WO2023116042A1 - Method and device for recovering positive electrode material from lithium battery slurry - Google Patents

Method and device for recovering positive electrode material from lithium battery slurry Download PDF

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Publication number
WO2023116042A1
WO2023116042A1 PCT/CN2022/116251 CN2022116251W WO2023116042A1 WO 2023116042 A1 WO2023116042 A1 WO 2023116042A1 CN 2022116251 W CN2022116251 W CN 2022116251W WO 2023116042 A1 WO2023116042 A1 WO 2023116042A1
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Prior art keywords
slurry
stage
pyrolysis
positive electrode
drying
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PCT/CN2022/116251
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French (fr)
Chinese (zh)
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徐治伟
申魁文
彭冬
江志国
杨云广
李长东
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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
屏南时代新材料技术有限公司
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Publication of WO2023116042A1 publication Critical patent/WO2023116042A1/en

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    • 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
    • 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 lithium battery recovery, and in particular relates to a method and a device for recovering positive electrode materials from lithium battery slurry.
  • the positive electrode sheet is made of nickel-cobalt-manganese lithium manganate as the positive electrode active material and coated on the current collector.
  • its components include NMP (N-methylpyrrolidone), water, conductive agent, positive electrode material and polyvinylidene fluoride (PVDF), etc., also contains foreign materials such as slurry packaging plastic bags, rags and gloves.
  • the positive electrode material in the waste slurry contains Ni, Co, and Mn metals, the waste slurry has a great recyclable value; in addition, during the long-term storage of the waste slurry, it is easy to make the waste slurry agglomerate, which is inconvenient The recovery of slurry, and if the waste slurry is not handled properly, it will not only cause waste of resources, but also cause environmental pollution, and there is a huge potential safety hazard.
  • the treatment method for the waste slurry produced by lithium battery coating is mainly to incinerate it.
  • the specific process is: put the waste slurry produced by coating into the incinerator for combustion and pyrolysis, and produce slag and a large amount of tail gas. Then the exhaust gas is treated to make it meet the emission standards.
  • This method can remove organic matter, and the slag produced can be directly leached, but the whole process will produce tail gas such as nitrogen oxides, carbon oxides, and hydrogen fluoride, and the tail gas needs to be treated before being discharged.
  • the treatment pressure is high, and the incineration process The material is easy to agglomerate and stick to the wall, and it is difficult for the barreled material to enter the incinerator.
  • a method for recovering positive electrode materials from lithium battery slurry is provided.
  • the method effectively separates and recycles positive electrode materials and solvents, and can reduce tail gas emissions.
  • the total content of Ni, Co, Mn and Li metals in the positive electrode powder recovered by the solution of the invention is more than 50%, which has great economic benefits.
  • the technical solution adopted in the present invention is:
  • the solid phase part is dried, crushed and pyrolyzed to obtain the positive electrode material.
  • the waste materials include waste slurry containing foreign matter such as plastics and cloth strips.
  • the step-by-step overflow crushing includes transporting the first slurry whose size is smaller than the discharge hole into the matching primary slurry pool, and passing through the bubble drum in the crushing area of the primary slurry pool.
  • the fine particle slurry is brought into the next crushing area by the solvent through the overflow, and the air bubbles are crushed again in the next crushing area, so that the slurry that meets the requirements can be obtained after multiple overflow crushing, and then enters the next stage process.
  • the waste material has a volume of 1000-2000L.
  • the invention can process waste materials in large quantities.
  • the solvent includes at least one of N-methylpyrrolidone, propylene glycol methyl ether acetate, and propylene glycol methyl ether.
  • the volume of the solvent is 1000-2000L.
  • the pressure at which the bubbles are broken is 0.4-0.8 MPa.
  • the air bubble crushing can peel off the waste slurry adhered to the foreign matter, and preliminarily crush the waste slurry.
  • the air bubble crushing can also split larger air bubbles to form smaller diameter air bubbles, which improves air and air contact.
  • the contact area of the slurry can peel off the waste slurry adhered to the foreign matter, and preliminarily crush the waste slurry.
  • the air bubble crushing can also split larger air bubbles to form smaller diameter air bubbles, which improves air and air contact. The contact area of the slurry.
  • the slurry and foreign matters with a size larger than the discharge hole are left on the conveyor belt, and the first slurry with a size smaller than the diameter of the discharge hole is gradually Stage overflow broken.
  • the prepared flocculant before the flocculation step, is mixed with the second slurry, and the solid and liquid in the second slurry are separated by stirring and dispersing.
  • the flocculant is ferric sulfate or a mixture of ferric sulfate and cationic PAM, and the volume ratio between the slurry and the flocculant is 1000:5-20.
  • the stirring speed during stirring and dispersing is 20-50 r/min
  • the dispersing speed is 1000-1600 r/min
  • the dispersing time is 10-30 min.
  • the moisture content in the filter cake can be reduced, and the phenomenon of wall sticking and agglomeration during the drying process can be alleviated.
  • the pressure filtration includes squeeze filtration.
  • the pressure of the filter press is 0.2-0.5Mpa, and the filter press time is 10-30min.
  • the method further includes recovering the solvent in the liquid phase obtained after solid-liquid separation to obtain a first waste liquid, and the first waste liquid is used to prepare a flocculant.
  • the filter cake obtained by the method has a low moisture content and is not easy to block the filter screen; the solvent content in the filter cake is low, avoiding an excessively high solvent content, It leads to combustion in the subsequent high-temperature calcination process, producing a large amount of nitrogen oxides and carbon oxides to pollute the environment.
  • the filter cake is dried and crushed to obtain a powdery material, which increases the pyrolysis contact area of the next process and improves the pyrolysis effect.
  • the drying is divided into two stages of drying.
  • the drying temperature of the first stage is 100-160°C, and the drying time is 0.5-2h; the drying temperature of the second stage is 160-220°C, and the drying time is 2-2 hours. 6h.
  • the exhaust gas generated during the pyrolysis process is discharged after tail gas treatment.
  • the two-stage drying reduces sticking and agglomeration by gradually increasing the temperature and drying, and prolongs the maintenance period of the equipment.
  • the volatilized gas in the drying process is condensed, distilled, and the solvent is separated to obtain a second waste liquid, which is used to prepare a flocculant.
  • the solvent produced during the process of purification, filtration and drying by distillation can realize the recycling of the solvent, and the waste water produced after distillation can also be recycled and used in the preparation of the flocculant solution to realize recycling.
  • the distillation is preferably rectification, and the solvent is preferably NMP solution.
  • more than 98% of NMP can be separated and recovered in the stages of slurry press filtration and filter cake double-cone vacuum drying, and the recovered NMP can be sold to the outside world after reaching a certain concentration through atmospheric distillation, creating income.
  • Less than 2% of NMP enters the heat treatment stage, which greatly reduces the burden of tail gas treatment, and the recovered powder fully meets the requirements of the leaching process.
  • the pyrolysis includes multi-stage pyrolysis, preferably four-stage pyrolysis, the first stage pyrolysis temperature is 300-360°C, the second stage pyrolysis temperature is 400-600°C, and the second stage pyrolysis temperature is 400-600°C.
  • the pyrolysis temperature of the third stage is 400-600°C, and the pyrolysis temperature of the fourth stage is 260-320°C.
  • the four-stage pyrolysis is first carried out at 300-360°C to volatilize the residual NMP and water in the crushed powder, and then proceed at 400-600°C Pyrolysis, to pyrolyze the conductive agent and PVDF contained in the filter residue to remove the conductive agent and PVDF.
  • Adopting this kind of step-by-step pyrolysis with gradually increasing temperature can reduce the decomposition of NMP in the pyrolysis process, thereby reducing the generation of tail gas, and can recycle NMP to save costs.
  • this pyrolysis method can effectively reduce the degree of pyrolysis agglomeration, make pyrolysis sufficient, effectively remove impurities in the positive electrode powder, and improve the purity of the recovered positive electrode powder.
  • the four-stage pyrolysis can avoid volatilization of lithium, thereby effectively recovering lithium.
  • the pyrolysis can remove the residual solvent, moisture in the powdery material, polyvinylidene fluoride (PVDF) and conductive agent originally contained in the waste.
  • PVDF polyvinylidene fluoride
  • the solid content of the second slurry is 20%-40%.
  • the solid content has a great influence on the production capacity. If the solid content is too low, the liquid content in the slurry will be more, resulting in less filter cakes for each pressing filter; if the solid content is too high, the flocculation and dispersion effect will be poor, and the solid The liquid separation is not obvious, and the liquid cannot be effectively separated from the solid during the filter press, resulting in a large water content in the filter cake, resulting in wall sticking, agglomeration, long drying time, high energy consumption, and low production efficiency during drying.
  • the foreign matter is separated from the waste slurry through the bubble drum, and the waste slurry is initially crushed, and then dispersed through gradual overflow and bubble crushing, which can effectively
  • the solid content and particle size of the prepared slurry are controlled to keep the solid content of the slurry between 20% and 40%, so as to ensure the effect of subsequent flocculation and pressure filtration, as well as the production capacity.
  • the method can realize continuous and large-scale treatment of waste lithium battery slurry, and simplify the slurry recycling process.
  • the positive electrode material and solvent are effectively separated and recycled to reduce recycling costs.
  • the whole process is environmentally friendly and energy-saving, which is convenient for later processing of the positive electrode powder.
  • the total content of Ni, Co, Mn, and Li metals in the recovered positive electrode powder is more than 50%. Great recycling value.
  • the solvent is preferably NMP.
  • the technical solution adopted in the present invention is:
  • a preparation tank is connected between the stirred tank and the rectifying tower;
  • Condensing equipment is connected between the double-cone drying equipment and the rectifying tower;
  • the rectifying tower is connected with a liquid storage tank
  • the pyrolysis furnace is connected with tail gas treatment equipment.
  • the first crusher is a double-shaft shredder
  • the second crusher is a double-shaft shredder
  • the double-cone drying equipment is provided with two temperature zones.
  • the pyrolysis furnace is a multi-stage heating rotary kiln.
  • the discharge end of the first crusher is connected to the feed end of the bubble crusher through a conveyor, and the conveyor is used to remove the waste materials shredded by the first crusher.
  • the slurry is sent to the bubble breaker, and the conveyor is set upwardly from the discharge end of the first crusher to the feed end of the bubble breaker, and the conveyor belt on the conveyor is evenly spaced with a number of spacers.
  • the board prevents the shredded slurry from slipping during the conveying process.
  • the preparation tank is used for preparing a flocculant solution.
  • the air bubble breaker includes a conveyor belt, a cleaning area, a crushing area and a slurry tank;
  • One end of the conveyor belt is located below the discharge port of the first crusher, and the other end is located at the discharge port of the bubble crusher;
  • discharge holes are provided on the conveyor belt passing through the cleaning area, and the first slurry falling from the discharge holes enters into the cleaning area below the discharge holes.
  • equidistant partitions are arranged on the conveyor belt to prevent the crushed slurry from slipping during conveyance, and the conveyor belt circulates through a motor and a chain.
  • the bottom of the bubble breaker is provided with a bubble drum, and several discharge holes are opened on the conveyor belt, and the cleaned slurry falls from the conveyor belt to the bottom of the conveyor belt through the discharge holes. area, and then fall into the slurry tank, and the cleaned rags, plastics, etc. are transported to the outlet through the conveyor belt and fall into the slag collection barrel.
  • the foreign matter is separated from the waste slurry through a bubble drum, and the waste slurry is initially crushed, and then dispersed through gradual overflow and bubble crushing. It can effectively control the solid content and particle size of the prepared slurry, so that the solid content of the slurry can be kept between 20% and 40%, ensuring the effect of subsequent flocculation and filter pressing, and ensuring production capacity;
  • multi-stage pyrolysis is adopted, which can reduce the decomposition of the solvent in the pyrolysis process, thereby reducing the generation of tail gas, and can recycle the solvent to save costs.
  • multi-stage pyrolysis can effectively reduce the degree of pyrolysis agglomeration, make pyrolysis sufficient, effectively remove impurities in the positive electrode powder, and improve the purity of the recovered positive electrode powder.
  • the method can realize continuous and large-scale processing of waste lithium battery slurry, and simplifies the slurry recycling process.
  • the positive electrode material and solvent are effectively separated and recycled to reduce recycling costs.
  • the whole process is environmentally friendly and energy-saving, which is convenient for later processing of the positive electrode powder.
  • the total content of Ni, Co, Mn, and Li metals in the recovered positive electrode powder is more than 50%. Great recycling value.
  • Fig. 1 is the process flow diagram of the method for recovering positive electrode material from lithium battery slurry in embodiment 1;
  • Fig. 2 is the structural diagram of the device of embodiment 5 anode material recovery
  • Fig. 3 is the structural diagram of the air bubble breaker in Example 5.
  • orientation descriptions such as the orientation or positional relationship indicated by up, down, left, right, etc., are based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present invention.
  • the invention and the simplified description do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operate in a specific orientation, and thus should not be construed as limiting the present invention.
  • the NMP solution with a concentration of 70% to 90% in the examples is a mixed solvent of NMP and water.
  • the method for recovering positive electrode material from lithium battery slurry comprises the following steps:
  • Two-stage drying is used to dry the filter cake to obtain a block solid dry material.
  • the drying temperature of the first stage is 100°C, and the drying time is 2h; the drying temperature of the second stage is 160°C, and the drying time is 6h;
  • the powdery material is pyrolyzed by 4-stage pyrolysis, the pyrolysis temperature of the first stage is 300°C, the pyrolysis temperature of the second stage is 400°C, the pyrolysis temperature of the third stage is 400°C, and the pyrolysis temperature of the fourth stage is 260°C , to produce finished powder materials, and the exhaust gas generated during the pyrolysis process is discharged after tail gas treatment;
  • the method for recovering positive electrode material from lithium battery slurry comprises the following steps:
  • the powdery material is pyrolyzed by 4-stage pyrolysis, the pyrolysis temperature of the first stage is 360°C, the pyrolysis temperature of the second stage is 600°C, the pyrolysis temperature of the third stage is 600°C, and the pyrolysis temperature of the fourth stage is 320°C , to produce finished powder materials, and the exhaust gas generated during the pyrolysis process is discharged after tail gas treatment;
  • the method for recovering positive electrode material from lithium battery slurry comprises the following steps:
  • S1 Take 1500L of waste slurry containing foreign matter such as plastics and cloth strips and shred it in a double-shaft shredder.
  • the A-axis crushing speed is 20r/min
  • the B-axis crushing speed is 20r/min;
  • the powdery material is pyrolyzed by 4-stage pyrolysis, the pyrolysis temperature of the first stage is 320°C, the pyrolysis temperature of the second stage is 450°C, the pyrolysis temperature of the third stage is 450°C, and the pyrolysis temperature of the fourth stage is 280°C , to produce finished powder materials, and the exhaust gas generated during the pyrolysis process is discharged after tail gas treatment;
  • the method for recovering positive electrode material from lithium battery slurry comprises the following steps:
  • the powdery material is pyrolyzed by 4-stage pyrolysis, the pyrolysis temperature of the first stage is 350°C, the pyrolysis temperature of the second stage is 500°C, the pyrolysis temperature of the third stage is 500°C, and the pyrolysis temperature of the fourth stage is 300°C , to produce finished powder materials, and the exhaust gas generated during the pyrolysis process is discharged after tail gas treatment;
  • the device for recovering positive electrode materials includes:
  • Bubble breaker 200 the discharge end of the double-shaft shredder is connected to the feed end of the bubble breaker 200 through a conveyor, and the conveyor is used to transfer the waste pulp shredded by the shredder to the bubble breaker 200,
  • the conveyor is set upwards from the discharge end of the double-shaft shredder to the feed end of the bubble crusher 200, and the conveyor belt on the conveyor is evenly spaced with several partitions to prevent the shredded pulp from slipping during the transmission process;
  • the bubble breaker 200 includes a conveyor belt 220 for conveying the shredded slurry, a slurry cleaning device and a slurry tank 230 below it;
  • One end of the conveyor belt 220 is located below the discharge port of the shredder, and the other end extends upwards to the discharge port of the pulp cleaning equipment at a certain angle, and equidistant partitions are set on the conveyor belt 220 to prevent the crushed pulp from slipping during conveying;
  • the conveyor belt 220 circulates through the motor and the chain, and at least a part of the conveyor belt 220 is located in the slurry cleaning equipment;
  • Bubble drums are provided at the bottom of the bubble breaker 200, and several discharge holes are provided on the conveyor belt 220.
  • the cleaned slurry falls from the conveyor belt 220 through the discharge holes into the cleaning area 210 below the conveyor belt 220, and then falls into the In the slurry tank 230, cleaned rags, plastics, etc. are conveyed to the outlet through the conveyor belt 220 and fall into the slag collection barrel 260;
  • the devices used in the step by step overflow crushing step are as follows:
  • a number of overflow plates 250 are arranged in the slurry pool 230, and the overflow plates 250 divide the slurry pool 230 into a plurality of crushing areas 240, and each crushing area 240 is equipped with a bubble drum;
  • An overflow port for the overflow of the slurry is left between the overflow plate 250 and the top of the slurry pool 230, and the height of the overflow plate 250 provided at the discharge end from the feed end of the slurry pool 230 gradually decreases, so that The waste slurry is separated from foreign matter, and the waste slurry is gradually broken into a slurry with a size and a solid content that meet the requirements;
  • Stirring tank 300 is used for dispersing and stirring, so that the solid components in the slurry can be fully flocculated to achieve preliminary solid-liquid separation;
  • the condensing equipment 600 connected with the double-cone drying equipment 700 is used to condense NMP and water vapor produced in the drying process;
  • the second crusher 1000 connected with the double-cone drying equipment 700 is used to crush the dried block solid dry material to obtain powdery material, so as to increase the pyrolysis contact area;
  • the pyrolysis furnace 1200 pyrolyzes the crushed powdery materials to remove impurities such as binders and conductive agents to obtain finished powder materials.
  • the tail gas generated during the pyrolysis process passes through the tail gas treatment equipment 1100 connected to the pyrolysis furnace 1200 Empty after treatment, the pyrolysis furnace 1200 is a multi-stage heating rotary kiln, and the material is gradually heated and pyrolyzed to reduce the generation of tail gas, reduce the loss on ignition rate, and reduce the phenomenon of sticking to the wall and agglomeration;
  • the packing machine 1300 is used for packing the finished powder materials.
  • Two-stage drying is used to dry the filter cake to obtain a block solid dry material.
  • the drying temperature of the first stage is 100°C, and the drying time is 2h; the drying temperature of the second stage is 160°C, and the drying time is 6h;
  • the powdery material is pyrolyzed by 4-stage pyrolysis, the pyrolysis temperature of the first stage is 300°C, the pyrolysis temperature of the second stage is 400°C, the pyrolysis temperature of the third stage is 400°C, and the pyrolysis temperature of the fourth stage is 260°C , to produce finished powder materials, and the exhaust gas generated during the pyrolysis process is discharged after tail gas treatment;
  • the method for recovering positive electrode material from lithium battery slurry comprises the following steps:
  • the powdery material is pyrolyzed by 4-stage pyrolysis, the pyrolysis temperature of the first stage is 360°C, the pyrolysis temperature of the second stage is 600°C, the pyrolysis temperature of the third stage is 600°C, and the pyrolysis temperature of the fourth stage is 320°C , to produce finished powder materials, and the exhaust gas generated during the pyrolysis process is discharged after tail gas treatment;
  • 2Moisture content the ratio of the liquid content in the filter cake after pressing to the total amount of the filter cake
  • Ni content - refers to the content of Ni, Co, Mn, Li in the positive electrode powder obtained after pyrolysis.
  • Ni, Co, Mn and Ni were detected by inductively coupled plasma optical emission spectrometer (IPC-OES).
  • the solid content in the slurry after cleaning and dispersion of Examples 1 to 4 is between 20% and 40%, which can ensure the production capacity while ensuring the effect of subsequent flocculation and pressure filtration; the moisture content is all controlled at Between 20% and 30%, it can reduce the sticking and agglomeration phenomenon during the drying process, and control the drying time to avoid energy consumption caused by too long drying time; the loss on ignition rate is controlled below 4%, and the loss on ignition rate is controlled Below 3%, it shows that the loss on ignition rate and the loss on ignition rate are both small, and the tail gas produced in the pyrolysis process is less, and the pyrolysis is relatively sufficient.
  • the total content of Ni, Co, Mn and Li metals in the positive electrode powder obtained after pyrolysis is more than 50%, which shows that the recovery effect is good and has great recovery value.

Abstract

Disclosed in the present invention are a method and a device for recovering a positive electrode material from a lithium battery slurry. The method comprises the following steps: shredding waste material, adding a solvent, and subjecting same to bubble crushing to obtain a first slurry; sieving the first slurry through a discharging hole; subjecting the first slurry with a size smaller than the diameter of the discharging hole to stage-by-stage overflow crushing to obtain a second slurry; subjecting the second slurry to flocculation and filter pressing to obtain a filter cake and a filtrate; and drying, crushing and pyrolyzing the filter cake to obtain a positive electrode material. The method can achieve continuous and large-batch treatment of the waste lithium battery slurry, and simplifies the slurry recovery process. In addition, the positive electrode material and the solvent are effectively separated and recycled; the recovery cost is reduced; and the whole process is environmentally friendly and energy-saving, such that the positive electrode powder can be conveniently treated at a later period. The total content of Ni, Co, Mn and Li metal in the recycled positive electrode powder is 50% or more, and the method has a good recovery value.

Description

一种从锂电池浆料中回收正极材料的方法及其装置A method and device for recovering positive electrode material from lithium battery slurry 技术领域technical field
本发明属于锂电池回收技术领域，具体涉及一种从锂电池浆料中回收正极材料的方法及其装置。The invention belongs to the technical field of lithium battery recovery, and in particular relates to a method and a device for recovering positive electrode materials from lithium battery slurry.
背景技术Background technique
在镍钴锰三元锂离子电池的制备过程中，正极片是以镍钴锰酸锂作为正极活性材料制成浆料涂布在集流体上制成的，在这个过程中不可避免的会产生废弃浆料，其成分包括NMP(N-甲基吡咯烷酮)、水、导电剂、正极材料和聚偏氟乙烯(PVDF)等，还包含浆料包装塑料袋、抹布和手套等异物。因废弃浆料中的正极材料包含Ni、Co、Mn金属，故废弃浆料具有极大的可回收价值；此外，在废弃浆料长期存放过程中，易使废弃浆料结块，从而不便于浆料的回收，并且若废弃浆料处理不当，不仅会造成资源浪费，还会导致环境污染，存在巨大的安全隐患。In the preparation process of nickel-cobalt-manganese ternary lithium-ion batteries, the positive electrode sheet is made of nickel-cobalt-manganese lithium manganate as the positive electrode active material and coated on the current collector. In this process, it is inevitable to produce Waste slurry, its components include NMP (N-methylpyrrolidone), water, conductive agent, positive electrode material and polyvinylidene fluoride (PVDF), etc., also contains foreign materials such as slurry packaging plastic bags, rags and gloves. Because the positive electrode material in the waste slurry contains Ni, Co, and Mn metals, the waste slurry has a great recyclable value; in addition, during the long-term storage of the waste slurry, it is easy to make the waste slurry agglomerate, which is inconvenient The recovery of slurry, and if the waste slurry is not handled properly, it will not only cause waste of resources, but also cause environmental pollution, and there is a huge potential safety hazard.
目前，对锂电池涂布产生的废弃浆料的处理方法主要是对其进行焚烧处理，具体过程为：将涂布产生的废弃浆料投入焚烧炉进行燃烧热解，产出炉渣和大量尾气，然后再对废气进行处理使之达标排放。这种方法能将有机物除去，产出的炉渣可以直接进行浸出，但是整个过程会产生氮氧化物、碳氧化物以及氟化氢等尾气，需对尾气进行处理后排放，处理压力大，且焚烧过程中物料容易结块、粘壁，桶装物料进入焚烧炉较难。At present, the treatment method for the waste slurry produced by lithium battery coating is mainly to incinerate it. The specific process is: put the waste slurry produced by coating into the incinerator for combustion and pyrolysis, and produce slag and a large amount of tail gas. Then the exhaust gas is treated to make it meet the emission standards. This method can remove organic matter, and the slag produced can be directly leached, but the whole process will produce tail gas such as nitrogen oxides, carbon oxides, and hydrogen fluoride, and the tail gas needs to be treated before being discharged. The treatment pressure is high, and the incineration process The material is easy to agglomerate and stick to the wall, and it is difficult for the barreled material to enter the incinerator.
因此，提供一种既能有效回收废弃浆料，又可降低尾气排放的方法具有重要意义。Therefore, it is of great significance to provide a method that can effectively recycle waste pulp and reduce tail gas emissions.
发明内容Contents of the invention
本发明所要解决的第一个技术问题是：The first technical problem to be solved by the present invention is:
提供一种从锂电池浆料中回收正极材料的方法。A method for recovering positive electrode materials from lithium battery slurry is provided.
所述方法将正极材料和溶剂有效分离回收利用，且可减少尾气排放。通过本发明方案回收得到的正极粉末中Ni、Co、Mn、Li金属总含量在50％以上，具有极大的经济利益。The method effectively separates and recycles positive electrode materials and solvents, and can reduce tail gas emissions. The total content of Ni, Co, Mn and Li metals in the positive electrode powder recovered by the solution of the invention is more than 50%, which has great economic benefits.
本发明所要解决的第二个技术问题是：The second technical problem to be solved by the present invention is:
提供一种使用所述方法进行正极材料回收的装置。Provided is a device for recovering cathode materials using the method.
为了解决所述第一个技术问题，本发明采用的技术方案为：In order to solve the first technical problem, the technical solution adopted in the present invention is:
从锂电池浆料中回收正极材料的方法，Method for recovering positive electrode material from lithium battery slurry,
包括以下步骤：Include the following steps:
将废料撕碎，加入溶剂，经气泡破碎后，得到第一浆料；Shred the waste, add a solvent, and get the first slurry after being broken by air bubbles;
通过出料孔进行筛分；Screening through discharge holes;
将尺寸小于出料孔直径的第一浆料进行逐级溢流破碎，得到第二浆料；performing stepwise overflow crushing of the first slurry whose size is smaller than the diameter of the discharge hole to obtain the second slurry;
经絮凝、固液分离后，收集固相部分；After flocculation and solid-liquid separation, the solid phase is collected;
固相部分经干燥、破碎、热解后，得到正极材料。The solid phase part is dried, crushed and pyrolyzed to obtain the positive electrode material.
所述废料包括含有塑料、布条等异物的废弃浆料。The waste materials include waste slurry containing foreign matter such as plastics and cloth strips.
根据本发明的一种实施方式，所述逐级溢流破碎，包括将尺寸小于出料孔的第一浆料输送入配套的一级浆料池，经过一级浆料池破碎区内气泡鼓进一步破碎，通过溢流细小颗粒浆料被溶剂带入下一级破碎区，在下一级破碎区内再次进行气泡破碎，以此进行多次溢流破碎后得到满足要求的浆液，再进入下道工序。According to one embodiment of the present invention, the step-by-step overflow crushing includes transporting the first slurry whose size is smaller than the discharge hole into the matching primary slurry pool, and passing through the bubble drum in the crushing area of the primary slurry pool. For further crushing, the fine particle slurry is brought into the next crushing area by the solvent through the overflow, and the air bubbles are crushed again in the next crushing area, so that the slurry that meets the requirements can be obtained after multiple overflow crushing, and then enters the next stage process.
根据本发明的一种实施方式，所述废料的体积为1000～2000L。本发明可以进行大批量的废料处理。According to one embodiment of the present invention, the waste material has a volume of 1000-2000L. The invention can process waste materials in large quantities.
根据本发明的一种实施方式，所述溶剂包括N-甲基吡咯烷酮、丙二醇甲醚醋酸酯、丙二醇甲醚中的至少一种。According to one embodiment of the present invention, the solvent includes at least one of N-methylpyrrolidone, propylene glycol methyl ether acetate, and propylene glycol methyl ether.
根据本发明的一种实施方式，所述溶剂的体积为1000～2000L。According to one embodiment of the present invention, the volume of the solvent is 1000-2000L.
根据本发明的一种实施方式，所述气泡破碎的压力为0.4～0.8Mpa。According to one embodiment of the present invention, the pressure at which the bubbles are broken is 0.4-0.8 MPa.
所述气泡破碎能够将异物上粘附的废弃浆料剥落下来，并将废弃浆料进行初步破碎，所述气泡破碎还能够将较大的空气气泡割裂，形成直径更小的气泡，提高空气与浆液的接触面积。The air bubble crushing can peel off the waste slurry adhered to the foreign matter, and preliminarily crush the waste slurry. The air bubble crushing can also split larger air bubbles to form smaller diameter air bubbles, which improves air and air contact. The contact area of the slurry.
根据本发明的一种实施方式，所述通过出料孔进行筛分之后，将尺寸大于出料孔的浆料和异物留在传送带上，将尺寸小于出料孔直径的第一浆料进行逐级溢流破碎。According to one embodiment of the present invention, after the sieving through the discharge hole, the slurry and foreign matters with a size larger than the discharge hole are left on the conveyor belt, and the first slurry with a size smaller than the diameter of the discharge hole is gradually Stage overflow broken.
根据本发明的一种实施方式，在絮凝步骤之前，先将配制好的絮凝剂与所述第二浆料混合，通过搅拌分散使所述第二浆料中的固体与液体实现固液分离。According to an embodiment of the present invention, before the flocculation step, the prepared flocculant is mixed with the second slurry, and the solid and liquid in the second slurry are separated by stirring and dispersing.
根据本发明的一种实施方式，所述絮凝剂为硫酸铁或硫酸铁和阳离子PAM的混合物，浆液与絮凝剂之间的体积比为1000：5～20。According to one embodiment of the present invention, the flocculant is ferric sulfate or a mixture of ferric sulfate and cationic PAM, and the volume ratio between the slurry and the flocculant is 1000:5-20.
根据本发明的一种实施方式，所述搅拌分散时的搅拌速度为20～50r/min，分散速度为1000～1600r/min，分散时间为10～30min。According to one embodiment of the present invention, the stirring speed during stirring and dispersing is 20-50 r/min, the dispersing speed is 1000-1600 r/min, and the dispersing time is 10-30 min.
通过对浆液进行分散搅拌絮凝，然后再进行压滤，可使滤饼中的含湿率降低，减轻干燥过程中的粘壁、结块现象。By dispersing, stirring and flocculating the slurry, and then performing pressure filtration, the moisture content in the filter cake can be reduced, and the phenomenon of wall sticking and agglomeration during the drying process can be alleviated.
根据本发明的一种实施方式，所述压滤包括挤压压滤。According to an embodiment of the present invention, the pressure filtration includes squeeze filtration.
根据本发明的一种实施方式，所述压滤压力为0.2～0.5Mpa，压滤时间为10～30min。According to one embodiment of the present invention, the pressure of the filter press is 0.2-0.5Mpa, and the filter press time is 10-30min.
根据本发明的一种实施方式，所述方法还包括将固液分离后所得的液相中的溶剂回收，得到第一废液，所述第一废液用于配制絮凝剂。According to one embodiment of the present invention, the method further includes recovering the solvent in the liquid phase obtained after solid-liquid separation to obtain a first waste liquid, and the first waste liquid is used to prepare a flocculant.
根据本发明的一种实施方式，经过所述方法处理得到的所述滤饼，其含湿率低、不容易堵塞滤网；所述滤饼中溶剂含量低，避免了过高的溶剂含量，导致在后续的在高温煅烧过程中燃烧，产生大量氮氧化物、碳氧化物污染环境。According to one embodiment of the present invention, the filter cake obtained by the method has a low moisture content and is not easy to block the filter screen; the solvent content in the filter cake is low, avoiding an excessively high solvent content, It leads to combustion in the subsequent high-temperature calcination process, producing a large amount of nitrogen oxides and carbon oxides to pollute the environment.
根据本发明的一种实施方式，所述滤饼经干燥、破碎后，得到粉状物料，增大下道工序热解接触面积，提高热解效果。According to one embodiment of the present invention, the filter cake is dried and crushed to obtain a powdery material, which increases the pyrolysis contact area of the next process and improves the pyrolysis effect.
根据本发明的一种实施方式，所述干燥分为两段干燥，第一段干燥温度为100～160℃，干燥时间0.5～2h；第二段干燥温度为160～220℃，干燥时间2～6h。热解过程中产生的废气经尾气处理后排放。According to one embodiment of the present invention, the drying is divided into two stages of drying. The drying temperature of the first stage is 100-160°C, and the drying time is 0.5-2h; the drying temperature of the second stage is 160-220°C, and the drying time is 2-2 hours. 6h. The exhaust gas generated during the pyrolysis process is discharged after tail gas treatment.
所述两段式干燥，通过逐步升温干燥减轻粘壁、结块现象，延长设备的保养周期。The two-stage drying reduces sticking and agglomeration by gradually increasing the temperature and drying, and prolongs the maintenance period of the equipment.
根据本发明的一种实施方式，所述干燥中挥发的气体经冷凝后、蒸馏，分离溶剂，得到第二废液，所述第二废液用于配制絮凝剂。According to one embodiment of the present invention, the volatilized gas in the drying process is condensed, distilled, and the solvent is separated to obtain a second waste liquid, which is used to prepare a flocculant.
通过蒸馏提纯压滤、干燥过程中产生的溶剂，可实现溶剂的回收利用，且蒸馏后产生的废水也可回收利用于絮凝剂溶液的配制中，实现循环回收利用。其中蒸馏优选为精馏，溶剂优选为NMP溶液。The solvent produced during the process of purification, filtration and drying by distillation can realize the recycling of the solvent, and the waste water produced after distillation can also be recycled and used in the preparation of the flocculant solution to realize recycling. Wherein the distillation is preferably rectification, and the solvent is preferably NMP solution.
根据本发明的一种实施方式，浆料压滤及滤饼双锥真空干燥阶段可分离回收98％以上的NMP，回收的NMP通过常压精馏达到一定浓度可对外出售，创造收益，仅有不到2％的NMP进入热处理阶段，大大减轻尾气处理负担，且回收得到的粉末完全满足浸出工序要求。According to one embodiment of the present invention, more than 98% of NMP can be separated and recovered in the stages of slurry press filtration and filter cake double-cone vacuum drying, and the recovered NMP can be sold to the outside world after reaching a certain concentration through atmospheric distillation, creating income. Less than 2% of NMP enters the heat treatment stage, which greatly reduces the burden of tail gas treatment, and the recovered powder fully meets the requirements of the leaching process.
根据本发明的一种实施方式，所述热解包括多段热解，优选为四段热解，第一段热解温度为300～360℃，第二段热解温度为400～600℃，第三段热解温度为400～600℃，第四段热解温度为260～320℃。According to one embodiment of the present invention, the pyrolysis includes multi-stage pyrolysis, preferably four-stage pyrolysis, the first stage pyrolysis temperature is 300-360°C, the second stage pyrolysis temperature is 400-600°C, and the second stage pyrolysis temperature is 400-600°C. The pyrolysis temperature of the third stage is 400-600°C, and the pyrolysis temperature of the fourth stage is 260-320°C.
根据本发明的一种实施方式，所述四段热解，先在300～360℃下进行热解，使破碎后的粉料中残留的NMP和水分挥发，然后再在400～600℃下进行热解，使滤渣中含有的导电剂、PVDF等热解，以去除导电剂、PVDF。According to one embodiment of the present invention, the four-stage pyrolysis is first carried out at 300-360°C to volatilize the residual NMP and water in the crushed powder, and then proceed at 400-600°C Pyrolysis, to pyrolyze the conductive agent and PVDF contained in the filter residue to remove the conductive agent and PVDF.
采用这种逐步升温分段式热解，可减少热解过程中NMP的分解，从而减少尾气的产生，并可对NMP进行回收利用，节约成本。此外，这种热解方式可有效降低热解结块程度，使热解充分，有效去除正极粉末中的杂质，提高回收得到的正极粉末的纯度。Adopting this kind of step-by-step pyrolysis with gradually increasing temperature can reduce the decomposition of NMP in the pyrolysis process, thereby reducing the generation of tail gas, and can recycle NMP to save costs. In addition, this pyrolysis method can effectively reduce the degree of pyrolysis agglomeration, make pyrolysis sufficient, effectively remove impurities in the positive electrode powder, and improve the purity of the recovered positive electrode powder.
根据本发明的一种实施方式，所述四段热解，能够避免锂的挥发，从而有效回收锂。According to an embodiment of the present invention, the four-stage pyrolysis can avoid volatilization of lithium, thereby effectively recovering lithium.
所述热解能够去除粉状物料中残余的溶剂、水分和废料中原本含有的聚偏氟乙烯(PVDF)、 导电剂。The pyrolysis can remove the residual solvent, moisture in the powdery material, polyvinylidene fluoride (PVDF) and conductive agent originally contained in the waste.
根据本发明的一种实施方式，所述第二浆料的固含量为20％～40％。According to one embodiment of the present invention, the solid content of the second slurry is 20%-40%.
在浆料回收过程中，固含量对产能影响较大，固含量过低则浆料中液体含量较多，导致每次压滤滤饼较少；固含量过高，则絮凝分散效果差，固液分离不明显，在压滤时液体不能有效的从固体中分离出来，导致滤饼含水量大，干燥时造成粘壁、结块、烘干时间长、能耗大、生产效率低下等后果。In the process of slurry recycling, the solid content has a great influence on the production capacity. If the solid content is too low, the liquid content in the slurry will be more, resulting in less filter cakes for each pressing filter; if the solid content is too high, the flocculation and dispersion effect will be poor, and the solid The liquid separation is not obvious, and the liquid cannot be effectively separated from the solid during the filter press, resulting in a large water content in the filter cake, resulting in wall sticking, agglomeration, long drying time, high energy consumption, and low production efficiency during drying.
将含有塑料、布条等异物的废弃浆料进行撕碎后，通过气泡鼓将异物与废弃浆料分离，并将废弃浆料进行初步破碎，然后通过逐级溢流、气泡破碎分散，可有效控制制得的浆液的固含量以及颗粒大小，使浆液的固含量保持在20％～40％之间，保证后续絮凝、压滤效果，并保证产能。After shredding the waste slurry containing foreign matter such as plastics and cloth strips, the foreign matter is separated from the waste slurry through the bubble drum, and the waste slurry is initially crushed, and then dispersed through gradual overflow and bubble crushing, which can effectively The solid content and particle size of the prepared slurry are controlled to keep the solid content of the slurry between 20% and 40%, so as to ensure the effect of subsequent flocculation and pressure filtration, as well as the production capacity.
所述方法，可实现连续地、大批量处理废锂电池浆料，简化浆料回收工艺。并将正极材料和溶剂有效分离回收利用，降低回收成本，整个过程环保节能，便于后期对正极粉末进行处理，回收得到的正极粉末中Ni、Co、Mn、Li金属总含量在50％以上，具有很大的回收价值。其中，溶剂优选为NMP。The method can realize continuous and large-scale treatment of waste lithium battery slurry, and simplify the slurry recycling process. The positive electrode material and solvent are effectively separated and recycled to reduce recycling costs. The whole process is environmentally friendly and energy-saving, which is convenient for later processing of the positive electrode powder. The total content of Ni, Co, Mn, and Li metals in the recovered positive electrode powder is more than 50%. Great recycling value. Among them, the solvent is preferably NMP.
为了解决所述第二个技术问题，本发明采用的技术方案为：In order to solve the second technical problem, the technical solution adopted in the present invention is:
使用如所述的方法进行正极材料回收的装置，A device for positive electrode material recovery using the method as described,
包括依次连接的第一破碎机、气泡破碎机、搅拌釜、压滤机、双锥干燥设备、精馏塔、第二破碎机和热解炉；Including the first crusher, bubble crusher, stirring tank, filter press, double-cone drying equipment, rectification tower, second crusher and pyrolysis furnace connected in sequence;
所述搅拌釜和精馏塔之间连接配制罐；A preparation tank is connected between the stirred tank and the rectifying tower;
所述双锥干燥设备与所述精馏塔之间连接冷凝设备；Condensing equipment is connected between the double-cone drying equipment and the rectifying tower;
所述精馏塔连接储液罐；The rectifying tower is connected with a liquid storage tank;
所述热解炉连接尾气处理设备。The pyrolysis furnace is connected with tail gas treatment equipment.
根据本发明的一种实施方式，所述第一破碎机为双轴撕碎机，所述第二破碎机为双轴撕碎机。According to an embodiment of the present invention, the first crusher is a double-shaft shredder, and the second crusher is a double-shaft shredder.
根据本发明的一种实施方式，所述双锥干燥设备内设有两个温区。According to an embodiment of the present invention, the double-cone drying equipment is provided with two temperature zones.
根据本发明的一种实施方式，所述热解炉为多段加热式回转窑。According to one embodiment of the present invention, the pyrolysis furnace is a multi-stage heating rotary kiln.
根据本发明的一种实施方式，所述第一破碎机的出料端通过传输机与所述气泡破碎机的进料端连接，传输机用于将经所述第一破碎机撕碎的废弃浆料传送至所述气泡破碎机内，传输机由所述第一破碎机出料端至所述气泡破碎机进料端向上倾斜设置，且传输机上的传输带上间隔均匀地设置有若干隔板，防止撕碎浆料在传送过程中滑落。According to an embodiment of the present invention, the discharge end of the first crusher is connected to the feed end of the bubble crusher through a conveyor, and the conveyor is used to remove the waste materials shredded by the first crusher. The slurry is sent to the bubble breaker, and the conveyor is set upwardly from the discharge end of the first crusher to the feed end of the bubble breaker, and the conveyor belt on the conveyor is evenly spaced with a number of spacers. The board prevents the shredded slurry from slipping during the conveying process.
根据本发明的一种实施方式，所述配制罐用于配制絮凝剂溶液。According to one embodiment of the present invention, the preparation tank is used for preparing a flocculant solution.
根据本发明的一种实施方式，所述气泡破碎机包括传送带、清洗区、破碎区和浆料池；According to one embodiment of the present invention, the air bubble breaker includes a conveyor belt, a cleaning area, a crushing area and a slurry tank;
所述传送带一端位于所述第一破碎机出料口下方，另一端位于所述气泡破碎机出料口；One end of the conveyor belt is located below the discharge port of the first crusher, and the other end is located at the discharge port of the bubble crusher;
经过所述清洗区的所述传送带上设有若干出料孔，所述出料孔中落下的所述第一浆料进入到出料孔下方的所述清洗区中。Several discharge holes are provided on the conveyor belt passing through the cleaning area, and the first slurry falling from the discharge holes enters into the cleaning area below the discharge holes.
根据本发明的一种实施方式，所述传送带上设置等距隔板，防止破碎浆料在输送过程中滑落，该传送带通过电机和链条循环运转。According to one embodiment of the present invention, equidistant partitions are arranged on the conveyor belt to prevent the crushed slurry from slipping during conveyance, and the conveyor belt circulates through a motor and a chain.
根据本发明的一种实施方式，所述气泡破碎机底部设有气泡鼓，传送带上开设有若干个出料孔，清洗后的浆料通过出料孔从传送带上落入到传送带下方所述清洗区，然后再落入浆料池内，清洗干净的碎布、塑料等通过传送带输送至出口并落至收渣桶内。According to one embodiment of the present invention, the bottom of the bubble breaker is provided with a bubble drum, and several discharge holes are opened on the conveyor belt, and the cleaned slurry falls from the conveyor belt to the bottom of the conveyor belt through the discharge holes. area, and then fall into the slurry tank, and the cleaned rags, plastics, etc. are transported to the outlet through the conveyor belt and fall into the slag collection barrel.
所述技术方案中的一个技术方案至少具有如下优点或有益效果之一：One of the technical solutions has at least one of the following advantages or beneficial effects:
1.将含有塑料、布条等异物的废弃浆料进行撕碎后，通过气泡鼓将异物与废弃浆料分离，并将废弃浆料进行初步破碎，然后通过逐级溢流、气泡破碎分散，可有效控制制得的浆液的固含量以及颗粒大小，使浆液的固含量保持在20％～40％之间，保证后续絮凝、压滤效果，并保证产能；1. After shredding the waste slurry containing foreign matter such as plastics and cloth strips, the foreign matter is separated from the waste slurry through a bubble drum, and the waste slurry is initially crushed, and then dispersed through gradual overflow and bubble crushing. It can effectively control the solid content and particle size of the prepared slurry, so that the solid content of the slurry can be kept between 20% and 40%, ensuring the effect of subsequent flocculation and filter pressing, and ensuring production capacity;
2.所述方法中，采用了多段热解，可减少热解过程中溶剂的分解，从而减少尾气的产生，并可对溶剂进行回收利用，节约成本。此外，多段热解可有效降低热解结块程度，使热解充分，有效去除正极粉末中的杂质，提高回收得到的正极粉末的纯度。2. In the method, multi-stage pyrolysis is adopted, which can reduce the decomposition of the solvent in the pyrolysis process, thereby reducing the generation of tail gas, and can recycle the solvent to save costs. In addition, multi-stage pyrolysis can effectively reduce the degree of pyrolysis agglomeration, make pyrolysis sufficient, effectively remove impurities in the positive electrode powder, and improve the purity of the recovered positive electrode powder.
3.所述方法中，浆料压滤及滤饼双锥真空干燥阶段可分离回收98％以上的溶剂，回收的溶剂通过常压精馏达到一定浓度可对外出售，创造收益，仅有不到2％的溶剂进入热处理阶段，大大减轻尾气处理负担，且回收得到的粉末完全满足浸出工序要求；3. In the method, more than 98% of the solvent can be separated and recovered in the stage of slurry press filtration and double-cone vacuum drying of the filter cake, and the recovered solvent can be sold to the outside world through atmospheric distillation to a certain concentration, creating income, and only less than 2% of the solvent enters the heat treatment stage, which greatly reduces the burden of tail gas treatment, and the recovered powder fully meets the requirements of the leaching process;
4.所述方法，可实现连续地、大批量处理废锂电池浆料，简化了浆料回收工艺。并将正极材料和溶剂有效分离回收利用，降低回收成本，整个过程环保节能，便于后期对正极粉末进行处理，回收得到的正极粉末中Ni、Co、Mn、Li金属总含量在50％以上，具有很大的回收价值。4. The method can realize continuous and large-scale processing of waste lithium battery slurry, and simplifies the slurry recycling process. The positive electrode material and solvent are effectively separated and recycled to reduce recycling costs. The whole process is environmentally friendly and energy-saving, which is convenient for later processing of the positive electrode powder. The total content of Ni, Co, Mn, and Li metals in the recovered positive electrode powder is more than 50%. Great recycling value.
附图说明Description of drawings
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention, and the schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations to the present invention.
图1为实施例1从锂电池浆料中回收正极材料的方法的工艺流程图；Fig. 1 is the process flow diagram of the method for recovering positive electrode material from lithium battery slurry in embodiment 1;
图2为实施例5正极材料回收的装置的结构图；Fig. 2 is the structural diagram of the device of embodiment 5 anode material recovery;
图3实施例5气泡破碎机结构图。Fig. 3 is the structural diagram of the air bubble breaker in Example 5.
附图标记：Reference signs:
100-第一破碎机，200-气泡破碎机，210-清洗区，220-传送带，230-浆料池，240-破碎区，250-溢流板，260-收渣桶，300-搅拌釜，400-配制罐，500-压滤机，600-冷凝设备，700-双锥干燥设备，800-精馏塔，900-储液罐，1000-第二破碎机，1100-尾气处理设备，1200-热解炉，1300-包装机。100-first crusher, 200-bubble crusher, 210-cleaning area, 220-conveyor belt, 230-slurry pool, 240-crushing area, 250-overflow plate, 260-slag collecting bucket, 300-stirring tank, 400-preparation tank, 500-filter press, 600-condensing equipment, 700-double cone drying equipment, 800-rectification tower, 900-liquid storage tank, 1000-second crusher, 1100-tail gas treatment equipment, 1200- Pyrolysis furnace, 1300-packing machine.
具体实施方式Detailed ways
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。Embodiments of the present invention are described in detail below, examples of which are shown in the drawings, wherein the same or similar reference numerals designate the same or similar elements or elements having the same or similar functions throughout.
下面通过参考附图描述的实施例是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。The embodiments described below by referring to the figures are exemplary only for explaining the present invention and should not be construed as limiting the present invention.
在本发明的描述中，如果有描述到第一、第二、第三等只是用于区分技术特征为目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量或者隐含指明所指示的技术特征的先后关系。In the description of the present invention, if the first, second, third, etc. are described only for the purpose of distinguishing technical features, it cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features Or implicitly indicate the sequence relationship of the indicated technical features.
在本发明的描述中，需要理解的是，涉及到方位描述，例如上、下、左、右等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。In the description of the present invention, it should be understood that the orientation descriptions, such as the orientation or positional relationship indicated by up, down, left, right, etc., are based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present invention. The invention and the simplified description do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operate in a specific orientation, and thus should not be construed as limiting the present invention.
本发明的描述中，需要说明的是，除非另有明确的限定，设置、安装、连接等词语应做广义理解，所属技术领域技术人员可以结合技术方案的具体内容合理确定词语在本发明中的具体含义。In the description of the present invention, it should be noted that unless otherwise clearly defined, words such as setting, installation, and connection should be understood in a broad sense, and those skilled in the art can reasonably determine the meaning of words in the present invention in combination with the specific content of the technical solution. Concrete meaning.
实施例中浓度为70％～90％的NMP溶液，为NMP与水的混合溶剂。The NMP solution with a concentration of 70% to 90% in the examples is a mixed solvent of NMP and water.
实施例1Example 1
从锂电池浆料中回收正极材料的方法，包括以下步骤：The method for recovering positive electrode material from lithium battery slurry comprises the following steps:
S1：取1000L含有塑料、布条等异物的废弃浆料在双轴撕碎机中进行撕碎，A轴破碎转速15r/min，B轴破碎转速25r/min；S1: Take 1000L of waste slurry containing foreign matter such as plastics and cloth strips and shred it in a double-shaft shredder. The A-axis crushing speed is 15r/min, and the B-axis crushing speed is 25r/min;
S2：撕碎后的废弃浆料与2000L浓度为70％～85％的NMP溶液混合，然后进行气泡破碎，气泡破碎压力为0.4Mpa，以将异物上粘附的废弃浆料从异物上剥落下来，并将废弃浆料进行破碎，再通过逐级溢流进一步破碎；S2: The shredded waste slurry is mixed with 2000L of NMP solution with a concentration of 70% to 85%, and then the bubbles are broken, and the pressure of the bubble break is 0.4Mpa, so as to peel off the waste slurry adhered to the foreign matter from the foreign matter , and crush the waste slurry, and then further crush it through step-by-step overflow;
S3：以硫酸铁作为絮凝剂，以浆液与絮凝剂之间的体积比为1000：5进行分散搅拌絮凝，其中搅拌速度为20r/min，分散速度为1000r/min，分散时间为30min；S3: Using ferric sulfate as flocculant, the volume ratio between slurry and flocculant is 1000:5 for dispersion stirring and flocculation, wherein the stirring speed is 20r/min, the dispersion speed is 1000r/min, and the dispersion time is 30min;
S4：在压滤压力为0.2Mpa下，对絮凝后的浆液进行挤压压滤30min，得到滤饼和滤液，滤液为NMP与水的混合溶液，通过精馏将NMP和废水进行分离，废水作为回用水与絮凝剂混合配制絮凝剂溶液；S4: Under the filter pressure of 0.2Mpa, squeeze and filter the flocculated slurry for 30 minutes to obtain filter cake and filtrate. The filtrate is a mixed solution of NMP and water. NMP and waste water are separated by rectification, and the waste water is used as The recycled water is mixed with the flocculant to prepare the flocculant solution;
S5：采用两段干燥对滤饼进行干燥得到块状固体干料，第一段干燥温度为100℃，干燥时间2h，第二段干燥温度为160℃，干燥时间6h；S5: Two-stage drying is used to dry the filter cake to obtain a block solid dry material. The drying temperature of the first stage is 100°C, and the drying time is 2h; the drying temperature of the second stage is 160°C, and the drying time is 6h;
S6：对块状固体干料进行破碎处理得到粉状物料，增大热解接触面积；S6: Crushing the bulk solid dry material to obtain powdery material, increasing the pyrolysis contact area;
S7：采用4段热解对粉状物料进行热解，第一段热解温度300℃，第二段热解温度400℃，第三段热解温度400℃，第四段热解温度260℃，以制得成品粉末材料，热解过程中产生的废气经尾气处理后排放；S7: The powdery material is pyrolyzed by 4-stage pyrolysis, the pyrolysis temperature of the first stage is 300°C, the pyrolysis temperature of the second stage is 400°C, the pyrolysis temperature of the third stage is 400°C, and the pyrolysis temperature of the fourth stage is 260°C , to produce finished powder materials, and the exhaust gas generated during the pyrolysis process is discharged after tail gas treatment;
S8：将制得的成品粉末材料打包。S8: packing the finished powder material.
实施例2Example 2
从锂电池浆料中回收正极材料的方法，包括以下步骤：The method for recovering positive electrode material from lithium battery slurry comprises the following steps:
S1：取2000L含有塑料、布条等异物的废弃浆料在双轴撕碎机中进行撕碎，A轴破碎转速25r/min，B轴破碎转速15r/min；S1: Take 2000L of waste slurry containing foreign matter such as plastics and cloth strips and shred it in a double-shaft shredder. The A-axis crushing speed is 25r/min, and the B-axis crushing speed is 15r/min;
S2：撕碎后的废弃浆料与1000L浓度为70％～90％的NMP溶液混合，然后进行气泡破碎，气泡破碎压力为0.8Mpa，以将异物上粘附的废弃浆料从异物上剥落下来，并将废弃浆料进行破碎，再通过逐级溢流破碎进一步将废弃浆料破碎为尺寸大小、固含量满足要求的浆液；S2: The shredded waste slurry is mixed with 1000L of NMP solution with a concentration of 70% to 90%, and then the bubbles are broken, and the pressure of the bubble break is 0.8Mpa, so as to peel off the waste slurry adhered to the foreign matter from the foreign matter , and crush the waste slurry, and then further crush the waste slurry into a slurry with a size and a solid content that meets the requirements through step-by-step overflow crushing;
S3：以硫酸铁作为絮凝剂，以浆液与絮凝剂之间的体积比为1000:20进行分散搅拌絮凝，其中搅拌速度为50r/min，分散速度为1600r/min，分散时间为10min；S3: Using ferric sulfate as flocculant, the volume ratio between slurry and flocculant is 1000:20 for dispersion stirring and flocculation, wherein the stirring speed is 50r/min, the dispersion speed is 1600r/min, and the dispersion time is 10min;
S4：在压滤压力为0.5Mpa下，对絮凝后的浆液进行挤压压滤10min，得到滤饼和滤液，滤液为NMP与水的混合溶液，通过精馏将NMP和废水进行分离，废水作为回用水与絮凝剂混合配制絮凝剂溶液；S4: Under the filter pressure of 0.5Mpa, squeeze and filter the flocculated slurry for 10 minutes to obtain the filter cake and filtrate, the filtrate is a mixed solution of NMP and water, and the NMP and waste water are separated by rectification, and the waste water is used as The recycled water is mixed with the flocculant to prepare the flocculant solution;
S5：采用两段干燥对滤饼进行干燥得到块状固体干料，第一段干燥温度为160℃，干燥时间0.5h，第二段干燥温度为220℃，干燥时间2h；S5: Two-stage drying is used to dry the filter cake to obtain massive solid dry material. The drying temperature of the first stage is 160°C, and the drying time is 0.5h; the drying temperature of the second stage is 220°C, and the drying time is 2h;
S6：对干燥后的滤饼进行破碎得到粉状物料，增大热解接触面积；S6: crushing the dried filter cake to obtain powdery material, increasing the pyrolysis contact area;
S7：采用4段热解对粉状物料进行热解，第一段热解温度360℃，第二段热解温度600℃，第三段热解温度600℃，第四段热解温度320℃，以制得成品粉末材料，热解过程中产生的废气经尾气处理后排放；S7: The powdery material is pyrolyzed by 4-stage pyrolysis, the pyrolysis temperature of the first stage is 360°C, the pyrolysis temperature of the second stage is 600°C, the pyrolysis temperature of the third stage is 600°C, and the pyrolysis temperature of the fourth stage is 320°C , to produce finished powder materials, and the exhaust gas generated during the pyrolysis process is discharged after tail gas treatment;
S8：将制得的成品粉末材料打包。S8: packing the finished powder material.
实施例3Example 3
从锂电池浆料中回收正极材料的方法，包括以下步骤：The method for recovering positive electrode material from lithium battery slurry comprises the following steps:
S1：取1500L含有塑料、布条等异物的废弃浆料在双轴撕碎机中进行撕碎，A轴破碎转速20r/min，B轴破碎转速20r/min；S1: Take 1500L of waste slurry containing foreign matter such as plastics and cloth strips and shred it in a double-shaft shredder. The A-axis crushing speed is 20r/min, and the B-axis crushing speed is 20r/min;
S2：撕碎后的废弃浆料与1500L浓度为70％～85％的NMP溶液混合，然后进行气泡破碎，气泡破碎压力为0.6Mpa，以将异物上粘附的废弃浆料从异物上脱落下来，并将废弃浆料进行破碎，再通过逐级溢流破碎进一步将废弃浆料破碎为尺寸大小、固含量满足要求的浆液；S2: The shredded waste slurry is mixed with 1500L of NMP solution with a concentration of 70% to 85%, and then the bubbles are crushed. The pressure of the bubble crushing is 0.6Mpa, so as to remove the waste slurry adhering to the foreign matter from the foreign matter. , and crush the waste slurry, and then further crush the waste slurry into a slurry with a size and a solid content that meets the requirements through step-by-step overflow crushing;
S3：以硫酸铁作为絮凝剂，以浆液与絮凝剂之间的体积比为1000:10进行分散搅拌絮凝，其中搅拌速度为30r/min，分散速度为1300r/min，分散时间为20min；S3: Using ferric sulfate as flocculant, the volume ratio between slurry and flocculant is 1000:10 for dispersion stirring and flocculation, wherein the stirring speed is 30r/min, the dispersion speed is 1300r/min, and the dispersion time is 20min;
S4：在压滤压力为0.3Mpa下，对絮凝后的浆液进行挤压压滤20min，得到滤饼和滤液，滤液为NMP与水的混合溶液，通过精馏将NMP和废水进行分离，废水作为回用水与絮凝剂混合配制絮凝剂溶液；S4: Under the filter pressure of 0.3Mpa, squeeze and filter the flocculated slurry for 20 minutes to obtain filter cake and filtrate. The filtrate is a mixed solution of NMP and water. NMP and waste water are separated by rectification, and the waste water is used as The recycled water is mixed with the flocculant to prepare the flocculant solution;
S5：采用两段干燥对滤饼进行干燥得到块状固体干料，第一段干燥温度为130℃，干燥时间1.5h，第二段干燥温度为180℃，干燥时间5h，以降低滤饼含湿率；S5: Two-stage drying is used to dry the filter cake to obtain massive solid dry material. The drying temperature of the first stage is 130°C, and the drying time is 1.5h; the drying temperature of the second stage is 180°C, and the drying time is 5h, so as to reduce the Humidity rate;
S6：对块状固体干料进行破碎得到粉状物料，增大热解接触面积；S6: Crushing the bulk solid dry material to obtain powdery material, increasing the pyrolysis contact area;
S7：采用4段热解对粉状物料进行热解，第一段热解温度320℃，第二段热解温度450℃，第三段热解温度450℃，第四段热解温度280℃，以制得成品粉末材料，热解过程中产生的废气经尾气处理后排放；S7: The powdery material is pyrolyzed by 4-stage pyrolysis, the pyrolysis temperature of the first stage is 320°C, the pyrolysis temperature of the second stage is 450°C, the pyrolysis temperature of the third stage is 450°C, and the pyrolysis temperature of the fourth stage is 280°C , to produce finished powder materials, and the exhaust gas generated during the pyrolysis process is discharged after tail gas treatment;
S8：将制得的成品粉末材料打包。S8: packing the finished powder material.
实施例4Example 4
从锂电池浆料中回收正极材料的方法，包括以下步骤：The method for recovering positive electrode material from lithium battery slurry comprises the following steps:
S1：取1800L含有塑料、布条等异物的废弃浆料在双轴撕碎机中进行撕碎，A轴破碎转速22r/min，B轴破碎转速20r/min；S1: Take 1800L of waste slurry containing foreign matter such as plastics and cloth strips and shred it in a double-shaft shredder. The A-axis crushing speed is 22r/min, and the B-axis crushing speed is 20r/min;
S2：撕碎后的废弃浆料与1200L浓度为70％～90％的NMP溶液混合，然后进行气泡破碎，气泡破碎压力为0.5Mpa，以将异物上粘附的废弃浆料从异物上脱落下来，并将废弃浆料进行破碎，再通过逐级溢流破碎进一步将废弃浆料破碎为尺寸大小、固含量满足要求的浆液；S2: The shredded waste slurry is mixed with 1200L NMP solution with a concentration of 70% to 90%, and then the bubbles are broken, and the pressure of the bubble break is 0.5Mpa, so as to remove the waste slurry adhered to the foreign matter from the foreign matter. , and crush the waste slurry, and then further crush the waste slurry into a slurry with a size and a solid content that meets the requirements through step-by-step overflow crushing;
S3：以硫酸铁和阳离子PAM作为絮凝剂，以浆液与絮凝剂之间的体积比为1000:15进行分散搅拌絮凝，其中搅拌速度为40r/min，分散速度为1500r/min，分散时间为10min；S3: Using ferric sulfate and cationic PAM as flocculant, the volume ratio between slurry and flocculant is 1000:15 for dispersion stirring and flocculation, wherein the stirring speed is 40r/min, the dispersion speed is 1500r/min, and the dispersion time is 10min ;
S4：在压滤压力为0.4Mpa下，对絮凝后的浆液进行挤压压滤25min，得到滤饼和滤液，滤液为NMP与水的混合溶液，通过精馏将NMP和废水进行分离，废水作为回用水与絮凝剂混合配制絮凝剂溶液；S4: Under the filter pressure of 0.4Mpa, squeeze and filter the flocculated slurry for 25 minutes to obtain filter cake and filtrate. The filtrate is a mixed solution of NMP and water. NMP and waste water are separated by rectification, and the waste water is used as The recycled water is mixed with the flocculant to prepare the flocculant solution;
S5：采用两段干燥对滤饼进行干燥得到块状固体干料，第一段干燥温度为140℃，干燥时间1h，第二段干燥温度为200℃，干燥时间4h；S5: Two-stage drying is used to dry the filter cake to obtain massive solid dry material. The drying temperature of the first stage is 140°C, and the drying time is 1h; the drying temperature of the second stage is 200°C, and the drying time is 4h;
S6：对块状固体干料进行破碎处理得到粉状物料，增大热解面积；S6: Crushing the bulk solid dry material to obtain powdery material, increasing the pyrolysis area;
S7：采用4段热解对粉状物料进行热解，第一段热解温度350℃，第二段热解温度500℃，第三段热解温度500℃，第四段热解温度300℃，以制得成品粉末材料，热解过程中产生的废气经尾气处理后排放；S7: The powdery material is pyrolyzed by 4-stage pyrolysis, the pyrolysis temperature of the first stage is 350°C, the pyrolysis temperature of the second stage is 500°C, the pyrolysis temperature of the third stage is 500°C, and the pyrolysis temperature of the fourth stage is 300°C , to produce finished powder materials, and the exhaust gas generated during the pyrolysis process is discharged after tail gas treatment;
S8：将制得的成品粉末材料打包。S8: packing the finished powder material.
实施例5Example 5
所述正极材料回收的装置包括：The device for recovering positive electrode materials includes:
用于撕碎含有塑料、布条等异物的第一破碎机100，第一破碎机100为双轴撕碎机；The first shredder 100 for shredding foreign matter containing plastics, cloth strips, etc., the first shredder 100 is a double-shaft shredder;
气泡破碎机200，双轴撕碎机出料端通过传输机与气泡破碎机200的进料端连接，传输机用于将经撕碎机撕碎的废弃浆料传送至气泡破碎机200内，传输机由双轴撕碎机出料端至气泡破碎机200进料端向上倾斜设置，且传输机上的传输带上间隔均匀地设置有若干隔板，防止撕碎浆料在传送过程中滑落； Bubble breaker 200, the discharge end of the double-shaft shredder is connected to the feed end of the bubble breaker 200 through a conveyor, and the conveyor is used to transfer the waste pulp shredded by the shredder to the bubble breaker 200, The conveyor is set upwards from the discharge end of the double-shaft shredder to the feed end of the bubble crusher 200, and the conveyor belt on the conveyor is evenly spaced with several partitions to prevent the shredded pulp from slipping during the transmission process;
气泡破碎机200包括用于传送撕碎浆料的传送带220、浆料清洗设备和位于其下方的浆料池230；The bubble breaker 200 includes a conveyor belt 220 for conveying the shredded slurry, a slurry cleaning device and a slurry tank 230 below it;
传送带220一端位于撕碎机出料口下方，另一端按一定角度向上延伸至浆料清洗设备出料口，并且传送带220上设置等距隔板，防止破碎浆料在输送过程中滑落；One end of the conveyor belt 220 is located below the discharge port of the shredder, and the other end extends upwards to the discharge port of the pulp cleaning equipment at a certain angle, and equidistant partitions are set on the conveyor belt 220 to prevent the crushed pulp from slipping during conveying;
传送带220通过电机和链条循环运转，传送带220至少一部分位于浆料清洗设备内；The conveyor belt 220 circulates through the motor and the chain, and at least a part of the conveyor belt 220 is located in the slurry cleaning equipment;
气泡破碎机200底部设有气泡鼓，传送带220上开设有若干个出料孔，清洗后的浆料通过出料孔从传送带220上落入到传送带220下方的清洗区210内，然后再落入浆料池230内，清洗干净的碎布、塑料等通过传送带220输送至出口并落至收渣桶260内；Bubble drums are provided at the bottom of the bubble breaker 200, and several discharge holes are provided on the conveyor belt 220. The cleaned slurry falls from the conveyor belt 220 through the discharge holes into the cleaning area 210 below the conveyor belt 220, and then falls into the In the slurry tank 230, cleaned rags, plastics, etc. are conveyed to the outlet through the conveyor belt 220 and fall into the slag collection barrel 260;
逐级溢流破碎步骤中所使用的装置如下：The devices used in the step by step overflow crushing step are as follows:
浆料池230内设有若干个溢流板250，溢流板250将浆料池230划分为多个破碎区240，每个破碎区240内均安装有气泡鼓；A number of overflow plates 250 are arranged in the slurry pool 230, and the overflow plates 250 divide the slurry pool 230 into a plurality of crushing areas 240, and each crushing area 240 is equipped with a bubble drum;
溢流板250与浆料池230顶部之间留有一个供浆料溢流的溢流口，从浆料池230的进料端到出料端设置的溢流板250的高度逐渐降低，使废弃浆料与异物分离，并将废弃浆料逐步破碎为尺寸大小、固含量满足要求的浆液；An overflow port for the overflow of the slurry is left between the overflow plate 250 and the top of the slurry pool 230, and the height of the overflow plate 250 provided at the discharge end from the feed end of the slurry pool 230 gradually decreases, so that The waste slurry is separated from foreign matter, and the waste slurry is gradually broken into a slurry with a size and a solid content that meet the requirements;
与气泡破碎机200连接的搅拌釜300，气泡破碎机200与搅拌釜300之间还设有缓存罐；A stirring tank 300 connected to the bubble breaker 200, and a buffer tank is also arranged between the bubble breaker 200 and the stirring tank 300;
搅拌釜300用于分散搅拌，使浆液中的固体成分充分絮凝实现初步固液分离； Stirring tank 300 is used for dispersing and stirring, so that the solid components in the slurry can be fully flocculated to achieve preliminary solid-liquid separation;
与搅拌釜300连接的配制罐400，配制罐400用于配制絮凝剂溶液；A preparation tank 400 connected to the stirred tank 300, the preparation tank 400 is used to prepare the flocculant solution;
与搅拌釜300连接的压滤机500，压滤机500用于对絮凝后的浆液进行挤压压滤，得滤饼和滤液，滤液为NMP与水的混合溶液；A filter press 500 connected to the stirred tank 300, the filter press 500 is used to squeeze and filter the flocculated slurry to obtain a filter cake and a filtrate, and the filtrate is a mixed solution of NMP and water;
与压滤机500连接的双锥干燥设备700，双锥干燥设备700采用两段式逐步升温干燥，以对滤饼进行干燥得到块状固体干料，降低其含湿率，减轻粘壁、结块现象；The double-cone drying equipment 700 connected with the filter press 500, the double-cone drying equipment 700 adopts a two-stage drying method to gradually increase the temperature to dry the filter cake to obtain a block solid dry material, reduce its moisture content, and reduce sticking to the wall. block phenomenon;
与双锥干燥设备700连接的冷凝设备600，用于对干燥过程中产生的NMP、水蒸气进行冷凝；The condensing equipment 600 connected with the double-cone drying equipment 700 is used to condense NMP and water vapor produced in the drying process;
与双锥干燥设备700连接的第二破碎机1000，用于对干燥后的块状固体干料进行破碎得粉状物料，增大热解接触面积；The second crusher 1000 connected with the double-cone drying equipment 700 is used to crush the dried block solid dry material to obtain powdery material, so as to increase the pyrolysis contact area;
热解炉1200，对破碎后的粉状物料进行热解，除去粘接剂、导电剂等杂质，得到成品粉末材料，热解过程中产生的尾气通过与热解炉1200连通的尾气处理设备1100进行处理后排空，热解炉1200为多段加热式回转窑，物料经逐步升温热解以减少尾气的产生，降低灼失率，减轻粘壁、结块现象；The pyrolysis furnace 1200 pyrolyzes the crushed powdery materials to remove impurities such as binders and conductive agents to obtain finished powder materials. The tail gas generated during the pyrolysis process passes through the tail gas treatment equipment 1100 connected to the pyrolysis furnace 1200 Empty after treatment, the pyrolysis furnace 1200 is a multi-stage heating rotary kiln, and the material is gradually heated and pyrolyzed to reduce the generation of tail gas, reduce the loss on ignition rate, and reduce the phenomenon of sticking to the wall and agglomeration;
包装机1300，用于对制得的成品粉末材料进行打包。The packing machine 1300 is used for packing the finished powder materials.
还包括精馏塔800，精馏塔800的进料端与压滤机500、冷凝设备600连接，压滤过程中及冷凝后的废水、NMP溶液进入精馏塔800进行提纯处理，分离NMP溶液和水，精馏塔800的顶部与配制罐400连通，分离提纯后的水作为回用水进入配制罐400内配制絮凝剂溶液，底部与储液罐900连通，储液罐900用于存储精馏提纯后的NMP溶液。It also includes a rectification tower 800, the feed end of the rectification tower 800 is connected with the filter press 500 and the condensation device 600, and the waste water and NMP solution in the filtration process and after condensation enter the rectification tower 800 for purification and separation of the NMP solution and water, the top of rectification tower 800 communicates with preparation tank 400, the water after separation and purification enters preparation tank 400 as reuse water to prepare flocculant solution, the bottom communicates with liquid storage tank 900, and liquid storage tank 900 is used for storing rectification Purified NMP solution.
对比例1Comparative example 1
从锂电池浆料中回收正极材料的方法，Method for recovering positive electrode material from lithium battery slurry,
包括以下步骤：Include the following steps:
S1：取500L含有塑料、布条等异物的废弃浆料在双轴撕碎机中进行撕碎，A轴破碎转速15r/min，B轴破碎转速25r/min；S1: Take 500L of waste slurry containing foreign matter such as plastics and cloth strips and shred it in a double-shaft shredder. The A-axis crushing speed is 15r/min, and the B-axis crushing speed is 25r/min;
S2：撕碎后的废弃浆料与2500L浓度为70％～85％的NMP溶液混合，然后进行气泡破碎，气泡破碎压力为0.4Mpa，以将异物上粘附的废弃浆料从异物上剥落下来，并将废弃浆料进行破碎，再通过逐级溢流进一步破碎；S2: The shredded waste slurry is mixed with 2500L of NMP solution with a concentration of 70% to 85%, and then the bubbles are crushed. The pressure of the bubble crushing is 0.4Mpa, so as to peel off the waste slurry adhering to the foreign matter from the foreign matter , and crush the waste slurry, and then further crush it through step-by-step overflow;
S3：以硫酸铁作为絮凝剂，以浆液与絮凝剂之间的体积比为1000：5进行分散搅拌絮凝，其中搅拌速度为20r/min，分散速度为1000r/min，分散时间为30min；S3: Using ferric sulfate as flocculant, the volume ratio between slurry and flocculant is 1000:5 for dispersion stirring and flocculation, wherein the stirring speed is 20r/min, the dispersion speed is 1000r/min, and the dispersion time is 30min;
S4：在压滤压力为0.2Mpa下，对絮凝后的浆液进行挤压压滤30min，得到滤饼和滤液，滤液为含水的NMP溶液，通过精馏将NMP和废水进行分离，废水作为回用水与絮凝剂混合配制 絮凝剂溶液；S4: Under the filter pressure of 0.2Mpa, squeeze and filter the flocculated slurry for 30 minutes to obtain the filter cake and filtrate. The filtrate is an aqueous NMP solution, and the NMP and waste water are separated by rectification, and the waste water is used as reused water Mix with flocculant to prepare flocculant solution;
S5：采用两段干燥对滤饼进行干燥得到块状固体干料，第一段干燥温度为100℃，干燥时间2h，第二段干燥温度为160℃，干燥时间6h；S5: Two-stage drying is used to dry the filter cake to obtain a block solid dry material. The drying temperature of the first stage is 100°C, and the drying time is 2h; the drying temperature of the second stage is 160°C, and the drying time is 6h;
S6：对块状固体干料进行破碎处理得到粉状物料，增大热解接触面积；S6: Crushing the bulk solid dry material to obtain powdery material, increasing the pyrolysis contact area;
S7：采用4段热解对粉状物料进行热解，第一段热解温度300℃，第二段热解温度400℃，第三段热解温度400℃，第四段热解温度260℃，以制得成品粉末材料，热解过程中产生的废气经尾气处理后排放；S7: The powdery material is pyrolyzed by 4-stage pyrolysis, the pyrolysis temperature of the first stage is 300°C, the pyrolysis temperature of the second stage is 400°C, the pyrolysis temperature of the third stage is 400°C, and the pyrolysis temperature of the fourth stage is 260°C , to produce finished powder materials, and the exhaust gas generated during the pyrolysis process is discharged after tail gas treatment;
S8：将制得的成品粉末材料打包。S8: packing the finished powder material.
对比例2Comparative example 2
从锂电池浆料中回收正极材料的方法，包括以下步骤：The method for recovering positive electrode material from lithium battery slurry comprises the following steps:
S1：取2500L含有塑料、布条等异物的废弃浆料在双轴撕碎机中进行撕碎，A轴破碎转速25r/min，B轴破碎转速15r/min；S1: Take 2500L of waste slurry containing foreign matter such as plastics and cloth strips and shred it in a double-shaft shredder. The A-axis crushing speed is 25r/min, and the B-axis crushing speed is 15r/min;
S2：撕碎后的废弃浆料与500L浓度为70％～90％的NMP溶液混合，然后进行气泡破碎，气泡破碎压力为0.8Mpa，以将异物上粘附的废弃浆料从异物上剥落下来，并将废弃浆料进行破碎，再通过逐级溢流破碎进一步将废弃浆料破碎为尺寸大小、固含量满足要求的浆液；S2: The shredded waste slurry is mixed with 500L of NMP solution with a concentration of 70% to 90%, and then the bubbles are broken, and the pressure of the bubble break is 0.8Mpa, so as to peel off the waste slurry adhered to the foreign matter from the foreign matter , and crush the waste slurry, and then further crush the waste slurry into a slurry with a size and a solid content that meets the requirements through step-by-step overflow crushing;
S3：以硫酸铁作为絮凝剂，以浆液与絮凝剂之间的体积比为1000:20进行分散搅拌絮凝，其中搅拌速度为50r/min，分散速度为1600r/min，分散时间为10min；S3: Using ferric sulfate as flocculant, the volume ratio between slurry and flocculant is 1000:20 for dispersion stirring and flocculation, wherein the stirring speed is 50r/min, the dispersion speed is 1600r/min, and the dispersion time is 10min;
S4：在压滤压力为0.5Mpa下，对絮凝后的浆液进行挤压压滤10min，得到滤饼和滤液，滤液为含水的NMP溶液，通过精馏将NMP和废水进行分离，废水作为回用水与絮凝剂混合配制絮凝剂溶液；S4: Under the filter pressure of 0.5Mpa, squeeze and filter the flocculated slurry for 10 minutes to obtain the filter cake and filtrate. The filtrate is an aqueous NMP solution, and the NMP and waste water are separated by rectification, and the waste water is used as reused water Mix with flocculant to prepare flocculant solution;
S5：采用两段干燥对滤饼进行干燥得到块状固体干料，第一段干燥温度为160℃，干燥时间0.5h，第二段干燥温度为220℃，干燥时间2h；S5: Two-stage drying is used to dry the filter cake to obtain massive solid dry material. The drying temperature of the first stage is 160°C, and the drying time is 0.5h; the drying temperature of the second stage is 220°C, and the drying time is 2h;
S6：对干燥后的滤饼进行破碎得到粉状物料，增大热解接触面积；S6: crushing the dried filter cake to obtain powdery material, increasing the pyrolysis contact area;
S7：采用4段热解对粉状物料进行热解，第一段热解温度360℃，第二段热解温度600℃，第三段热解温度600℃，第四段热解温度320℃，以制得成品粉末材料，热解过程中产生的废气经尾气处理后排放；S7: The powdery material is pyrolyzed by 4-stage pyrolysis, the pyrolysis temperature of the first stage is 360°C, the pyrolysis temperature of the second stage is 600°C, the pyrolysis temperature of the third stage is 600°C, and the pyrolysis temperature of the fourth stage is 320°C , to produce finished powder materials, and the exhaust gas generated during the pyrolysis process is discharged after tail gas treatment;
S8：将制得的成品粉末材料打包。S8: packing the finished powder material.
性能测试：Performance Testing:
对实施例1～4和对比例1～2制得的成品粉末材料进行测试，测试结果见表1。The finished powder materials prepared in Examples 1-4 and Comparative Examples 1-2 were tested, and the test results are shown in Table 1.
表1实施例1～4回收料各参数情况Table 1 embodiment 1～4 reclaimed material each parameter situation
Figure PCTCN2022116251-appb-000001
Figure PCTCN2022116251-appb-000001
其中：in:
①固含量——步骤S2清洗分散后得到的浆液中固体含量与浆液总量之比；① solid content - the ratio of the solid content in the slurry obtained after washing and dispersing in step S2 to the total amount of the slurry;
②含湿率——压滤后滤饼中液体含量与滤饼总量之比；②Moisture content—the ratio of the liquid content in the filter cake after pressing to the total amount of the filter cake;
③烧失率——相比干燥前，干燥后物料的损失率；③Loss on ignition rate—compared with before drying, the loss rate of the material after drying;
④干燥后粘壁率——干燥后粘壁量占总物料的比率；④ Wall sticking rate after drying - the ratio of the wall sticking amount to the total material after drying;
⑤灼失率——相比热解前，热解后物料的损失率；⑤Ignition loss rate—compared with before pyrolysis, the loss rate of materials after pyrolysis;
⑥热解后粘壁率——热解后粘壁量占总物料的比率；⑥ Wall sticking rate after pyrolysis - the ratio of wall sticking amount to the total material after pyrolysis;
⑦热解后结块情况——肉眼观察热解后热解炉内物料是否结块；⑦Agglomeration after pyrolysis - visually observe whether the material in the pyrolysis furnace is agglomerated after pyrolysis;
⑧Ni、Co、Mn、Ni含量——指热解后得到的正极粉末中Ni、Co、Mn、Li的含量。⑧Ni, Co, Mn, Ni content - refers to the content of Ni, Co, Mn, Li in the positive electrode powder obtained after pyrolysis.
Ni、Co、Mn、Ni含量通过电感耦合等离子体发射光谱仪(IPC-OES)进行检测。The contents of Ni, Co, Mn and Ni were detected by inductively coupled plasma optical emission spectrometer (IPC-OES).
从表1可以看出，实施例1～4清洗分散后的浆液中固含量均在20％～40％之间，可在保证后续絮凝、压滤效果的同时保证产能；含湿率均控制在20％～30％之间，可减轻干燥过程中发 生的粘壁、结块现象，并控制干燥时间，避免干燥时间过长引起的能耗；烧失率控制在4％以下，灼失率控制在3％以下，表明烧失率和灼失率均较小，热解过程中产生的尾气较少，热解比较充分。It can be seen from Table 1 that the solid content in the slurry after cleaning and dispersion of Examples 1 to 4 is between 20% and 40%, which can ensure the production capacity while ensuring the effect of subsequent flocculation and pressure filtration; the moisture content is all controlled at Between 20% and 30%, it can reduce the sticking and agglomeration phenomenon during the drying process, and control the drying time to avoid energy consumption caused by too long drying time; the loss on ignition rate is controlled below 4%, and the loss on ignition rate is controlled Below 3%, it shows that the loss on ignition rate and the loss on ignition rate are both small, and the tail gas produced in the pyrolysis process is less, and the pyrolysis is relatively sufficient.
此外，现有技术中，使用直接焚烧来处理废料，其直接焚烧灼失率为8.5-11.2％。In addition, in the prior art, direct incineration is used to treat waste, and the direct incineration loss on ignition rate is 8.5-11.2%.
热解后得到的正极粉末中Ni、Co、Mn、Li金属总含量在50％以上，表明回收效果好，具有极大的回收价值。The total content of Ni, Co, Mn and Li metals in the positive electrode powder obtained after pyrolysis is more than 50%, which shows that the recovery effect is good and has great recovery value.
以上仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书内容所作的等同变换，或直接或间接运用在相关的技术领域，均同理包括在本发明的专利保护范围内。The above are only examples of the present invention, and are not intended to limit the patent scope of the present invention. All equivalent transformations made by using the content of the description of the present invention, or directly or indirectly used in related technical fields, are equally included in the patent protection of the present invention. within range.

Claims (10)

  1. 一种从锂电池浆料中回收正极材料的方法，其特征在于：A method for recovering positive electrode material from lithium battery slurry, characterized in that:
    包括以下步骤：Include the following steps:
    将废料撕碎，加入溶剂，经气泡破碎后，得到第一浆料；Shred the waste, add a solvent, and get the first slurry after being broken by air bubbles;
    通过出料孔进行筛分；Screening through discharge holes;
    将尺寸小于出料孔直径的第一浆料进行逐级溢流破碎，得到第二浆料；performing stepwise overflow crushing of the first slurry whose size is smaller than the diameter of the discharge hole to obtain the second slurry;
    经絮凝、固液分离后，收集固相部分；After flocculation and solid-liquid separation, the solid phase is collected;
    固相部分经干燥、破碎、热解后，得到正极材料。The solid phase part is dried, crushed and pyrolyzed to obtain the positive electrode material.
  2. 根据权利要求1所述的方法，其特征在于：所述溶剂包括N-甲基吡咯烷酮、丙二醇甲醚醋酸酯、丙二醇甲醚中的至少一种。The method according to claim 1, characterized in that: the solvent comprises at least one of N-methylpyrrolidone, propylene glycol methyl ether acetate, and propylene glycol methyl ether.
  3. 根据权利要求1所述的方法，其特征在于：所述气泡破碎的压力为0.4～0.8Mpa。The method according to claim 1, characterized in that: the pressure at which the bubbles are broken is 0.4-0.8Mpa.
  4. 根据权利要求1所述的方法，其特征在于：所述方法还包括将固液分离后所得的液相中的溶剂回收，得到第一废液，所述第一废液用于配制絮凝剂。The method according to claim 1, characterized in that: the method further comprises recovering the solvent in the liquid phase obtained after solid-liquid separation to obtain a first waste liquid, and the first waste liquid is used to prepare a flocculant.
  5. 根据权利要求1所述的方法，其特征在于：所述干燥分为两段干燥，第一段干燥温度为100～160℃；第二段干燥温度为160～220℃。The method according to claim 1, characterized in that: the drying is divided into two stages of drying, the drying temperature of the first stage is 100-160°C; the drying temperature of the second stage is 160-220°C.
  6. 根据权利要求5所述的方法，其特征在于：所述干燥中挥发的气体经冷凝后、蒸馏，分离溶剂，得到第二废液，所述第二废液用于配制絮凝剂。The method according to claim 5, characterized in that: the volatilized gas in the drying process is condensed, distilled, and the solvent is separated to obtain a second waste liquid, and the second waste liquid is used to prepare a flocculant.
  7. 根据权利要求1所述的方法，其特征在于：所述热解包括多段热解，第一段热解温度为300～360℃，第二段热解温度为400～600℃，第三段热解温度为400～600℃，第四段热解温度为260～320℃。The method according to claim 1, characterized in that: the pyrolysis includes multi-stage pyrolysis, the pyrolysis temperature of the first stage is 300-360°C, the pyrolysis temperature of the second stage is 400-600°C, and the pyrolysis temperature of the third stage is The pyrolysis temperature is 400-600°C, and the fourth-stage pyrolysis temperature is 260-320°C.
  8. 根据权利要求1所述的方法，其特征在于：所述第二浆料的固含量为20％～40％。The method according to claim 1, characterized in that: the solid content of the second slurry is 20%-40%.
  9. 一种正极材料回收的装置，其特征在于：A device for recovering positive electrode materials, characterized in that:
    包括依次连接的第一破碎机(100)、气泡破碎机(200)、搅拌釜(300)、压滤机(500)、双锥干燥设备(700)、精馏塔(800)、第二破碎机(1000)和热解炉(1200)。Including first crusher (100), bubble crusher (200), stirring tank (300), filter press (500), double cone drying equipment (700), rectification tower (800), second crushing machine (1000) and pyrolysis furnace (1200).
  10. 根据权利要求9所述的装置，其特征在于：The device according to claim 9, characterized in that:
    所述气泡破碎机(200)包括传送带(220)、清洗区(210)、破碎区(240)和浆料池(230)；The bubble breaker (200) includes a conveyor belt (220), a cleaning area (210), a crushing area (240) and a slurry tank (230);
    所述传送带(220)一端位于所述第一破碎机(100)出料口下方，另一端位于所述气泡破碎机(200)出料口；One end of the conveyor belt (220) is located below the outlet of the first crusher (100), and the other end is located at the outlet of the bubble crusher (200);
    经过所述清洗区(210)的所述传送带(220)上设有若干出料孔，所述出料孔中落下的所述第一浆料进入到出料孔下方的所述清洗区(210)中。The conveyor belt (220) passing through the cleaning area (210) is provided with several discharge holes, and the first slurry falling from the discharge holes enters the cleaning area (210) below the discharge holes. )middle.
PCT/CN2022/116251 2021-12-21 2022-08-31 Method and device for recovering positive electrode material from lithium battery slurry WO2023116042A1 (en)

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114388921A (en) * 2021-12-21 2022-04-22 广东邦普循环科技有限公司 Method and device for recovering cathode material from lithium battery slurry
CN115472946A (en) * 2022-09-16 2022-12-13 广东邦普循环科技有限公司 Recovery method and application of waste lithium ion battery positive electrode slurry

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104157924A (en) * 2013-12-17 2014-11-19 中航锂电（洛阳）有限公司 Equipment for separating current collector of lithium ion battery from active material on current collector
CN104157925A (en) * 2013-12-17 2014-11-19 中航锂电（洛阳）有限公司 Recycling device and recycling method for lithium ion battery pole piece
CN108461855A (en) * 2018-02-26 2018-08-28 荆门市格林美新材料有限公司 A kind of the dismantling recovery system and dismantling recovery method of waste lithium cell
WO2019205984A1 (en) * 2018-04-27 2019-10-31 Do Fluoride New Energy Tech Co Ltd Method for recycling of positive electrode plates from lithium-ion battery
CN113540602A (en) * 2021-06-22 2021-10-22 广东邦普循环科技有限公司 Processing method and application of scrapped positive electrode slurry
CN113690502A (en) * 2021-07-23 2021-11-23 广东邦普循环科技有限公司 Method for recycling waste battery slurry
CN114388921A (en) * 2021-12-21 2022-04-22 广东邦普循环科技有限公司 Method and device for recovering cathode material from lithium battery slurry

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109786882A (en) * 2019-02-25 2019-05-21 上海毅信环保科技有限公司 A kind of dry-type pulverizing recovery method of waste and old lithium ion battery
CN113745684A (en) * 2021-08-25 2021-12-03 金川集团股份有限公司 Method for recycling anode material of waste lithium iron phosphate battery

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104157924A (en) * 2013-12-17 2014-11-19 中航锂电（洛阳）有限公司 Equipment for separating current collector of lithium ion battery from active material on current collector
CN104157925A (en) * 2013-12-17 2014-11-19 中航锂电（洛阳）有限公司 Recycling device and recycling method for lithium ion battery pole piece
CN108461855A (en) * 2018-02-26 2018-08-28 荆门市格林美新材料有限公司 A kind of the dismantling recovery system and dismantling recovery method of waste lithium cell
WO2019205984A1 (en) * 2018-04-27 2019-10-31 Do Fluoride New Energy Tech Co Ltd Method for recycling of positive electrode plates from lithium-ion battery
CN113540602A (en) * 2021-06-22 2021-10-22 广东邦普循环科技有限公司 Processing method and application of scrapped positive electrode slurry
CN113690502A (en) * 2021-07-23 2021-11-23 广东邦普循环科技有限公司 Method for recycling waste battery slurry
CN114388921A (en) * 2021-12-21 2022-04-22 广东邦普循环科技有限公司 Method and device for recovering cathode material from lithium battery slurry

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