WO2022252602A1 - Method for safely leaching waste battery and application - Google Patents

Method for safely leaching waste battery and application Download PDF

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Publication number
WO2022252602A1
WO2022252602A1 PCT/CN2021/142932 CN2021142932W WO2022252602A1 WO 2022252602 A1 WO2022252602 A1 WO 2022252602A1 CN 2021142932 W CN2021142932 W CN 2021142932W WO 2022252602 A1 WO2022252602 A1 WO 2022252602A1
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Prior art keywords
leaching
filter residue
waste
agent
roasting
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PCT/CN2021/142932
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French (fr)
Chinese (zh)
Inventor
余海军
钟应声
谢英豪
李长东
张学梅
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
湖南邦普汽车循环有限公司
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Publication of WO2022252602A1 publication Critical patent/WO2022252602A1/en

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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
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • 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
    • 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
    • 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
    • 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
    • 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 technical field of recycling waste batteries, and in particular relates to a method and application for safe leaching of waste batteries.
  • Waste lithium-ion batteries are composed of positive electrodes, negative electrodes, electrolytes, and separators.
  • the negative electrode is composed of graphite, binder, conductive agent and current collector
  • the positive electrode is made of active material powder, binder and conductive agent coated on the current collector.
  • Metals with potential recycling value include Ni, Mn, Co, Li, Al, etc.
  • the current recycling of waste lithium-ion batteries mainly includes a series of operations such as coarse crushing, physical screening, and fine crushing of waste lithium-ion batteries to obtain the particulate matter of waste lithium battery powder, but the recycled waste lithium battery powder contains a low amount of aluminum.
  • Slag particle impurities whose particle size is similar to that of waste lithium-ion battery powder, are mixed with active material powder, binder and other particles, and can react with acid and alkali, so the treatment of aluminum slag impurity particles is difficult. Due to the generation of flammable and explosive hydrogen during the recovery process of aluminum and subsequent valuable metals, it is dangerous.
  • the current use of hydrometallurgical recycling to prepare positive electrode materials mostly faces the problem of excessive aluminum content.
  • the treatment methods mainly focus on the front-end treatment of the battery, using acid leaching, high-temperature heat treatment or alkali leaching, but these three methods have their own advantages.
  • the disadvantages of each are high cost of acid leaching and the generation of unsafe hydrogen, high-temperature treatment consumes a lot of energy and cannot remove aluminum, and the aluminum content in the positive electrode material prepared after alkaline leaching is still higher than the battery-grade standard. Therefore, it is necessary to improve the removal rate of aluminum slag particles in battery powder particles and improve the safety of metal leaching processes such as Ni, Co, and Li.
  • the present invention aims to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the present invention proposes a method and application of safe leaching of waste batteries.
  • This method combines safe, efficient, and low-energy physical methods such as roasting, sorting, and flotation with chemical methods such as dilute alkali dissolution. to remove aluminum from waste lithium batteries.
  • the present invention adopts the following technical solutions:
  • a method for leaching waste batteries comprising the following steps:
  • the calcination temperature is 240°C-580°C
  • the calcination time is 1.5-5h
  • the calcination heating rate is 5-30°C/min.
  • step (1) the gas generated by the roasting is collected with lye.
  • the lye is at least one of sodium hydroxide, magnesium hydroxide, potassium hydroxide, barium hydroxide, zinc hydroxide or calcium hydroxide.
  • the concentration of the lye is 0.01-0.15 mol/L.
  • the solid-to-liquid ratio of the battery powder and water is 1:(1.5-4) g/ml.
  • the flotation agent is one of oxidized paraffin soap, sodium oleate or laurylamine.
  • the density of the flotation agent in the flotation is 1.80-2.65 g/cm 3 .
  • the lye is at least one of sodium hydroxide, magnesium hydroxide, potassium hydroxide or calcium hydroxide.
  • the concentration of the lye is 0.10-0.80 mol/L.
  • the solid-to-liquid ratio of the floating material and the lye is 5g/L-15g/L.
  • the density of aluminum slag is 2.70g/cm 3
  • the density of waste lithium battery powder is for example: the bulk density of lithium iron phosphate is 1.523g/cm 3
  • the tap density is 1.2g/cm 3
  • the tap density of nickel cobalt lithium manganate is 2.0- 2.4 g/cm 3 .
  • the density difference is used for flotation, and the density of aluminum slag is higher than that of waste lithium battery powder.
  • the leaching time is 10-120 min, and the leaching temperature is 30-90°C.
  • step (3) ventilate the gas that produces in the process of described leaching, utilize hydrogen detection instrument to monitor the concentration of hydrogen at exhaust port simultaneously; Ventilation keeps hydrogen concentration lower than 0.5% VOL (air volume ratio) or 5000ppm.
  • VOL air volume ratio
  • the solid-to-liquid ratio during leaching is 2-30 g/L.
  • the leaching time is 1-6 hours, and the leaching temperature is 40-95°C.
  • the leaching agent is an organic acid.
  • the concentration of the organic acid is 0.5-5 mol/L.
  • the organic acid is tartaric acid.
  • the reducing agent is hydrogen peroxide.
  • step (4) the washed washing solution e is mixed with the filtrate d of step (3) to obtain a mixed solution, which can be used as lye in step (3) for recycling.
  • the present invention also provides the application of the above-mentioned waste battery leaching method in recycling valuable metals.
  • the leaching solution obtained by the above method of leaching waste batteries is an acid solution containing Li + , Co 2+ , Mn 2+ , and Ni 2+ , and Li, Co, Mn, and Ni can be recovered further.
  • the present invention combines safe, efficient, and low-energy physical methods such as roasting, screening, and flotation with chemical methods such as dilute alkali dissolution to remove aluminum in waste lithium batteries from the source.
  • the present invention uses roasting and screening to separate aluminum foil and battery powder first, and then uses flotation agent to sink the aluminum slag, copper and other impurities in the battery powder to the bottom, further removes aluminum, avoids a large amount of hydrogen gas generated in the subsequent leaching process, and improves the leaching process. Therefore, the residual aluminum slag can be removed, which is also to avoid the generation of hydrogen gas during the leaching of the positive active material powder and improve the safety of leaching.
  • the positive electrode material produced by leaching with leaching solution meets the battery-grade standard, and there will be no safety problems during storage, which is especially suitable for industrial production.
  • the present invention is roasting the waste lithium battery powder
  • the bonding performance of the binder polyvinylidene fluoride, polytetrafluoroethylene
  • the waste lithium battery powder becomes brittle.
  • the fluid falls off, and the binder and conductive agent graphite gradually decompose and burn at high temperature.
  • the roasting process changes the molecular structure of the positive electrode material, reduces the charge of transition metal ions in the positive electrode material, and creates conditions for subsequent leaching and recovery.
  • the waste lithium battery powder is mainly black, the aluminum foil is bright silver, and the copper foil is light yellow. It is very convenient to sort and remove most of the aluminum foil and copper foil by using a color sorter.
  • the present invention adopts a low solid-liquid ratio for both leaching, which can reduce the amount of acid-base consumption, further efficiently leaching aluminum and positive electrode active material powder, and at the same time mixing the filtrate b and washing liquid d to obtain a mixed solution that can be recycled, reducing Alkali dosage.
  • the leaching of the present invention adopts organic acid tartaric acid, while ensuring the leaching rate of valuable metal elements, its leaching reaction is relatively mild, avoiding the production of sulfur dioxide, Adverse effects of gases such as hydrochloric acid on the environment and equipment.
  • the boiling point of tartaric acid is about 399°C.
  • hydrochloric acid it is less volatile at the leaching reaction temperature of 30-95°C. Therefore, tartaric acid is used for leaching, and the whole leaching process is more environmentally friendly and safer.
  • Fig. 1 is a flowchart of a method for safely leaching waste batteries according to Embodiment 1 of the present invention.
  • the recovered lithium iron phosphate battery is disassembled and discharged, and after being coarsely crushed by machinery, the broken waste lithium battery is placed in a sintering kiln for roasting.
  • the roasting temperature is controlled at 350°C, and the roasting is stable for 4.8 hours.
  • the heating rate is controlled At about 15°C/min, the gas generated by roasting is collected with 0.01mol/L sodium hydroxide lye, and the waste lithium batteries after roasting are vibrated and screened, and the aluminum foil and copper foil are sorted by the color sorter, and then sorted
  • the finished waste lithium battery powder is ground by a ball mill;
  • step (3) On the basis of step (3), the filter residue a is washed 4 times with pure water, the washing liquid d is collected by filtration, and the filter residue c is separated, and the filter residue c is 1.5% hydrogen peroxide with 0.5mol/L tartaric acid and a volume ratio
  • the solid-to-liquid ratio during leaching is 5g/L
  • the temperature of the leaching reaction system is controlled at 42°C
  • Residue f, filtrate b, and washing liquid d are mixed in a volume ratio of 1:1, and the mixed solution is used for leaching in step (3).
  • Fig. 1 is the flow chart of the method for safe leaching of waste batteries according to Example 1 of the present invention. It can be seen from Fig. 1 that in the leaching of waste batteries, aluminum is mainly removed through four steps of sieving, sorting, flotation and adding lye.
  • the recovered lithium iron phosphate battery is disassembled and discharged, and after being roughly crushed mechanically, the broken waste lithium battery is placed in a sintering kiln for roasting.
  • the roasting temperature is controlled at 580°C, and the roasting is stable for 2.4 hours. During the period, the heating rate is controlled.
  • the gas generated by roasting is collected with 0.04mol/L sodium hydroxide lye, and the waste lithium batteries after roasting are vibrated and screened.
  • the color sorter sorts aluminum foil and copper foil, and then the sorting is completed.
  • the waste lithium battery powder is ground by a ball mill;
  • step (3) On the basis of step (3), the filter residue a is washed with pure water for 2 times, the washing liquid d is collected by filtration, and the filter residue c is separated, and the filter residue c is 3.4% hydrogen peroxide with 2.5mol/L tartaric acid and a volume ratio Carry out leaching, the solid-to-liquid ratio during leaching is 5g/L, the temperature of the leaching reaction system is controlled at 58°C, and after leaching is completed, filter to obtain an acid solution containing Li + , Co 2+ , Mn 2+ , Ni 2+ , residue f, and filtrate b. Washing solution d is mixed according to the volume ratio of 1:1.4, and the mixed solution is used for leaching in step (3).
  • the recovered lithium iron phosphate battery is disassembled and discharged, and after being coarsely crushed by machinery, the broken waste lithium battery is placed in a sintering kiln for roasting.
  • the roasting temperature is controlled at 420°C, and the roasting is stable for 3.5 hours. During the period, the heating rate is controlled.
  • the gas generated by roasting is collected with 0.09mol/L sodium hydroxide lye, and the waste lithium batteries after roasting are vibrated and screened, and the color sorter sorts aluminum foil and copper foil, and then the sorting is completed
  • the waste lithium battery powder is ground by a ball mill;
  • step (3) On the basis of step (3), the filter residue a is washed 3 times with pure water, the washing liquid d is collected by filtration, and the filter residue c is separated, and the filter residue c is 5.5% hydrogen peroxide with tartaric acid of 3.8mol/L and a volume ratio Carry out leaching, the solid-to-liquid ratio during leaching is 12g/L, the temperature of the leaching reaction system is controlled at 61°C, and after leaching is completed, the acid solution containing Li + , Co 2+ , Mn 2+ , Ni 2+ , residue f, filtrate b. Washing solution d is mixed according to the volume ratio of 1:1.8, and the mixed solution is used for leaching in step (3).
  • step (3) On the basis of step (3), the filter residue a is washed 3 times with pure water, the washing liquid d is collected by filtration, and the filter residue c is separated, and the filter residue c is 8.0% hydrogen peroxide with tartaric acid of 4.78mol/L and a volume ratio of 8.0%.
  • the solid-to-liquid ratio during leaching is 15g/L
  • the temperature of the leaching reaction system is controlled at 94°C
  • filter to obtain an acid solution containing Li + , Co 2+ , Mn 2+ , Ni 2+ , residue f, filtrate b.
  • Washing solution d is mixed according to the volume ratio of 1:2.3, and the mixed solution is used for leaching in step (3).
  • a method for leaching waste batteries comprising the following specific steps:
  • Example 1 The difference from Example 1 is that no flotation is carried out in step (2).
  • a method for leaching waste batteries comprising the following specific steps:
  • Example 1 The difference from Example 1 is that no sodium hydroxide is added in step (3) for leaching.
  • Example 1 adopt sulfuric acid leaching leaching in the step (4), other reaction conditions are all the same. Including: 1.3mol/L sulfuric acid and 1.5% hydrogen peroxide for leaching, the solid-liquid ratio during leaching is 5g/L, and the temperature of the leaching reaction system is controlled at 60°C.
  • step (2) As known from Table 1, compared with the quality of aluminum in the waste lithium battery powder in step (1) of Examples 1, 2, 3, and 4, the quality of aluminum in the filter residue c in step (3) decreased by 0.53%, 0.16%, and 0.60%, 0.26%; Comparative Example 1 and Comparative Example 1, step (2) has reduced the 0.23% hydrogen concentration through flotation; Comparative Example 1 and Comparative Example 2, utilize alkali leaching aluminum in the step (3), reduce The mass of aluminum in filter residue c was 0.11%; comparative example 3 was leached by sulfuric acid, and the reaction was violent, while the leaching reactions in examples 1, 2, 3, 4 and ratios 1 and 2 were mild. Therefore, it can be concluded that steps (2) and (3) can effectively reduce the aluminum content in the waste lithium battery powder, reduce the generation of hydrogen, and improve the safety during leaching.
  • the leaching of organic acid tartaric acid Compared with the leaching of inorganic acids such as sulfuric acid, the leaching of organic acid tartaric acid has a relatively mild leaching reaction while ensuring the leaching rate of valuable metal elements, and avoids the adverse effects of the generated gas on the environment and equipment.

Abstract

The present invention relates to the technical field of waste battery recovery. Disclosed are a method for safely leaching a waste battery and an application. The method comprises the following steps: discharging, roasting, and screening a waste lithium battery to obtain copper aluminum foil and battery powder; adding the battery powder to water, and then adding a floatation agent for performing floatation to obtain a floating material and a sediment; using lye to leach the floating material and filtering to obtain a filtrate b and a filter residue a; and washing the filter residue a, filtering to obtain a filter residue c, and adding a leaching agent and a reducing agent for leaching to obtain a leaching liquid. In the present invention, safe, efficient, and low-energy-consumption physical methods such as roasting, screening, and flotation are combined with chemical methods such as dilute alkali dissolution, and aluminum in the waste lithium battery can be removed from the source.

Description

一种废旧电池安全浸出的方法和应用A method and application of safe leaching of waste batteries 技术领域technical field
本发明属于废旧电池回收技术领域，具体涉及一种废旧电池安全浸出的方法和应用。The invention belongs to the technical field of recycling waste batteries, and in particular relates to a method and application for safe leaching of waste batteries.
背景技术Background technique
废锂离子电池由正极、负极、电解质和隔膜等组成。其中，负极由石墨、黏结剂、导电剂和集流体组成，正极由活性物质粉末、黏结剂以及导电剂涂覆在集流体上制成。其中具有潜在回收利用价值的金属有Ni、Mn、Co、Li、Al等。Waste lithium-ion batteries are composed of positive electrodes, negative electrodes, electrolytes, and separators. Among them, the negative electrode is composed of graphite, binder, conductive agent and current collector, and the positive electrode is made of active material powder, binder and conductive agent coated on the current collector. Metals with potential recycling value include Ni, Mn, Co, Li, Al, etc.
当前废锂离子电池回收处理主要包括对废锂离子电池进行粗粉碎、物理筛分、精细粉碎等一系列操作后得到废弃锂电池粉末的颗粒物质，但是回收的废锂电池粉含有低量的铝渣颗粒杂质，杂质的粒度大小与废锂离子电池粉末相近，与活性物质粉末、粘结剂等颗粒混杂一起，能与酸碱反应，因此铝渣杂质颗粒处理难度较大。由于铝与后续有价金属的回收过程中有易燃、易爆氢气的产生，具有危险性。The current recycling of waste lithium-ion batteries mainly includes a series of operations such as coarse crushing, physical screening, and fine crushing of waste lithium-ion batteries to obtain the particulate matter of waste lithium battery powder, but the recycled waste lithium battery powder contains a low amount of aluminum. Slag particle impurities, whose particle size is similar to that of waste lithium-ion battery powder, are mixed with active material powder, binder and other particles, and can react with acid and alkali, so the treatment of aluminum slag impurity particles is difficult. Due to the generation of flammable and explosive hydrogen during the recovery process of aluminum and subsequent valuable metals, it is dangerous.
而且目前使用湿法冶金回收制备正极材料，大多面临着铝含量超标的问题，其处理方法主要集中在电池的前段处理，采用酸浸出、高温热处理或碱浸，但这三种方法却又有其各自的缺点，酸浸出成本高还会产生氢气发生不安全问题，高温处理能耗高而且并不能除去铝，碱浸除铝后制备的正极材料中铝含量仍高于电池级的标准。因此需要提高电池粉颗粒中铝渣颗粒的去除率，提高Ni、Co、Li等金属浸出过程的安全性。Moreover, the current use of hydrometallurgical recycling to prepare positive electrode materials mostly faces the problem of excessive aluminum content. The treatment methods mainly focus on the front-end treatment of the battery, using acid leaching, high-temperature heat treatment or alkali leaching, but these three methods have their own advantages. The disadvantages of each are high cost of acid leaching and the generation of unsafe hydrogen, high-temperature treatment consumes a lot of energy and cannot remove aluminum, and the aluminum content in the positive electrode material prepared after alkaline leaching is still higher than the battery-grade standard. Therefore, it is necessary to improve the removal rate of aluminum slag particles in battery powder particles and improve the safety of metal leaching processes such as Ni, Co, and Li.
发明内容Contents of the invention
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种废旧电池安全浸出的方法和应用，该方法利用焙烧、分拣、浮选等安全、高效、低能耗的物理方法以及稀碱溶解等化学方法相结合，能从源头上除掉废弃锂电池中的铝。The present invention aims to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the present invention proposes a method and application of safe leaching of waste batteries. This method combines safe, efficient, and low-energy physical methods such as roasting, sorting, and flotation with chemical methods such as dilute alkali dissolution. to remove aluminum from waste lithium batteries.
为实现上述目的，本发明采用以下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种废旧电池浸出的方法，包括以下步骤：A method for leaching waste batteries, comprising the following steps:
(1)将废旧锂电池进行放电，焙烧，筛选，得到铜铝箔和电池粉；(1) Discharging, roasting and screening waste lithium batteries to obtain copper and aluminum foil and battery powder;
(2)将所述电池粉加入水中，再加入浮选剂进行浮选，得到漂浮物料和沉淀物质；(2) adding the battery powder into water, and then adding a flotation agent for flotation to obtain floating materials and sedimentary materials;
(3)将所述漂浮物料用碱液进行浸出，过滤，得到滤液b和滤渣a；(3) leaching the floating material with alkali solution, filtering to obtain filtrate b and filter residue a;
(4)将所述滤渣a进行洗涤，过滤取滤渣c，加入浸出剂和还原剂进行浸出，得到含Li +、Co 2+、Mn 2+、Ni 2+的酸溶液。 (4) Wash the filter residue a, filter the filter residue c, add a leaching agent and a reducing agent for leaching, and obtain an acid solution containing Li + , Co 2+ , Mn 2+ , and Ni 2+ .
优选地，步骤(1)中，所述焙烧的温度为240℃～580℃，焙烧的时间为1.5～5h，焙烧的升温速度为5～30℃/min。Preferably, in step (1), the calcination temperature is 240°C-580°C, the calcination time is 1.5-5h, and the calcination heating rate is 5-30°C/min.
优选地，步骤(1)中，所述焙烧产生的气体用碱液收集。Preferably, in step (1), the gas generated by the roasting is collected with lye.
进一步优选地，所述碱液为氢氧化钠、氢氧化镁、氢氧化钾、氢氧化钡、氢氧化锌或氢氧化钙中的至少一种。Further preferably, the lye is at least one of sodium hydroxide, magnesium hydroxide, potassium hydroxide, barium hydroxide, zinc hydroxide or calcium hydroxide.
更优选地，所述碱液的浓度为0.01～0.15mol/L。More preferably, the concentration of the lye is 0.01-0.15 mol/L.
优选地，步骤(2)中，所述电池粉和水的固液比为1:(1.5～4)g/ml。Preferably, in step (2), the solid-to-liquid ratio of the battery powder and water is 1:(1.5-4) g/ml.
优选地，步骤(2)中，所述浮选剂为氧化石蜡皂、油酸钠或十二胺中的一种。Preferably, in step (2), the flotation agent is one of oxidized paraffin soap, sodium oleate or laurylamine.
优选地，步骤(2)中，所述浮选中浮选剂的密度为1.80～2.65g/cm 3。 Preferably, in step (2), the density of the flotation agent in the flotation is 1.80-2.65 g/cm 3 .
优选地，步骤(3)中，所述碱液为氢氧化钠、氢氧化镁、氢氧化钾或氢氧化钙中至少一种。Preferably, in step (3), the lye is at least one of sodium hydroxide, magnesium hydroxide, potassium hydroxide or calcium hydroxide.
进一步优选地，所述碱液的浓度为0.10～0.80mol/L。Further preferably, the concentration of the lye is 0.10-0.80 mol/L.
优选地，步骤(3)中，所述漂浮物料和碱液的固液比为5g/L～15g/L。Preferably, in step (3), the solid-to-liquid ratio of the floating material and the lye is 5g/L-15g/L.
浮选沉铝的原理：The principle of flotation sinking aluminum:
铝渣密度在2.70g/cm 3，废弃锂电池粉的密度比如：磷酸铁锂松密度1.523g/cm 3，振实密度1.2g/cm 3，镍钴锰酸锂的振实密度在2.0-2.4g/cm 3。利用密度差进行浮选，铝渣密度大于废弃锂电池粉的密度。 The density of aluminum slag is 2.70g/cm 3 , the density of waste lithium battery powder is for example: the bulk density of lithium iron phosphate is 1.523g/cm 3 , the tap density is 1.2g/cm 3 , the tap density of nickel cobalt lithium manganate is 2.0- 2.4 g/cm 3 . The density difference is used for flotation, and the density of aluminum slag is higher than that of waste lithium battery powder.
优选地，步骤(3)中，所述浸出的时间为10～120min，浸出的温度为30～90℃。Preferably, in step (3), the leaching time is 10-120 min, and the leaching temperature is 30-90°C.
优选地，步骤(3)中，所述浸出的过程中通风排去产生的气体，同时利用氢气检测仪器监测排气口氢气的浓度；通风保持氢浓度低于0.5％VOL(空气体积比)或5000ppm。Preferably, in step (3), ventilate the gas that produces in the process of described leaching, utilize hydrogen detection instrument to monitor the concentration of hydrogen at exhaust port simultaneously; Ventilation keeps hydrogen concentration lower than 0.5% VOL (air volume ratio) or 5000ppm.
优选地，步骤(4)中，所述浸出时的固液比为2～30g/L。Preferably, in step (4), the solid-to-liquid ratio during leaching is 2-30 g/L.
优选地，步骤(4)中，所述浸出的时间为1～6h，浸出的温度为40-95℃。Preferably, in step (4), the leaching time is 1-6 hours, and the leaching temperature is 40-95°C.
优选地，步骤(4)中，所述浸出剂为有机酸。Preferably, in step (4), the leaching agent is an organic acid.
优选地，步骤(4)中，所述有机酸的浓度在0.5～5mol/L。Preferably, in step (4), the concentration of the organic acid is 0.5-5 mol/L.
优选地，步骤(4)中，所述有机酸为酒石酸。Preferably, in step (4), the organic acid is tartaric acid.
优选地，步骤(4)中，所述还原剂为过氧化氢。Preferably, in step (4), the reducing agent is hydrogen peroxide.
优选地，步骤(4)中，所述洗涤后的水洗液e和步骤(3)的滤液d进行混合，得到混合液，混合液可做为步骤(3)中的碱液，进行循环利用。Preferably, in step (4), the washed washing solution e is mixed with the filtrate d of step (3) to obtain a mixed solution, which can be used as lye in step (3) for recycling.
本发明还提供上述的废旧电池浸出的方法在回收有价金属中的应用。The present invention also provides the application of the above-mentioned waste battery leaching method in recycling valuable metals.
上述的废旧电池浸出的方法得到的浸出液为含有Li +、Co 2+、Mn 2+、Ni 2+的酸溶液，进一步可以回收Li、Co、Mn、Ni。 The leaching solution obtained by the above method of leaching waste batteries is an acid solution containing Li + , Co 2+ , Mn 2+ , and Ni 2+ , and Li, Co, Mn, and Ni can be recovered further.
相对于现有技术，本发明的有益效果如下：Compared with the prior art, the beneficial effects of the present invention are as follows:
1、本发明利用焙烧、筛选、浮选等安全、高效、低能耗的物理方法以及稀碱溶解等化学方法相结合，能从源头上除掉废弃锂电池中的铝。1. The present invention combines safe, efficient, and low-energy physical methods such as roasting, screening, and flotation with chemical methods such as dilute alkali dissolution to remove aluminum in waste lithium batteries from the source.
2、本发明先利用焙烧和筛选分离铝箔和电池粉，再利用浮选剂将电池粉中的铝渣、铜等杂质沉底，进一步除去铝，避免后续浸出过程中产生大量氢气，提高浸出过程的安全性，再用稀碱浸出，稀碱不会溶解废弃锂电池粉而溶解铝，因此能将残余的铝渣除尽，同样是为避免正极活性物质粉末浸出时产生氢气，提高浸出的安全性，采用浸出液浸出生产的正极材料符合电池级的标准，而且存放时不会有安全问题产生，尤其适用于工业化生产。2. The present invention uses roasting and screening to separate aluminum foil and battery powder first, and then uses flotation agent to sink the aluminum slag, copper and other impurities in the battery powder to the bottom, further removes aluminum, avoids a large amount of hydrogen gas generated in the subsequent leaching process, and improves the leaching process. Therefore, the residual aluminum slag can be removed, which is also to avoid the generation of hydrogen gas during the leaching of the positive active material powder and improve the safety of leaching. The positive electrode material produced by leaching with leaching solution meets the battery-grade standard, and there will be no safety problems during storage, which is especially suitable for industrial production.
3、本发明在焙烧废弃锂电池粉时，粘结剂(聚偏氟乙烯、聚四氟乙烯)粘合性能降低，废弃锂电池粉变脆，同时经过振动，废弃锂电池粉更容易从集流体上脱落，黏结剂和导电剂石墨在高温下逐渐分解燃烧，焙烧工艺改变正极材料的分子结构，降低正极材料中过渡金属离子的电荷，为后续的浸出、回收创造条件。焙烧后，废弃锂电池粉以黑色为主，铝箔为银亮色、铜箔为浅黄色，利用色选机筛选能十分便捷的分拣除去大部分铝箔、铜箔。3. When the present invention is roasting the waste lithium battery powder, the bonding performance of the binder (polyvinylidene fluoride, polytetrafluoroethylene) is reduced, and the waste lithium battery powder becomes brittle. At the same time, through vibration, the waste lithium battery powder is more easily removed from the collection. The fluid falls off, and the binder and conductive agent graphite gradually decompose and burn at high temperature. The roasting process changes the molecular structure of the positive electrode material, reduces the charge of transition metal ions in the positive electrode material, and creates conditions for subsequent leaching and recovery. After roasting, the waste lithium battery powder is mainly black, the aluminum foil is bright silver, and the copper foil is light yellow. It is very convenient to sort and remove most of the aluminum foil and copper foil by using a color sorter.
4、本发明两次浸出均采用低固液比可降低消耗酸碱的用量，进一步可高效率地浸出铝以及正极活性物质粉末，同时滤液b和水洗液d混合得到混合液可循环利用，降低碱用量。4. The present invention adopts a low solid-liquid ratio for both leaching, which can reduce the amount of acid-base consumption, further efficiently leaching aluminum and positive electrode active material powder, and at the same time mixing the filtrate b and washing liquid d to obtain a mixed solution that can be recycled, reducing Alkali dosage.
5、本发明采用有机酸酒石酸的浸出与硫酸、盐酸、磷酸等无机酸的浸出相比，在保证有价金属元素浸出率的同时，其浸出反应相对来说比较温和，避免了产生的二氧化 硫、盐酸等气体对环境、设备的不良影响。同时，酒石酸沸点约为399℃，与盐酸相比，在30～95℃的浸出反应温度下不易挥发。因此采用酒石酸进行浸出，整个浸出过程更环保、安全。5. Compared with the leaching of inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, the leaching of the present invention adopts organic acid tartaric acid, while ensuring the leaching rate of valuable metal elements, its leaching reaction is relatively mild, avoiding the production of sulfur dioxide, Adverse effects of gases such as hydrochloric acid on the environment and equipment. At the same time, the boiling point of tartaric acid is about 399°C. Compared with hydrochloric acid, it is less volatile at the leaching reaction temperature of 30-95°C. Therefore, tartaric acid is used for leaching, and the whole leaching process is more environmentally friendly and safer.
附图说明Description of drawings
图1为本发明实施例1的废旧电池安全浸出的方法的流程图。Fig. 1 is a flowchart of a method for safely leaching waste batteries according to Embodiment 1 of the present invention.
具体实施方式Detailed ways
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。The conception and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments, so as to fully understand the purpose, features and effects of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, rather than all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative efforts belong to The protection scope of the present invention.
实施例1Example 1
本实施例的废旧电池安全浸出的方法，包括以下具体步骤：The method for the safe leaching of waste batteries of the present embodiment comprises the following specific steps:
(1)回收的磷酸铁锂电池经拆解放电，经机械粗粉碎后，将破碎的废旧锂电池片置于烧结窑中焙烧，控制焙烧温度为350℃，稳定焙烧4.8h，期间升温速度控制在15℃/min左右，将焙烧产生的气体用0.01mol/L氢氧化钠碱液收集，焙烧后的废旧锂电池片进行振动分筛，色选机分拣铝箔、铜箔，再将分拣完毕的废弃锂电池粉利用磨球机研磨；(1) The recovered lithium iron phosphate battery is disassembled and discharged, and after being coarsely crushed by machinery, the broken waste lithium battery is placed in a sintering kiln for roasting. The roasting temperature is controlled at 350°C, and the roasting is stable for 4.8 hours. During the period, the heating rate is controlled At about 15°C/min, the gas generated by roasting is collected with 0.01mol/L sodium hydroxide lye, and the waste lithium batteries after roasting are vibrated and screened, and the aluminum foil and copper foil are sorted by the color sorter, and then sorted The finished waste lithium battery powder is ground by a ball mill;
(2)纯水中加入球磨后的废弃锂电池粉，废弃锂电池粉：水的固液比为1:1.5g/ml，搅拌并除去漂浮杂质，加入油酸钠，至浮选液密度约为2.06g/cm 3，回收漂浮物料； (2) Add waste lithium battery powder after ball milling into pure water, the solid-to-liquid ratio of waste lithium battery powder:water is 1:1.5g/ml, stir and remove floating impurities, add sodium oleate until the density of the flotation liquid is about 2.06g/cm 3 , recovery of floating materials;
(3)将漂浮物料用0.15mol/L氢氧化钠进行浸出，浸出时间控制在104min，浸出时的固液比为8g/L，反应体系温度在53℃左右，至不在产生气体时，迅速过滤，得到滤渣a、滤液b，通风排去产生的气体，同时利用快速测氢仪监测排气口氢气的浓度；(3) Leach the floating material with 0.15mol/L sodium hydroxide, the leaching time is controlled at 104min, the solid-liquid ratio during leaching is 8g/L, the temperature of the reaction system is around 53°C, and when no gas is generated, filter it quickly , to obtain filter residue a and filtrate b, ventilate to remove the generated gas, and use a rapid hydrogen detector to monitor the concentration of hydrogen at the exhaust port;
(4)在步骤(3)基础上将滤渣a用纯水水洗4次，过滤收集水洗液d，分离得到滤渣c，滤渣c以0.5mol/L的酒石酸、体积比为1.5％的过氧化氢进行浸出，浸出时固液比为5g/L，浸出反应体系温度控制在42℃，浸出完毕后过滤得含Li +、Co 2+、Mn 2+、Ni 2+的酸溶液(浸出液g)、残渣f，滤液b、水洗液d按体积比1:1进行混合，混合液用于步骤(3)中浸出。 (4) On the basis of step (3), the filter residue a is washed 4 times with pure water, the washing liquid d is collected by filtration, and the filter residue c is separated, and the filter residue c is 1.5% hydrogen peroxide with 0.5mol/L tartaric acid and a volume ratio Carry out leaching, the solid-to-liquid ratio during leaching is 5g/L, the temperature of the leaching reaction system is controlled at 42°C, after the leaching is completed, filter to obtain an acid solution containing Li + , Co 2+ , Mn 2+ , Ni 2+ (leach solution g), Residue f, filtrate b, and washing liquid d are mixed in a volume ratio of 1:1, and the mixed solution is used for leaching in step (3).
图1为本发明实施例1的废旧电池安全浸出的方法的流程图，从图1可知，在废旧电池浸出中，铝主要通过分筛、分拣、浮选、加碱液四个步骤除去。Fig. 1 is the flow chart of the method for safe leaching of waste batteries according to Example 1 of the present invention. It can be seen from Fig. 1 that in the leaching of waste batteries, aluminum is mainly removed through four steps of sieving, sorting, flotation and adding lye.
实施例2Example 2
本实施例的废旧电池安全浸出的方法，包括以下具体步骤：The method for the safe leaching of waste batteries of the present embodiment comprises the following specific steps:
(1)回收的磷酸铁锂电池经拆解放电，经机械粗粉碎后，将破碎的废旧锂电池片置于烧结窑中焙烧，控制焙烧温度为580℃，稳定焙烧2.4h，期间升温速度控制在23℃/min，将焙烧产生的气体用0.04mol/L氢氧化钠碱液收集，焙烧后的废旧锂电池片进行振动分筛，色选机分拣铝箔、铜箔，再将分拣完毕的废弃锂电池粉利用磨球机研磨；(1) The recovered lithium iron phosphate battery is disassembled and discharged, and after being roughly crushed mechanically, the broken waste lithium battery is placed in a sintering kiln for roasting. The roasting temperature is controlled at 580°C, and the roasting is stable for 2.4 hours. During the period, the heating rate is controlled. At 23°C/min, the gas generated by roasting is collected with 0.04mol/L sodium hydroxide lye, and the waste lithium batteries after roasting are vibrated and screened. The color sorter sorts aluminum foil and copper foil, and then the sorting is completed. The waste lithium battery powder is ground by a ball mill;
(2)纯水中加入球磨后的废弃锂电池粉，废弃锂电池粉：水的固液比为1:2.5g/ml，搅拌并除去漂浮杂质，加入油酸钠，至浮选液密度约为2.37g/cm 3，回收漂浮物料； (2) Add waste lithium battery powder after ball milling into pure water, the solid-to-liquid ratio of waste lithium battery powder:water is 1:2.5g/ml, stir and remove floating impurities, add sodium oleate until the density of flotation liquid is about 2.37g/cm 3 , recovery of floating materials;
(3)将漂浮物料用0.38mol/L氢氧化钙进行浸出，浸出时间控制在73min，浸出时的固液比为8g/L，反应体系温度在65℃，至不在产生气体时，迅速过滤，得到滤渣a、滤液b，通风排去产生的气体，同时利用快速测氢仪监测排气口氢气的浓度；(3) The floating material is leached with 0.38mol/L calcium hydroxide, the leaching time is controlled at 73min, the solid-liquid ratio during leaching is 8g/L, the temperature of the reaction system is at 65°C, and when gas is no longer generated, filter it quickly, Obtain filter residue a and filtrate b, ventilate to remove the generated gas, and use a rapid hydrogen detector to monitor the concentration of hydrogen at the exhaust port;
(4)在步骤(3)基础上将滤渣a用纯水水洗2次，过滤收集水洗液d，分离得到滤渣c，滤渣c以2.5mol/L的酒石酸、体积比为3.4％的过氧化氢进行浸出，浸出时固液比为5g/L，浸出反应体系温度控制在58℃，浸出完毕后过滤得含Li +、Co 2+、Mn 2+、Ni 2+的酸溶液、残渣f，滤液b、水洗液d按体积比1:1.4进行混合，混合液用于步骤(3)中浸出。 (4) On the basis of step (3), the filter residue a is washed with pure water for 2 times, the washing liquid d is collected by filtration, and the filter residue c is separated, and the filter residue c is 3.4% hydrogen peroxide with 2.5mol/L tartaric acid and a volume ratio Carry out leaching, the solid-to-liquid ratio during leaching is 5g/L, the temperature of the leaching reaction system is controlled at 58°C, and after leaching is completed, filter to obtain an acid solution containing Li + , Co 2+ , Mn 2+ , Ni 2+ , residue f, and filtrate b. Washing solution d is mixed according to the volume ratio of 1:1.4, and the mixed solution is used for leaching in step (3).
实施例3Example 3
本实施例的废旧电池安全浸出的方法，包括以下具体步骤：The method for the safe leaching of waste batteries of the present embodiment comprises the following specific steps:
(1)回收的磷酸铁锂电池经拆解放电，经机械粗粉碎后，将破碎的废旧锂电池片置于烧结窑中焙烧，控制焙烧温度为420℃，稳定焙烧3.5h，期间升温速度控制在18℃/min，将焙烧产生的气体用0.09mol/L氢氧化钠碱液收集，焙烧后的废旧锂电池片进行振动分筛，色选机分拣铝箔、铜箔，再将分拣完毕的废弃锂电池粉利用磨球机研磨；(1) The recovered lithium iron phosphate battery is disassembled and discharged, and after being coarsely crushed by machinery, the broken waste lithium battery is placed in a sintering kiln for roasting. The roasting temperature is controlled at 420°C, and the roasting is stable for 3.5 hours. During the period, the heating rate is controlled. At 18°C/min, the gas generated by roasting is collected with 0.09mol/L sodium hydroxide lye, and the waste lithium batteries after roasting are vibrated and screened, and the color sorter sorts aluminum foil and copper foil, and then the sorting is completed The waste lithium battery powder is ground by a ball mill;
(2)纯水中加入球磨后的废弃锂电池粉，废弃锂电池粉：水的固液比为1:2.5g/ml，搅拌并除去漂浮杂质，加入油酸钠，至浮选液密度约为2.18g/cm 3，回收漂浮物料； (2) Add waste lithium battery powder after ball milling into pure water, the solid-to-liquid ratio of waste lithium battery powder:water is 1:2.5g/ml, stir and remove floating impurities, add sodium oleate until the density of the flotation liquid is about 2.18g/cm 3 , recovery of floating materials;
(3)将漂浮物料用0.67mol/L氢氧化钠进行浸出，浸出时间控制在24min，浸出时的固液比为15g/L，反应体系温度在70℃左右，至不在产生气体时，迅速过滤，得到滤渣a、滤液b，通风排去产生的气体，同时利用快速测氢仪监测排气口氢气的浓度；(3) Leach the floating material with 0.67mol/L sodium hydroxide, the leaching time is controlled at 24min, the solid-liquid ratio during leaching is 15g/L, the temperature of the reaction system is around 70°C, and when no gas is generated, filter it quickly , to obtain filter residue a and filtrate b, ventilate to remove the generated gas, and use a rapid hydrogen detector to monitor the concentration of hydrogen at the exhaust port;
(4)在步骤(3)基础上将滤渣a用纯水水洗3次，过滤收集水洗液d，分离得到 滤渣c，滤渣c以3.8mol/L的酒石酸、体积比为5.5％的过氧化氢进行浸出，浸出时固液比为12g/L，浸出反应体系温度控制在61℃，浸出完毕后过滤得含Li +、Co 2+、Mn 2+、Ni 2+的酸溶液、残渣f，滤液b、水洗液d按体积比1:1.8进行混合，混合液用于步骤(3)中浸出。 (4) On the basis of step (3), the filter residue a is washed 3 times with pure water, the washing liquid d is collected by filtration, and the filter residue c is separated, and the filter residue c is 5.5% hydrogen peroxide with tartaric acid of 3.8mol/L and a volume ratio Carry out leaching, the solid-to-liquid ratio during leaching is 12g/L, the temperature of the leaching reaction system is controlled at 61°C, and after leaching is completed, the acid solution containing Li + , Co 2+ , Mn 2+ , Ni 2+ , residue f, filtrate b. Washing solution d is mixed according to the volume ratio of 1:1.8, and the mixed solution is used for leaching in step (3).
实施例4Example 4
本实施例的废旧电池安全浸出的方法，包括以下具体步骤：The method for the safe leaching of waste batteries of the present embodiment comprises the following specific steps:
(1)回收的镍钴锰酸锂电池经拆解放电，经机械粗粉碎后，将破碎的废旧锂电池片置于烧结窑中焙烧，控制焙烧温度为550℃，稳定焙烧1h，期间升温速度控制在20℃/min，将焙烧产生的气体用0.12mol/L氢氧化钠碱液收集，焙烧后的废旧锂电池片进行振动分筛，色选机分拣铝箔、铜箔，再将分拣完毕的废弃锂电池粉利用磨球机研磨；(1) After dismantling and discharging the recycled nickel-cobalt-manganese-manganese oxide batteries, and mechanically crushing them roughly, put the broken waste lithium battery pieces in a sintering kiln for roasting. Controlled at 20°C/min, the gas generated by roasting is collected with 0.12mol/L sodium hydroxide lye, and the waste lithium batteries after roasting are vibrated and sieved, and the color sorter sorts aluminum foil and copper foil, and then sorts The finished waste lithium battery powder is ground by a ball mill;
(2)纯水中加入球磨后的废弃锂电池粉，废弃锂电池粉：水的固液比为1:2g/ml，搅拌并除去漂浮杂质，加入油酸钠，至浮选液密度约为2.44g/cm 3，回收漂浮物料； (2) Add waste lithium battery powder after ball milling into pure water, the solid-to-liquid ratio of waste lithium battery powder:water is 1:2g/ml, stir and remove floating impurities, add sodium oleate until the density of flotation liquid is about 2.44g/cm 3 , recovery of floating materials;
(3)将漂浮物料用0.78mol/L氢氧化钙进行浸出，浸出时间控制在19min，浸出时的固液比为20g/L，反应体系温度在87℃左右，至不在产生气体时，迅速过滤，得到滤渣a、滤液b，通风排去产生的气体，同时利用快速测氢仪监测排气口氢气的浓度；(3) Leach the floating material with 0.78mol/L calcium hydroxide, the leaching time is controlled at 19min, the solid-liquid ratio during leaching is 20g/L, the temperature of the reaction system is about 87°C, and when no gas is generated, filter it quickly , to obtain filter residue a and filtrate b, ventilate to remove the generated gas, and use a rapid hydrogen detector to monitor the concentration of hydrogen at the exhaust port;
(4)在步骤(3)基础上将滤渣a用纯水水洗3次，过滤收集水洗液d，分离得到滤渣c，滤渣c以4.78mol/L的酒石酸、体积比为8.0％的过氧化氢进行浸出，浸出时固液比为15g/L，浸出反应体系温度控制在94℃，浸出完毕后过滤得含Li +、Co 2+、Mn 2+、Ni 2+的酸溶液、残渣f，滤液b、水洗液d按体积比1:2.3进行混合，混合液用于步骤(3)中浸出。 (4) On the basis of step (3), the filter residue a is washed 3 times with pure water, the washing liquid d is collected by filtration, and the filter residue c is separated, and the filter residue c is 8.0% hydrogen peroxide with tartaric acid of 4.78mol/L and a volume ratio of 8.0%. Carry out leaching, the solid-to-liquid ratio during leaching is 15g/L, the temperature of the leaching reaction system is controlled at 94°C, and after leaching is completed, filter to obtain an acid solution containing Li + , Co 2+ , Mn 2+ , Ni 2+ , residue f, filtrate b. Washing solution d is mixed according to the volume ratio of 1:2.3, and the mixed solution is used for leaching in step (3).
对比例1Comparative example 1
一种废旧电池浸出的方法，包括以下具体步骤：A method for leaching waste batteries, comprising the following specific steps:
与实施例1的区别在于：步骤(2)中不进行浮选。The difference from Example 1 is that no flotation is carried out in step (2).
对比例2Comparative example 2
一种废旧电池浸出的方法，包括以下具体步骤：A method for leaching waste batteries, comprising the following specific steps:
与实施例1的区别在于：步骤(3)中未加氢氧化钠进行浸出。The difference from Example 1 is that no sodium hydroxide is added in step (3) for leaching.
对比例3Comparative example 3
与实施例1的区别在于：步骤(4)中采用硫酸浸出浸出，其他反应条件均一致。包 括：1.3mol/L的硫酸、1.5％的过氧化氢进行浸出，浸出时固液比为5g/L，浸出反应体系温度控制在60℃。The difference with Example 1 is: adopt sulfuric acid leaching leaching in the step (4), other reaction conditions are all the same. Including: 1.3mol/L sulfuric acid and 1.5% hydrogen peroxide for leaching, the solid-liquid ratio during leaching is 5g/L, and the temperature of the leaching reaction system is controlled at 60°C.
实施例1、2、3、4与对比例1、2、3的分析比较：The analysis comparison of embodiment 1,2,3,4 and comparative example 1,2,3:
表1中铝利用分光光度法测定，氢浓度为快速测氢仪测定排气口氢气的浓度，废弃锂电池粉中铝质量分数(％)＝步骤(1)中废弃电池粉铝质量分数(％)/废弃电池粉质量*100，漂浮物料中铝质量分数(％)＝漂浮物料中铝质量/漂浮物料质量，滤渣c中铝质量分数(％)＝滤渣c中铝质量/滤渣c质量*100。Aluminum in Table 1 is measured by spectrophotometry, and the hydrogen concentration is the concentration of hydrogen gas at the exhaust port measured by the rapid hydrogen detector, and the mass fraction of aluminum in the waste lithium battery powder (%)=the mass fraction of aluminum in the waste battery powder (%) in the step (1) )/mass of waste battery powder*100, mass fraction of aluminum in floating material (%)=mass of aluminum in floating material/mass of floating material, mass fraction of aluminum in filter residue c (%)=mass of aluminum in filter residue c/mass of filter residue c*100 .
由表1知，实施例1、2、3、4在相较于步骤(1)废弃锂电池粉中铝质量，在步骤(3)滤渣c中铝的质量分别下降了0.53％、0.16％、0.60％、0.26％；对比实施例1与对比例1，步骤(2)经过浮选，降低了0.23％氢浓度；对比实施例1与对比例2，步骤(3)中利用碱浸出铝，降低了滤渣c中铝质量0.11％；对比例3采用硫酸进行浸出，反应剧烈，而施例1、2、3、4以及比例1、2中浸出反应温和。因此可以得出的是，步骤(2)、(3)能有效地降低废弃锂电池粉中铝含量，减少氢的产生量，提高浸出时安全性。As known from Table 1, compared with the quality of aluminum in the waste lithium battery powder in step (1) of Examples 1, 2, 3, and 4, the quality of aluminum in the filter residue c in step (3) decreased by 0.53%, 0.16%, and 0.60%, 0.26%; Comparative Example 1 and Comparative Example 1, step (2) has reduced the 0.23% hydrogen concentration through flotation; Comparative Example 1 and Comparative Example 2, utilize alkali leaching aluminum in the step (3), reduce The mass of aluminum in filter residue c was 0.11%; comparative example 3 was leached by sulfuric acid, and the reaction was violent, while the leaching reactions in examples 1, 2, 3, 4 and ratios 1 and 2 were mild. Therefore, it can be concluded that steps (2) and (3) can effectively reduce the aluminum content in the waste lithium battery powder, reduce the generation of hydrogen, and improve the safety during leaching.
表1 实施例与对比例铝、氢检测值Table 1 Example and comparative example aluminum, hydrogen detection value
Figure PCTCN2021142932-appb-000001
Figure PCTCN2021142932-appb-000001
Figure PCTCN2021142932-appb-000002
Figure PCTCN2021142932-appb-000002
有机酸酒石酸的浸出与硫酸等无机酸的浸出相比，在保证有价金属元素浸出率的同时，其浸出反应相对来说比较温和，避免了产生的气体对环境、设备有不利的影响。Compared with the leaching of inorganic acids such as sulfuric acid, the leaching of organic acid tartaric acid has a relatively mild leaching reaction while ensuring the leaching rate of valuable metal elements, and avoids the adverse effects of the generated gas on the environment and equipment.
上面结合附图对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。The embodiments of the present invention have been described in detail above in conjunction with the accompanying drawings, but the present invention is not limited to the above-mentioned embodiments, and within the scope of knowledge of those of ordinary skill in the art, various modifications can be made without departing from the spirit of the present invention. Variety. In addition, the embodiments of the present invention and the features in the embodiments can be combined with each other if there is no conflict.

Claims (10)

  1. 一种废旧电池浸出的方法，其特征在于，包括以下步骤：A method for leaching waste batteries is characterized in that it comprises the following steps:
    (1)将废旧锂电池进行放电，焙烧，筛选，得到铜铝箔和电池粉；(1) Discharging, roasting and screening waste lithium batteries to obtain copper and aluminum foil and battery powder;
    (2)将所述电池粉加入至水中，再加入浮选剂进行浮选，得到漂浮物料和沉淀物质；(2) adding the battery powder into water, and then adding a flotation agent for flotation to obtain floating materials and sedimentation materials;
    (3)将所述漂浮物料用碱液进行浸出，过滤，得到滤液b和滤渣a；(3) leaching the floating material with alkali solution, filtering to obtain filtrate b and filter residue a;
    (4)将所述滤渣a进行洗涤，过滤得滤渣c，加入浸出剂和还原剂进行浸出，得到含Li +、Co 2+、Mn 2+、Ni 2+的酸溶液。 (4) Wash the filter residue a, filter to obtain the filter residue c, add a leaching agent and a reducing agent for leaching, and obtain an acid solution containing Li + , Co 2+ , Mn 2+ , and Ni 2+ .
  2. 根据权利要求1所述的方法，其特征在于，步骤(1)中，所述焙烧的温度为240℃～580℃，焙烧的时间为1.5～5h，焙烧的升温速度为5～30℃/min。The method according to claim 1, characterized in that in step (1), the temperature of the calcination is 240°C-580°C, the time of calcination is 1.5-5h, and the heating rate of calcination is 5-30°C/min .
  3. 根据权利要求1所述的方法，其特征在于，步骤(2)中，所述浮选剂为氧化石蜡皂、油酸钠或十二胺中的一种。The method according to claim 1, characterized in that, in step (2), the flotation agent is one of oxidized paraffin wax soap, sodium oleate or laurylamine.
  4. 根据权利要求1所述的方法，其特征在于，步骤(3)中，所述碱液为氢氧化钠、氢氧化镁、氢氧化钾或氢氧化钙中至少一种。The method according to claim 1, characterized in that, in step (3), the lye is at least one of sodium hydroxide, magnesium hydroxide, potassium hydroxide or calcium hydroxide.
  5. 根据权利要求1所述的方法，其特征在于，步骤(3)中，所述浸出时的固液比为5g/L～15g/L；步骤(4)中，所述浸出时的固液比为2～30g/L。The method according to claim 1, characterized in that, in step (3), the solid-to-liquid ratio during the leaching is 5g/L to 15g/L; in the step (4), the solid-to-liquid ratio during the leaching 2~30g/L.
  6. 根据权利要求1所述的方法，其特征在于，步骤(4)中，所述浸出剂为有机酸。The method according to claim 1, characterized in that, in step (4), the leaching agent is an organic acid.
  7. 根据权利要求6所述的方法，其特征在于，步骤(4)中，所述有机酸为酒石酸。method according to claim 6, is characterized in that, in step (4), described organic acid is tartaric acid.
  8. 根据权利要求1所述的方法，其特征在于，步骤(4)中，所述还原剂为过氧化氢。The method according to claim 1, characterized in that, in step (4), the reducing agent is hydrogen peroxide.
  9. 根据权利要求1所述的方法，其特征在于，步骤(4)中，所述洗涤后的水洗液d和步骤(3)的滤液b按(1～2):1进行混合，得到混合液，混合液可做为步骤(3)中的碱液，进行循环利用。The method according to claim 1, characterized in that, in step (4), the washed washing liquid d and the filtrate b of step (3) are mixed according to (1～2):1 to obtain a mixed solution, Mixed liquor can be used as alkali liquor in step (3), and recycles.
  10. 权利要求1-9任一项所述的废旧电池安全浸出的方法在回收有价金属中的应用。The application of the method for safe leaching of waste batteries described in any one of claims 1-9 in the recovery of valuable metals.
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