WO2023045331A1 - 一种选择性回收废旧锂电池中有价金属的方法 - Google Patents

一种选择性回收废旧锂电池中有价金属的方法 Download PDF

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WO2023045331A1
WO2023045331A1 PCT/CN2022/090064 CN2022090064W WO2023045331A1 WO 2023045331 A1 WO2023045331 A1 WO 2023045331A1 CN 2022090064 W CN2022090064 W CN 2022090064W WO 2023045331 A1 WO2023045331 A1 WO 2023045331A1
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Prior art keywords
manganese
sulfate
leaching
iron
solid
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PCT/CN2022/090064
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English (en)
French (fr)
Inventor
陈鑫根
何然
曹磊军
黎亮
唐红辉
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Application filed by Hunan Brunp Recycling Technology Co Ltd, Guangdong Brunp Recycling Technology Co Ltd, Hunan Bangpu Automobile Circulation Co Ltd filed Critical Hunan Brunp Recycling Technology Co Ltd
Priority to DE112022002565.4T priority Critical patent/DE112022002565T5/de
Priority to ES202390202A priority patent/ES2976316B2/es
Priority to US18/682,455 priority patent/US20240347803A1/en
Priority to MX2023014734A priority patent/MX2023014734A/es
Priority to GB2318781.8A priority patent/GB2622169A/en
Priority to HU2400163A priority patent/HUP2400163A1/hu
Publication of WO2023045331A1 publication Critical patent/WO2023045331A1/zh
Anticipated expiration legal-status Critical
Priority to MA65129A priority patent/MA65129A1/fr
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides
    • 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
    • C01G53/00—Compounds of nickel
    • C01G53/10—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • 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
    • C22B1/06—Sulfating roasting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • C22B15/0091—Treating solutions by chemical methods by cementation
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043—Sulfurated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical 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
    • C22B47/00—Obtaining manganese
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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

Definitions

  • the invention belongs to the field of lithium ion battery recycling, and in particular relates to a method for selectively recycling valuable metals in waste lithium batteries.
  • Lithium battery recycling has achieved rapid development in China in recent years. Wasted ternary lithium batteries are dismantled, crushed, leached, copper removed, iron and aluminum removed, calcium and magnesium removed, extracted and co-precipitated to prepare ternary precursors. And lithium salt, achieved better economic benefits, and formed a larger scale.
  • sulfuric acid system sodium sulfite, hydrogen peroxide, and sodium thiosulfate are generally used as a reducing agent to transfer all valuable metals in the raw material into the sulfuric acid system, and the leaching rate of nickel, cobalt, and manganese can reach more than 99%.
  • This non-selective leaching also brings a large amount of impurities into the system, which greatly increases the difficulty of subsequent impurity removal treatment.
  • the main recovered valuable metals are nickel-cobalt-lithium.
  • the common wet process uses extractants to separate metal nickel-cobalt and manganese.
  • the leaching of manganese increases the consumption of liquid caustic soda and sulfuric acid. , increasing the extraction throughput, according to statistics, reducing the extraction of manganese once, saving about 10,000 yuan per ton of manganese.
  • the reducing agent has mild conditions, is easy to transport and store, and has a high conversion rate for selective low manganese leaching. craft technology.
  • the purpose of the present invention is to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the present invention provides a method for selectively recovering valuable metals in waste lithium batteries.
  • This method can selectively leach a small amount of manganese metal in ternary batteries, and simultaneously does not introduce hydrogen peroxide, which has a low utilization rate in the leaching process.
  • Sodium sulfite and other reducing agents solve the process problems such as low utilization rate of reducing agents in low-acid leaching, troublesome storage and transportation, and foam generation. Acid reaction avoids the problem of reaction hydrogen production, which greatly guarantees the safety of production.
  • the present invention adopts the following technical solutions:
  • a method for selectively reclaiming valuable metals in waste lithium batteries comprising the following steps:
  • the calcination temperature is 350-600°C.
  • the sulfate is one or both of ammonium sulfate or sodium sulfate; the sulfide is one or both of sodium sulfide or ammonium bisulfide solution.
  • the temperature of the water immersion is 50-90° C.
  • the liquid-solid ratio of the water immersion is (8-12): 1 g/ml.
  • the filter residue is a high-valent oxide of nickel-cobalt-manganese.
  • the pH of the sulfuric acid is 1-2.
  • the leaching temperature is 80°C-110°C.
  • the iron-containing compound is at least one of a divalent iron compound or a trivalent iron compound.
  • the divalent compound of iron is one of ferrous sulfate and ferrous chloride; the trivalent compound of iron is one of ferric sulfate and ferric chloride.
  • the concentration of the divalent or trivalent iron compound is 10-20 g/l.
  • the mass ratio of filter residue and iron-containing compound in the leaching process is 10:(0.5-2).
  • the pH of the leaching is 0.5-2, and the leaching time is 8-20 hours.
  • step (3) before the extraction, it also includes adding iron powder to the liquid phase after solid-liquid separation in step (2) for reduction reaction, solid-liquid separation, taking the liquid phase and adding it to the liquid phase described in step (1).
  • React the filter residue separate the solid and liquid, take the liquid phase and add sodium fluoride and calcium salt for reaction, separate the solid and liquid, take the liquid phase and add aluminum sulfate and calcium salt for reaction, and obtain nickel cobalt manganese sulfate solution.
  • the calcium salt is one or both of calcium sulfate or calcium carbonate.
  • step (1) for reaction after adding the liquid phase to the filter residue in step (1) for reaction, it also includes adjusting the pH to acidity.
  • adjusting the pH to acidity is adjusting the pH to 3.5-4.5.
  • the reagent used in the extraction is at least one of P204 or P507.
  • step (2) reaction The mechanism of step (2) reaction is as follows:
  • the mechanism is as in formula (I). After the reaction is carried out for a period of time, the reaction conditions are controlled, and the divalent manganese is converted into high manganese.
  • the mechanism is as in formula (II), and the ferric iron produced by the reaction Or the ferric iron introduced directly reacts with a small amount of aluminum and copper in the battery powder, and the mechanism is as shown in formula (III). Since the oxidation of high-valent nickel and cobalt is much greater than that of manganese dioxide, the manganese dioxide formed under the pH environment of this reaction is basically Will not be dissolved.
  • step (3) reaction is as follows:
  • Extraction is the transfer of a compound from one solvent to another by using the difference in solubility or distribution coefficient of the compound in two immiscible (or slightly soluble) solvents.
  • the manganese ions react with the extractant to form an extract that is insoluble in the water phase but easily soluble in the organic phase, so that the manganese is transferred from the water phase to the organic phase.
  • sulfuric acid is mixed with the organic phase to protonate the extractant to disintegrate the extract, and the manganese ions return to the water phase from the organic phase to realize stripping.
  • the method of the present invention selectively extracts lithium first, so that manganese can be single-extracted subsequently, and an iron compound or mixture is introduced in the leaching section as a reducing agent, so that lithium cobaltate and nickel in ternary battery powder can be leached safely and efficiently.
  • Cobalt metal element while manganese does not leach, effectively separates manganese metal element, and then selectively extracts manganese in the later stage, eliminating the flux of nickel and cobalt in the extraction section, reducing the flux of manganese in the extraction section, and achieving the positive electrode of waste lithium batteries
  • the material metal elements are selectively recovered, and a nickel-cobalt metal recovery method is provided that is safe, low-cost, has no risk of raw material transportation and storage, and has a mild reaction process.
  • Fig. 1 is the technological process schematic diagram of embodiment 1 and embodiment 2 of the present invention
  • Figure 2 is the sequence of metals extracted by P507 at different pHs
  • FIG. 3 shows the sequence of metals extracted by P204 at different pH.
  • step (4) Add 200kg sodium fluoride to the filtrate of step (4) to remove magnesium, add 850kg calcium sulfate to remove fluoride, then add 850kg aluminum sulfide and calcium carbonate to remove fluorine and iron and aluminum by precipitation, and finally add P2O4 to extract and remove calcium to obtain calcium magnesium slag, fluorine-containing slag (calcium fluoride) and filtrate;
  • step (6) Add P507 to the filtrate of step (5) for extraction to obtain nickel-cobalt sulfate solution and manganese sulfate solution.
  • the nickel-cobalt sulfate solution is evaporated and recrystallized to obtain qualified nickel-cobalt sulfate binary crystals, and the manganese extraction solution is processed to obtain battery-grade Manganese sulfate crystals.
  • the manganese dioxide slag in the step (1) is separated and dried to obtain a dry weight of about 250 kg of manganese dioxide, wherein the content of nickel is 0.02%, and the content of cobalt is 0.03%.
  • the dry weight of graphite slag is about 280 kg, the nickel content is 0.01%, the cobalt content is 0.02%, and the manganese content is 4.72%.
  • Step (6) obtains a total of 1700 kilograms of nickel-cobalt sulfate crystals, with a nickel content of 8.3%, a cobalt content of 11.3%, and 100 kilograms of manganese sulfate crystals with a manganese content of 31.64%.
  • step (2) reaction The mechanism of step (2) reaction is as follows:
  • step (3) 80Kg iron powder is added in the filtrate of step (2) and mixes, carry out reduction reaction, obtain sponge copper and liquid after copper removal;
  • step (2) Heating the liquid after copper removal to 80°C, adding 100 kilograms of filter residue after the roasting treatment in step (2) (the nickel content is 28.8%, the cobalt content is 17.9%, and the manganese content is 11.3%) to mix, react, adjust pH To 3.5-4.5, filter to obtain iron-aluminum slag and filtrate;
  • step (4) Add 200kg sodium fluoride to the filtrate of step (4) to remove magnesium, add 800Kg calcium sulfate to remove fluoride, then add 1000Kg aluminum sulfide and calcium carbonate to remove fluorine and iron and aluminum by precipitation, and finally add P2O4 to extract and remove calcium to obtain calcium magnesium slag, fluorine-containing slag (calcium fluoride) and filtrate;
  • step (6) Add P507 to the filtrate of step (5) for extraction to obtain nickel-cobalt sulfate solution and manganese sulfate solution.
  • the nickel-cobalt sulfate solution is evaporated and recrystallized to obtain qualified nickel-cobalt sulfate binary crystals, and the manganese extraction solution is processed to obtain battery-grade Manganese sulfate crystals.
  • the manganese dioxide slag in the step (1) is separated and dried to obtain a dry weight of about 150 kg of manganese dioxide, wherein the nickel content is 0.02%, and the cobalt content is 0.03%.
  • the dry weight of graphite slag is about 280 kg, the nickel content is 0.01%, the cobalt content is 0.02%, and the manganese content is 2.72%.
  • Step (6) obtains a total of 2300 kg of nickel-cobalt sulfate crystals, with a nickel content of 15.0%, a cobalt content of 3.54%, and 50 kg of manganese sulfate crystals with a manganese content of 31.7%.
  • the reaction mechanism is as follows:
  • Figure 1 is a process flow diagram of Examples 1 and 2 (the black box represents the process of processing, and the white box represents the obtained substance or added substance, such as battery pretreatment to obtain battery powder).
  • the method for the selective recovery of valuable metals in the waste lithium battery of this comparative example comprises the following steps:
  • the manganese dioxide slag in the step (1) is separated and dried to obtain a dry weight of about 150 kg of manganese dioxide, wherein the nickel content is 0.02%, and the cobalt content is 0.03%.
  • the dry weight of graphite slag is about 280 kg, the nickel content is 0.01%, the cobalt content is 0.02%, and the manganese content is 2.72%.
  • Step (6) obtains a total of 2300 kg of nickel-cobalt sulfate crystals, with a nickel content of 15.0%, a cobalt content of 3.54%, and 50 kg of manganese sulfate crystals with a manganese content of 31.7%.
  • Example 1 0.01 0.08 32.3 50 88.4
  • Example 2 0.01 0.08 25.5 60 92.8 Comparative example 1 0.2 0.3 0.4 80 0.01
  • the present invention adopts the process of preferentially extracting lithium by water leaching, and extracts lithium preferentially before leaching, which effectively simplifies the technological process and reduces metal loss.
  • Table 3 Element content table of iron-aluminum slag
  • Example 1 0.02 0.03 0.04 30 5.0 0.01
  • Example 2 0.02 0.03 0.04 30 5 0.01
  • Comparative example 1 0.02 0.03 0.04 15 7.0 0.01
  • Example 1-2 It can be seen from Table 3 that the iron and aluminum content of Example 1-2 is much higher than that of the filter residue with sodium sulfite added in Comparative Example 1, which is due to the introduction of a large amount of iron during the reduction process.
  • Example 1 31 39 0.2 2 3 1
  • Example 2 58 36 0.2 2 3 1
  • Table 5 Composition table of manganese sulfate content
  • Example 1 0.02 0.02 32.1 0.01 - -
  • Example 2 0.02 0.02 32.1 0.01 - - Comparative example 1 none none none none none none no such product
  • the invention adopts the process of preferentially extracting lithium by water leaching, and extracts lithium preferentially before leaching, which can improve the recovery rate of lithium, and then uses the process of non-leaching of manganese to further improve the recovery rate of nickel, cobalt and manganese.
  • Process/Yield Li (%) Process/Yield Ni+Co+Mn Lithium extraction by water leaching 95.35 Single Manganese Extraction Flux 12.6 conventional process 94.20 Total extraction throughput 350 Lithium yield 1.1% Reduced extraction throughput 96.4%

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Abstract

本发明属于锂离子电池回收领域，公开了一种选择性回收废旧锂电池中有价金属的方法，该方法包括以下步骤：向废旧锂电池中加入含硫化合物进行焙烧，水浸，得到碳酸锂溶液和滤渣；向滤渣中加入硫酸、含铁化合物进行浸出，固液分离，取固相得到二氧化锰和石墨渣；取固液分离的液相进行萃取，反萃，得到硫酸镍钴溶液和硫酸锰溶液。本发明的方法采用焙烧水浸法从废旧三元正极材料中选择性提锂，在浸出段基于二价锰可以还原镍钴的高氧化物的原理，从而实现选择性低锰浸出。

Description

一种选择性回收废旧锂电池中有价金属的方法 技术领域
本发明属于锂离子电池回收领域，具体涉及一种选择性回收废旧锂电池中有价金属的方法。
背景技术
锂电池回收近几年在中国取得较快的发展，废旧三元锂电池经过单体拆解、破碎、浸出、除铜、除铁铝、除钙镁、萃取以及共沉淀后制备三元前驱体和锂盐，取得了较好的经济效益，并形成了较大的规模。
目前普遍采用硫酸体系、亚硫酸钠、双氧水、硫代硫酸钠的一种或多种混合使用作为还原剂使原料中的有价金属全部转入硫酸体系中，镍钴锰的浸出率能达到99％以上，这种无选择性浸出也将大量杂质也带入到体系中大大增加了后续除杂处理的困难。
在三元电池的回收中，主要回收的有价金属为镍钴锂，目前常见湿法工艺在使用萃取剂分离金属镍钴和锰的工艺中，锰的浸出增加了萃取的液碱和硫酸消耗，增加了萃取通量，据统计减少一次锰的萃取，每一吨锰节约成本约为1万元。
因此，亟需研究出一种锰不浸出的工艺来解决现有工艺问题，从而实现选择性低锰浸出，同时本还原剂使用条件温和，易于运输保存，转化率高的选择性低锰浸出的工艺技术。
发明内容
本发明的目的在于至少解决上述现有技术中存在的技术问题之一。为此，本发明提供一种选择性回收废旧锂电池中有价金属的方法，该方法可将三元电池的锰金属先选择性少量浸出，同时不引入浸出工艺中利用率较低的双氧水、亚硫酸钠等还原剂，解决了低酸浸出中还原剂利用率低，存储运输麻烦、产泡等工艺问题，同时由于含铁化合物的引入，使得电池粉中杂质铝优先与铁离子反应，抑制铝与酸反应，避免了反应产氢问题，极大保证了生产的安全性。
为实现上述目的，本发明采用以下技术方案：
一种选择性回收废旧锂电池中有价金属的方法，包括以下步骤：
(1)向废旧锂电池中加入含硫化合物进行焙烧，水浸，得到碳酸锂溶液和滤渣；
(2)向所述滤渣中加入硫酸、含铁化合物进行浸出，固液分离，取固相得到二氧化锰和石墨渣；
(3)取所述固液分离的液相进行萃取，反萃，得到硫酸镍钴溶液和硫酸锰溶液；所述含硫化合物为硫酸盐或硫化盐中的一种或两种。
优选地，步骤(1)中，所述焙烧的温度为350-600℃。
优选地，所述硫酸盐为硫酸铵或硫酸钠中的一种或两种；所述硫化盐为硫化钠或硫氢化铵溶液中的一种或两种。
优选地，步骤(1)中，所述水浸的温度为50-90℃，水浸的液固比为(8-12)：1g/ml。
优选地，步骤(1)中，所述滤渣为镍钴锰的高价氧化物。
优选地，步骤(2)中，所述硫酸的pH为1-2。
优选地，步骤(2)中，所述浸出的温度为80℃-110℃。
优选地，步骤(2)中，所述含铁化合物为铁的二价化合物或铁的三价化合物中的至少一种。
进一步优选地，所述铁的二价化合物为硫酸亚铁、氯化亚铁中的一种；所述铁的三价化合物为硫酸铁、氯化铁中的一种。
优选地，步骤(2)中，所述铁的二价或三价化合物的浓度为10-20g/l。
优选地，步骤(2)中，所述浸出过程中滤渣和含铁化合物的质量比为10：(0.5-2)。
优选地，步骤(2)中，所述浸出的pH为0.5-2，浸出的时间为8-20小时。
优选地，步骤(3)中，所述萃取前还包括向步骤(2)固液分离后的液相中加入铁粉进行还原反应，固液分离，取液相加入步骤(1)中所述滤渣进行反应，固液分离，取液相加入氟化钠、钙盐反应，固液分离，取液相加入硫酸铝和钙盐反应，即得硫酸镍钴锰溶液。
进一步优选地，所述钙盐为硫酸钙或碳酸钙中的一种或两种。
进一步优选地，取液相加入步骤(1)中所述滤渣进行反应后，还包括调pH至酸性。
更优选地，所述调pH至酸性是将pH调至3.5-4.5。
优选地，步骤(3)中，所述萃取使用的试剂为P204或P507的至少一种。
步骤(2)反应的机理如下：
2Ni XCo YMn (1-x-y)O 2+4H 2SO 4+2FeSO 4＝Fe 2(SO 4) 3+2Ni XCo YMn (1-X-Y)SO 4+H 2O 式(Ⅰ)；
(x+y-0.5)MnSO 4+Ni xCo yMn (1-x-y)O 2+H 2SO 4＝0.5MnO 2+xNiSO 4+yCoSO 4+H 2O 式(Ⅱ)；
2Al+2Cu+5Fe 2(SO 4) 3＝10FeSO 4+2CuSO 4+Al 2(SO 4) 3   式(Ⅲ)；
当加入铁的化合物作为还原剂时，机理如式(Ⅰ)，反应进行到一段时间后，控制反应条件，二价锰转换成高加锰，机理如式(Ⅱ)，反应生成的三价铁或直接引入的三价铁与电池粉中少量铝、铜发生反应，机理如式(Ⅲ)，由于高价镍钴氧化性远大于二氧化锰，本反 应pH环境下所形成的二氧化锰后续基本不会被溶解。
步骤(3)反应的机理如下：
萃取是利用化合物在两种互不相溶(或微溶)的溶剂中溶解度或分配系数的不同，使化合物从一种溶剂内转移到另外一种溶剂中。锰离子与萃取剂发生反应，生成不溶于水相而易溶于有机相的萃合物，从而使得锰从水相中转入有机相中。然后采用硫酸与有机相混合，使萃取剂质子化而使萃合物解体，锰离子从有机相中回到水相，实现反萃。
反应式：2MeLn+nH 2SO 4＝Me 2(SO 4)n+2n(HL)。
本发明的有益效果：
本发明的方法通过首先选择性提锂，使得后续可以单萃锰，在浸出段引入一种铁的化合物或者混合物做还原剂，安全、高效的浸出钴酸锂、以及三元电池粉中的镍钴金属元素，同时锰不浸出，有效的分离了锰金属元素，后段再选择性萃取锰，免去了萃取段镍钴通量，减少了萃取段锰通量，做到了废旧锂电池的正极材料金属元素选择性回收，并且提供了一种安全、低成本和无原料运输保存风险、反应过程温和的镍钴金属回收方法。
附图说明
图1为本发明实施例1和实施例2的工艺流程示意图；
图2为不同pH下P507萃取金属顺序；
图3为不同pH下P204萃取金属顺序。
具体实施方式
为了对本发明进行深入的理解，下面结合实例对本发明优选实验方案进行描述，以进一步的说明本发明的特点和优点，任何不偏离本发明主旨的变化或者改变能够为本领域的技术人员理解，本发明的保护范围由所属权利要求范围确定。
实施例1
本实施例的选择性回收废旧锂电池中有价金属的方法，包括以下步骤：
(1)向废旧锂电池加入硫酸铵混合后，在500℃下进行焙烧，得到电池正极材料粉，再在温度为50℃下进行水浸浸出(水浸的固液比为10：1g/ml)，得到浸出液和滤渣；
(2)取上述滤渣粉1吨，镍含量为14.8％，钴含量为19.9％，锰含量为19.3％，制浆，加入硫酸亚铁至20g/l，定容到体积为5m 3加入质量分数为98％硫酸，调节pH至0.5，加热到70℃，反应12h，过滤，得到滤液和滤渣(二氧化锰渣和石墨渣)；
(3)将80kg铁粉加入步骤(2)中的滤液中进行还原，得到海绵铜和除铜后液；
(4)将除铜后液加热到80℃，加入100千克步骤(2)焙烧处理后的滤渣(镍含量为35.2％、 钴含量为8.32％、锰含量为8.3％)混合，反应，调pH至3.5-4.5，过滤，得到铁铝渣和滤液；
(5)向步骤(4)的滤液中加入200kg氟化钠进行除镁，加入850kg硫酸钙进行除氟，再加入850kg硫化铝和碳酸钙进行沉淀除氟除铁铝，最后加入P2O4进行萃取除钙，得到钙镁渣、含氟渣(氟化钙)和滤液；
(6)向步骤(5)的滤液中加入P507进行萃取，得到硫酸镍钴溶液和硫酸锰液，硫酸镍钴溶液蒸发重结晶得到合格硫酸镍钴二元晶体，萃锰液经处理得到电池级硫酸锰晶体。
将步骤(1)中的二氧化锰渣，分离、烘干可得二氧化锰干重约为250千克，其中镍含量为0.02％，钴含量为0.03％。石墨渣干重约为280千克，中镍含量为0.01％，钴含量为0.02％，锰含量为4.72％。
步骤(6)得到硫酸镍钴晶体共1700千克，镍含量为8.3％、钴含量为11.3％，硫酸锰晶体100千克锰含量为31.64％。
步骤(2)反应的机理如下：
2Ni XCo YMn (1-x-y)O 2+4H 2SO 4+2FeSO 4＝Fe 2(SO 4) 3+2Ni XCo YMn (1-X-Y)SO 4+H 2O 式(Ⅰ)；
(x+y-0.5)MnSO 4+Ni xCo yMn (1-x-y)O 2+H 2SO 4＝0.5MnO 2+xNiSO 4+yCoSO 4+H 2O 式(Ⅱ)；
2Al+2Cu+5Fe 2(SO 4) 3＝10FeSO 4+2CuSO 4+Al 2(SO 4) 3    式(Ⅲ)。
实施例2
本实施例的选择性回收废旧锂电池中有价金属的方法，包括以下步骤：
(1)向废旧锂电池加入硫酸铵混合后，在500℃下进行焙烧，得到电池正极材料粉，再在温度为50℃下进行水浸浸出(水浸的固液比为10：1g/ml)，得到浸出液和滤渣；
(2)取上述滤渣粉1吨，其中锂含量为3.8％，镍含量为28.8％，钴含量为17.9％，锰含量为11.3％，制浆，加入硫酸亚铁至10g/l，硫酸铁至10g/l，定容到体积为5m 3加入质量分数为98％的硫酸，调节pH至0.5，加热到70℃，反应12h，过滤，得到滤液和滤渣(二氧化锰渣和石墨渣)；
(3)将80Kg铁粉加入步骤(2)的滤液中混合，进行还原反应，得到海绵铜和除铜后液；
(4)将除铜后液加热到80℃，加入100千克步骤(2)焙烧处理后的滤渣(镍含量为28.8％、钴含量为17.9％、锰含量为11.3％)混合，反应，调pH至3.5-4.5，过滤，得到铁铝渣和滤液；
(5)向步骤(4)的滤液中加入200kg氟化钠进行除镁，加入800Kg硫酸钙进行除氟，再加入1000Kg硫化铝和碳酸钙进行沉淀除氟除铁铝，最后加入P2O4进行萃取除钙，得到钙镁渣、含氟渣(氟化钙)和滤液；
(6)向步骤(5)的滤液中加入P507进行萃取，得到硫酸镍钴溶液和硫酸锰液，硫酸镍钴溶液蒸发重结晶得到合格硫酸镍钴二元晶体，萃锰液经处理得到电池级硫酸锰晶体。
将步骤(1)中的二氧化锰渣，分离、烘干可得二氧化锰干重约为150千克，其中镍含量为0.02％，钴含量为0.03％。石墨渣干重约为280千克，中镍含量为0.01％，钴含量为0.02％，锰含量为2.72％。
步骤(6)得到硫酸镍钴晶体共2300千克，镍含量为15.0％、钴含量为3.54％，硫酸锰晶体50千克锰含量为31.7％。
反应机理如下：
2Ni XCo YMn (1-x-y)O 2+4H 2SO 4+2FeSO 4＝Fe 2(SO 4) 3+2Ni XCo YMn (1-X-Y)SO 4+H 2O 式(Ⅰ)；
(x+y-0.5)MnSO 4+Ni xCo yMn (1-x-y)O 2+H 2SO 4＝0.5MnO 2+xNiSO 4+yCoSO 4+H 2O 式(Ⅱ)；
2Al+2Cu+5Fe 2(SO 4) 3＝10FeSO 4+2CuSO 4+Al 2(SO 4) 3    式(Ⅲ)。
图1为实施例1和2的工艺流程图(黑色框中表示进行处理的工序，白色框中表示的得到物质或加入的物质，比如将电池预处理得到电池粉)。
对比例1
本对比例的选择性回收废旧锂电池中有价金属的方法，包括以下步骤：
(1)将废旧锂电池在500℃下进行焙烧，得到电池正极材料粉；
(2)取上述正极材料粉1吨，其中锂含量为4.2％，镍含量为14.8％，钴含量为19.9％，锰含量为19.3％，制浆，加入双氧水和亚硫酸钠，定容到体积为5m 3加入质量分数为98％硫酸，调节pH至1，加热到80℃，反应12h，过滤得到石墨渣和滤液；
(3)将80kg铁粉加入滤液中进行还原反应，得到海绵铜和除铜后液；
(4)将双氧水加入到滤液中，调节pH，过滤，得到铁铝渣和滤液；
(5)取滤液加入P5O7进行萃取，得到硫酸镍钴溶液和硫酸锰液；
(6)将硫酸镍钴溶液加入液碱沉镍钴，滤液除杂后碳酸钠沉锂，硫酸锰液经处理得到电池级硫酸锰晶体。
将步骤(1)中的二氧化锰渣，分离、烘干可得二氧化锰干重约为150千克，其中镍含量为0.02％，钴含量为0.03％。石墨渣干重约为280千克，中镍含量为0.01％，钴含量为0.02％，锰含量为2.72％。
步骤(6)得到硫酸镍钴晶体共2300千克，镍含量为15.0％、钴含量为3.54％，硫酸锰晶体50千克锰含量为31.7％。
检测实施例1-2和对比例1中石墨渣中元素成分，结果如表1所示：
表1
元素 Li(％) Ni+Co(％) Mn(％) C(％) 锰收率(％)
实施例1 0.01 0.08 32.3 50 88.4
实施例2 0.01 0.08 25.5 60 92.8
对比例1 0.2 0.3 0.4 80 0.01
从表1我们可以知道，采用本发明的所使用的锰不浸出工艺时，88.4％以上的锰随着石墨渣已经分离出来，有效地节省了后续工艺辅料投入及设备损耗。同时本发明的方法由于首先提锂，也减少了锂进入石墨渣中带来的损耗，有效提高了金属回收率。
检测实施例1-2和对比例1中步骤(2)的浸出液元素成分，结果如表2所示：
表2
元素 Li(g/L) Ni+Co(g/L) Mn(g/L) Fe2+Fe3(g/L)
实施例1 0.02 69.4 4.6 20
实施例2 0.02 69.4 3.7 22
对比例1 8.4 93.4 38.6 2.5
本发明采用优先水浸提锂工艺，于浸出前优先提锂，有效精简了工艺流程，减少金属流失。
检测实施例1-2和对比例1中浸出铁铝渣元素成分，结果如表3所示：
表3：铁铝渣元素含量表
元素 Ni(％) Co(％) Mn(％) Fe(％) Al(％) Cu(％)
实施例1 0.02 0.03 0.04 30 5.0 0.01
实施例2 0.02 0.03 0.04 30 5 0.01
对比例1 0.02 0.03 0.04 15 7.0 0.01
从表3可得，实施例1-2的铁铝含量相对于对比例1的加入亚硫酸钠的滤渣的高出很多，这是由于在还原过程中引入了大量的铁元素所致。
检测实施例1-2和对比例1中硫酸镍钴溶液或硫酸锰溶液成分，结果如表4和表5所示：
表4：硫酸镍钴溶液元素成分表
元素 Ni(g/L) Co(g/L) Mn(g/L) Fe(mg/L) Al(mg/L) Cu(mg/L)
实施例1 31 39 0.2 2 3 1
实施例2 58 36 0.2 2 3 1
对比例1 31 39 38 2 3 1
表5：硫酸锰含量成分表
元素 Ni(％) Co(％) Mn(％) Fe(％) Al(％) Cu(％)
实施例1 0.02 0.02 32.1 0.01 - -
实施例2 0.02 0.02 32.1 0.01 - -
对比例1 无 无 无 无 无 无此产品
实施例1-2和对比例1中各元素的回收率，结果如表6所示：
表6
元素 Ni Co Mn Li Fe Cu
实施例1 99.49％ 99.2％ 98.2％ 95.35％ 99.8％ 99.85％
实施例2 99.49％ 99.2％ 98.2％ 95.85％ 99.8％ 99.85％
对比例1 97.50％ 96.0％ 95.2％ 94.2％ 99.2％ 99.3％
本发明采用优先水浸提锂工艺，于浸出前优先提锂，可以提高锂的回收率，再使用锰不浸出工艺，进一步提高镍钴锰的回收率。
实施例1-2和对比例1中各元素的成本分析，结果如表7所示：
表7
工艺/收率 Li(％) 工艺/收率 Ni+Co+Mn
水浸提锂 95.35 单锰萃取通量 12.6
常规工艺 94.20 全萃萃取通量 350
锂收率 1.1％ 减少萃取通量 96.4％
从表7可知，锂的回收率提高了1.1％，同时减少工艺夹带，节约了大量能耗，提高了产能；选择性浸出的工艺实施，88％以上的锰被选择性优先分离，以常见的523系列为例，每吨电池粉含镍钴锰金属350Kg。单萃锰工艺，萃取通量仅为12.6，按每吨电池萃取成本3000元计算，节省至少2800元/吨，尤其对于后续的高镍料的回收，优势更加明显。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、简化均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种选择性回收废旧锂电池中有价金属的方法，其特征在于，包括以下步骤：
    (1)向废旧锂电池中加入含硫化合物进行焙烧，水浸，得到碳酸锂溶液和滤渣；
    (2)向所述滤渣中加入硫酸、含铁化合物进行浸出，固液分离，取固相得到二氧化锰和石墨渣；
    (3)取所述固液分离的液相进行萃取，反萃，得到硫酸镍钴溶液和硫酸锰溶液；所述含硫化合物为硫酸盐或硫化盐中的一种或两种。
  2. 根据权利要求1所述的方法，其特征在于，所述硫酸盐为硫酸铵或硫酸钠中的一种或两种；所述硫化盐为硫化钠或硫氢化铵溶液中的一种或两种。
  3. 根据权利要求1所述的方法，其特征在于，步骤(1)中，所述水浸的温度为50-90℃，水浸的液固比为(8-12):1。
  4. 根据权利要求1所述的方法，其特征在于，步骤(2)中，所述含铁化合物为铁的二价化合物或铁的三价化合物中的至少一种。
  5. 根据权利要求4所述的方法，其特征在于，所述铁的二价化合物为硫酸亚铁、氯化亚铁中的一种；所述铁的三价化合物为硫酸铁、氯化铁中的一种。
  6. 根据权利要求1所述的方法，其特征在于，步骤(2)中，所述浸出的pH为0.5-2，浸出的时间为10-20小时，浸出的温度为60-90℃；所述浸出过程中滤渣和含铁化合物的质量比为10：(0.5-2)。
  7. 根据权利要求1所述的方法，其特征在于，步骤(3)中，所述萃取前还包括向步骤(2)固液分离后的液相中加入铁粉进行还原反应，固液分离，取液相加入步骤(1)中所述滤渣进行反应，固液分离，取液相加入氟化钠、钙盐反应，固液分离，取液相加入硫酸铝和钙盐反应，即得硫酸镍钴锰溶液。
  8. 根据权利要求7所述的方法，其特征在于，所述钙盐为硫酸钙或碳酸钙中的一种或两种。
  9. 根据权利要求7所述的方法，其特征在于，所述取液相加入步骤(1)中所述滤渣后，还包括调pH至酸性。
  10. 根据权利要求1所述的方法，其特征在于，步骤(3)中，所述萃取使用的试剂为P204或P507中的至少一种。
PCT/CN2022/090064 2021-09-27 2022-04-28 一种选择性回收废旧锂电池中有价金属的方法 Ceased WO2023045331A1 (zh)

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