leaching slag obtained in the step (1), adding ammonia water and ammonium sulfite into the acid leaching slag to perform a secondary ammonia leaching reaction, and performing solid-liquid separation to obtain ammonia leaching slag and ammonia leaching liquid, wherein the ammonia leaching liquid enters the next step for use;
and (3) compound regulation: carrying out precipitation impurity removal treatment on the metal salt solution obtained in the step (1), mixing the metal salt clear solution obtained after solid-liquid separation with the ammonia immersion liquid obtained in the step (2) to obtain a mixed solution, detecting the content of each metal in the mixed solution, and adding metal salt into the mixed solution to carry out compound adjustment to obtain a ternary compound solution; removing impurities by precipitation and adopting sodium sulfide two-stage precipitation to remove impurity copper in the metal salt solution, and controlling the pH value of the reaction to be 2-3;
and (3) coprecipitation: adding caustic alkali into the ternary complex liquid obtained in the step (3) under the condition of heating and stirring to perform coprecipitation reaction, absorbing the obtained ammonia gas to obtain ammonia water, and repeating the step (2), wherein the ammonia water is recycled;
and (5) preparing a ternary precursor material: after the coprecipitation reaction in the step (4) is finished, carrying out solid-liquid separation to obtain a ternary coprecipitate and a lithium-containing filtrate, and washing and drying the ternary coprecipitate to obtain a ternary precursor material;
and (6) recovering lithium carbonate: and (3) carrying out carbonation method lithium precipitation reaction on the lithium-containing filtrate obtained in the step (5), and then carrying out solid-liquid separation, washing and drying to obtain a lithium carbonate product.
2. The method for recycling and preparing lithium carbonate and ternary precursor from waste lithium batteries according to claim 1, wherein in the step (2), the molar ratio of ammonia water to sulfur dioxide is more than or equal to 2:1, the concentration of the ammonium sulfite solution is 0.5-2mol/L, the concentration of the ammonia water is 2-5mol/L, and the ammonia leaching reaction temperature is controlled to be 30-90 ℃.
3. The method for recycling and preparing lithium carbonate and ternary precursor from waste lithium batteries according to claim 1, wherein in the step (3), li of the mixed solution is compounded and adjusted to be Ni+Co+Mn=1-1.15:1.
4. The method for recycling lithium carbonate and ternary precursor from waste lithium batteries according to claim 1, wherein the metal salts in step (3) are inorganic metal salts of nickel, cobalt and manganese.
5. The method for recycling and preparing lithium carbonate and ternary precursor from waste lithium batteries according to claim 1, wherein the heating temperature of the coprecipitation reaction in the step (4) is 40-80 ℃, ammonia water is used for absorption and adjustment of the pH value of the reaction to 10-12, and the reaction time is 0.5-6 h.
6. The method for recycling lithium carbonate and ternary precursor from waste lithium batteries according to claim 1, wherein the carbonation method in step (6) is a carbon dioxide precipitation method or a carbonate precipitation method.
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