[go: up one dir, main page]

CN111534697B - Method and device for comprehensive recovery of waste lithium-ion batteries by metallurgy - Google Patents

Method and device for comprehensive recovery of waste lithium-ion batteries by metallurgy Download PDF

Info

Publication number
CN111534697B
CN111534697B CN202010520232.5A CN202010520232A CN111534697B CN 111534697 B CN111534697 B CN 111534697B CN 202010520232 A CN202010520232 A CN 202010520232A CN 111534697 B CN111534697 B CN 111534697B
Authority
CN
China
Prior art keywords
unit
lithium
solution
graphite
inlet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010520232.5A
Other languages
Chinese (zh)
Other versions
CN111534697A (en
Inventor
陈学刚
付云枫
苟海鹏
王传龙
余跃
陈宋璇
于传兵
孙宁磊
王玮玮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China ENFI Engineering Corp
Original Assignee
China ENFI Engineering Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China ENFI Engineering Corp filed Critical China ENFI Engineering Corp
Priority to CN202010520232.5A priority Critical patent/CN111534697B/en
Publication of CN111534697A publication Critical patent/CN111534697A/en
Application granted granted Critical
Publication of CN111534697B publication Critical patent/CN111534697B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C22B7/001—Dry processes
    • 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
    • B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
    • B03B9/00—General arrangement of separating plant, e.g. flow sheets
    • B03B9/06—General arrangement of separating plant, e.g. flow sheets specially adapted for refuse
    • 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
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B03C1/02—Magnetic separation acting directly on the substance being separated
    • 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
    • B03D1/14—Flotation machines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • 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
    • 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
    • C22B15/00—Obtaining copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0002—Preliminary treatment
    • 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
    • C22B21/00—Obtaining aluminium
    • 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
    • C22B21/00—Obtaining aluminium
    • C22B21/0007—Preliminary treatment of ores or scrap or any other metal source
    • 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
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • C22B23/021—Obtaining nickel or cobalt by dry processes by reduction in solid state, e.g. by segregation 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • 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
    • Y02W30/52—Mechanical processing of waste for the recovery of materials, e.g. crushing, shredding, separation or disassembly
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

本发明提供了一种废旧锂离子电池的选冶联合综合回收方法及装置。该方法包括：S1，电池火法预处理；S2，预处理产物洗矿分级，得到粗粒级颗粒、中细粒级颗粒、细粒级颗粒和第一部分含锂溶液；S3，磁选各颗粒，得到的磁选精矿为镍钴锰中间产物，粗和中细粒级颗粒的磁选尾矿为铜铝产物，细粒级颗粒的磁选尾即为石墨和黑粉产物；石墨和黑粉产物进行调浆、石墨浮选，得到石墨产品和黑粉；S4，镍钴锰中间产物和黑粉进行还原焙烧，得到焙烧渣；焙烧渣提锂，得到第二部分含锂溶液和水浸渣；S5，合并第一和第二部分含锂溶液，制备锂产品；S6，水浸渣酸浸、除杂。本发明能有效回收废旧锂离子电池中的锂元素和其他各金属及石墨。

The present invention provides a method and device for comprehensive recovery of waste lithium-ion batteries by metallurgy. The method comprises: S1, battery pyrometallurgical pretreatment; S2, ore washing and classification of the pretreatment product to obtain coarse-grained particles, medium-fine-grained particles, fine-grained particles and the first part of lithium-containing solution; S3, magnetic separation of each particle, the magnetic separation concentrate obtained is a nickel-cobalt-manganese intermediate product, the magnetic separation tailings of coarse and medium-fine-grained particles are copper-aluminum products, and the magnetic separation tailings of fine-grained particles are graphite and black powder products; the graphite and black powder products are slurryed and graphite floated to obtain graphite products and black powder; S4, the nickel-cobalt-manganese intermediate product and the black powder are reduced and roasted to obtain roasted slag; lithium is extracted from the roasted slag to obtain the second part of lithium-containing solution and water-leached slag; S5, the first and second parts of lithium-containing solutions are combined to prepare lithium products; S6, acid leaching and impurity removal of water-leached slag. The present invention can effectively recover lithium elements and other metals and graphite in waste lithium-ion batteries.

Description

Dressing and smelting combined comprehensive recovery method and device for waste lithium ion batteries
Technical Field
The invention relates to waste lithium ion battery resource recovery, in particular to a dressing and smelting combined comprehensive recovery method and device for waste lithium ion batteries.
Background
Along with the coming of the scrapped tide of the lithium ion battery, a large amount of recovery processes are developed and applied at a time. At present, the main problems of the waste lithium ion battery recycling process are that the process is mainly focused on recycling of nickel and cobalt with high content and high market price in the waste lithium ion battery, and the recycling attention degree of lithium elements with low content is lower, so that the recycling rate of nickel, cobalt and manganese in most recycling processes is higher, and the recycling rate of lithium is lower. 2. At present, the definition of solid wastes generated in the field of battery recovery is not perfect, the treatment process of a large amount of fluorine-containing and phosphorus-containing diaphragm plastic parts is not perfect, but along with the maturity of the recovery industry, a large amount of solid wastes are subjected to harmless treatment.
CN 109935922a discloses a method for recovering valuable metals from waste lithium ion battery anode materials, which uses low-valence sulfate mixture such as sulfur, sulfide and the like as reducing agent to reduce high-valence compounds in the anode materials, then uses water or weak acid to leach reduction roasting slag, and the leaching solution is used for recovering lithium, and the leaching slag is used for recovering nickel and cobalt after acid leaching. The method is characterized in that low-valence sulfide is used as a reducing agent for reduction roasting, lithium is preferentially extracted after reduction, so that the recovery rate of lithium can be improved, but the reduction degree is difficult to control in the reduction roasting of sulfur or sulfide, the situation of oversulfide is easy to occur, nickel cobalt is roasted into low-valence sulfate, and the difficulty in separating lithium from nickel cobalt is increased.
CN 108264068a discloses a method for treating waste lithium ion power battery positive electrode material by electrochemical method, which uses sulfate and/or bisulfate as electrolyte solution to make reaction in an electrolytic device, the essence of the reaction is that lithium in the positive electrode material is leached out by acidic solution decomposed by electrolytic water.
CN 108767354a discloses a method for treating waste lithium ion battery positive electrode material by using ammonium salt roasting process, after ammonium salt roasting, water immersion is adopted, valuable metals of Ni, co, mn and Li are all transferred into solution, and then recovered from solution.
CN 106505270a also discloses a process for treating the anode material of the waste ternary lithium ion battery by an ammonium salt roasting method, after removing aluminum foil from roasting slag after ammonium salt roasting, leaching with acid to solubilize cobalt and lithium, then precipitating cobalt in the form of cobalt hydroxide by a precipitation method, and finally recovering lithium. The method avoids the extraction process and can effectively reduce the loss of lithium, but has limited applicability to waste lithium ion batteries with complex composition and scattered and difficult types.
Therefore, the problem of low recovery rate exists in the prior art when the lithium element in the waste lithium ion battery is recovered. In addition, at present, a method for comprehensively recovering metals such as lithium, nickel, cobalt, manganese, copper, aluminum and the like and graphite in waste lithium ion batteries is lacking, and the method is not effective for treating phosphorus-containing fluorine-containing diaphragms and plastic parts in batteries.
Disclosure of Invention
The invention mainly aims to provide a dressing and smelting combined comprehensive recovery method and device for waste lithium ion batteries, so as to improve the recovery rate of lithium elements in the waste lithium ion batteries, comprehensively recover metals such as lithium, nickel, cobalt, manganese, copper, aluminum and the like and graphite in the waste lithium ion batteries, and effectively treat phosphorus-containing fluorine-containing diaphragms and plastic parts in the batteries.
According to one aspect of the invention, the combined recovery method for the dressing and smelting of the waste lithium ion battery comprises the following steps of S1, carrying out fire pretreatment on the waste lithium ion battery to obtain a pretreated product, S2, carrying out ore washing classification treatment on the pretreated product to obtain coarse-grain-grade particles, medium-fine-grain-grade particles, fine-grain-grade particles and a first part of lithium-containing solution, wherein the particle size of the coarse-grain-grade particles is larger than that of the medium-fine-grain-grade particles, the particle size of the medium-fine-grain-grade particles is larger than that of the fine-grain-grade particles, S3, carrying out magnetic separation on the coarse-grain-grade particles, the medium-fine-grain-grade particles and the fine-grain-grade particles respectively, obtaining magnetic separation tailings of the coarse-grain-grade particles and the medium-fine-grain-grade particles as copper-aluminum products, carrying out ore washing classification treatment on the pretreated product to obtain a graphite and a black powder product, carrying out size adjustment and graphite floatation treatment on the graphite and a first part of the black powder in sequence, S4, carrying out reduction roasting on the nickel-cobalt-manganese-containing intermediate product and the black powder, carrying out water leaching treatment on the nickel-cobalt-containing solution, carrying out water leaching treatment on the second part of the lithium-containing solution, and carrying out water leaching solution leaching treatment to obtain a second part of lithium-containing solution, and combining the lithium-containing solution, and carrying out water leaching treatment to obtain a second part of the lithium-containing solution, and a second solution, and a step of combining the solution, and a step of obtaining a lithium-containing solution.
Further, in the step S1, the pyrogenic pretreatment process comprises the steps of disassembling and crushing the waste lithium ion batteries to obtain crushed materials, wherein the particle size of the crushed materials is preferably less than 50mm, carrying out low-temperature pyrolysis on the crushed materials in a protective atmosphere at 400-700 ℃ to obtain pretreated products, wherein the low-temperature pyrolysis temperature is preferably 600-650 ℃, more preferably 610-640 ℃, the low-temperature pyrolysis time is preferably 0.5-6 h, and the step S1 further comprises the step of discharging the waste lithium ion batteries before the step of disassembling and crushing the waste lithium ion batteries.
Further, in the step S2, the particle size of the coarse-size particles is larger than 2mm, the particle size of the fine-size particles is smaller than 0.2mm, the particle size of the medium-size particles is between the particle sizes of the coarse-size particles and the fine-size particles, and preferably, in the step S3, the magnetic separation magnetic field intensity of the coarse-size particles, the medium-size particles and the fine-size particles is 40-280 kA/m respectively.
The method comprises the steps of mixing graphite and black powder products in sequence, carrying out graphite flotation, and preparing the graphite and black powder products into flotation pulp with the concentration of 5-35 wt% by using water, and adding a regulator, a graphite collector and a foaming agent into the flotation pulp to carry out graphite flotation to obtain the graphite products and the black powder.
In step S4, the reducing agent adopted in the reduction roasting process is the graphite product obtained in step S3, or the reduction roasting process is carried out in a reducing atmosphere, preferably, the reducing atmosphere is composed of reducing gas and optional inert gas, the reducing gas is one or more of hydrogen, ammonia, methane and sulfur dioxide, the inert gas is nitrogen and/or argon, preferably, the temperature of the reduction roasting process is 400-700 ℃, and the reaction time is 0.5-6 h.
Further, in step S5, lithium in the combined solution is evaporated and crystallized in the form of lithium hydroxide, or carbon dioxide is introduced into the combined solution or soluble carbonate is added to precipitate lithium in the form of lithium carbonate to obtain a lithium product, preferably, before the step of preparing the lithium product by using the combined solution, step S5 further comprises the step of removing impurity ions in the combined solution by using chemical precipitation or ion exchange resin.
Further, in the step S6, the water leaching slag is subjected to acid leaching to obtain acid leaching liquid, the impurity removing step comprises the steps of adjusting the pH value of the acid leaching liquid to be more than 4.2, removing iron impurities and aluminum impurities to obtain an iron and aluminum removing solution, adding fluoride into the iron and aluminum removing solution to remove magnesium impurities to obtain a magnesium removing solution, preferably, the fluoride is sodium fluoride, adding sulfide salt and/or hydrogen sulfide into the magnesium removing solution to remove copper impurities and zinc impurities to obtain a nickel cobalt manganese containing solution product, preferably, the sulfide salt is sodium sulfide, or the impurity removing step comprises the step of extracting the acid leaching liquid by an extracting agent to obtain a nickel cobalt manganese containing solution product, preferably, the extracting agent is a P204 extracting agent.
Further, before the step of acid leaching the water leaching slag, the step S6 further comprises a step of reduction smelting the water leaching slag, preferably, the water leaching slag is subjected to reduction smelting for 0.5-5 h at the temperature of 1200-1600 ℃ to obtain nickel-cobalt-manganese alloy, and then acid leaching and impurity removal are sequentially carried out on the nickel-cobalt-manganese alloy to obtain a nickel-cobalt-manganese containing solution product.
Further, the first flue gas is obtained in the pyrogenic pretreatment step, the second flue gas is obtained in the reduction smelting step, and the recovery method further comprises the steps of secondary combustion, surface cooling, dust removal and tail gas purification on the first flue gas and the second flue gas in sequence.
Further, the waste lithium ion battery is one or more of a waste lithium cobalt oxide battery, a lithium manganate battery, a nickel-manganese binary composite lithium ion battery, a nickel-cobalt binary composite lithium ion battery, a cobalt-manganese binary composite lithium ion battery, a nickel-cobalt-manganese ternary composite lithium ion battery and a nickel-cobalt-aluminum ternary composite lithium ion battery.
According to another aspect of the invention, the invention also provides a dressing and smelting combined comprehensive recovery device of waste lithium ion batteries, which comprises a pyrogenic pretreatment unit, a pretreatment unit and a recovery unit, wherein the pyrogenic pretreatment unit is provided with a waste lithium ion battery inlet and a pretreatment product outlet and is used for carrying out pyrogenic pretreatment on the waste lithium ion batteries to obtain pretreatment products; the ore washing and classifying unit is used for carrying out ore washing and classifying treatment on the pretreated product to obtain coarse-size particles, medium-size particles, fine-size particles and a first part of lithium-containing solution, wherein the particle size of the coarse-size particles is larger than that of the medium-size particles, the particle size of the medium-size particles is larger than that of the fine-size particles, the magnetic separation unit is connected with the outlet of the ore washing and classifying unit and is used for carrying out magnetic separation on the coarse-size particles, the medium-size particles and the fine-size particles respectively to obtain nickel cobalt-manganese intermediate products, coarse-size particle magnetic tailings, medium-size particle magnetic tailings and fine-size particle magnetic tailings, the coarse-size particle magnetic tailings and the medium-size particle magnetic tailings are used as copper-aluminum products, the fine-size particle magnetic tailings are graphite and black powder products, the graphite recovery unit is connected with the outlet of the magnetic separation unit and comprises a pulp mixing unit and a flotation unit which are sequentially connected with each other and is used for carrying out magnetic separation on the graphite and black powder products, the graphite and the pulp mixing unit is used for carrying out magnetic separation on the graphite and the black powder products to obtain the calcined black powder products, the calcined black powder products and the calcined black powder products, the calcined black powder products are obtained by the magnetic separation unit and the calcined black powder unit is used for obtaining the calcined products, the lithium recovery unit is used for preparing a lithium product by adopting a combined solution of the first part of lithium-containing solution and the second part of lithium-containing solution, the acid leaching unit is provided with a water leaching slag inlet, an acid inlet and an acid leaching solution outlet, the water leaching slag inlet is connected with the outlet of the water leaching unit, the acid leaching unit is used for carrying out acid leaching on the water leaching slag to obtain acid leaching solution, the impurity removal unit is connected with the acid leaching solution outlet, and the impurity removal unit is used for removing impurities from the acid leaching solution to obtain a solution product containing nickel cobalt and manganese.
The pyrolysis unit is provided with a broken material inlet, an inert gas inlet and a pretreated product outlet, and the broken material inlet is connected with the broken material outlet.
Further, the pyrogenic pretreatment unit further comprises a discharge unit, the discharge unit is positioned at the upstream of the disassembly and crushing unit and connected with the inlet of the waste lithium ion battery, and the discharge unit is used for carrying out discharge treatment on the waste lithium ion battery.
Further, the graphite recovery unit further comprises a regulator supply unit connected with the flotation unit for supplying the regulator thereto, a graphite collector supply unit connected with the flotation unit for supplying the graphite collector thereto, and a foaming agent supply unit connected with the flotation unit for supplying the foaming agent thereto.
Further, the reduction roasting unit is also provided with a first reducing agent inlet which is connected with an outlet of the flotation unit and is used for taking a graphite product obtained in the graphite flotation process as a reducing agent in the reduction roasting process, or the reduction roasting unit is also provided with a reducing gas inlet, and the recovery device also comprises a reducing gas supply unit which is connected with the reducing gas inlet.
Further, the recovery device also comprises an inert gas supply unit which is respectively connected with the reducing gas inlet and the inert gas inlet of the low-temperature pyrolysis unit.
The lithium recovery unit further comprises a impurity removing agent supply unit for supplying an impurity removing agent, an impurity removing purification unit, a lithium product preparation unit and a lithium product preparation unit, wherein the inlet of the impurity removing purification unit is respectively connected with the outlet of the water leaching unit, the outlet of the ore washing classification unit and the impurity removing agent supply unit, the impurity removing purification unit is used for performing impurity removing reaction on the combined solution of the first part of lithium-containing solution and the second part of lithium-containing solution to obtain an impurity-removed lithium solution, the lithium product preparation unit is connected with the outlet of the impurity removing purification unit, and the lithium product preparation unit is used for performing evaporative crystallization on the impurity-removed lithium solution or precipitating lithium carbonate to obtain a lithium product.
The impurity removing unit comprises a pH adjusting unit, a magnesium removing unit and a copper and zinc removing unit, wherein the pH adjusting unit is connected with an acid leaching solution outlet and is used for adjusting the pH value of the acid leaching solution to be more than 4.2 so as to obtain an iron and aluminum removing solution, the magnesium removing unit is provided with a fluoride inlet and an iron and aluminum removing solution inlet, the iron and aluminum removing solution inlet is connected with the outlet of the pH adjusting unit and is used for removing magnesium impurities in the iron and aluminum removing solution so as to obtain a magnesium removing solution, the copper and zinc removing unit is provided with a magnesium removing solution inlet and a sulfide inlet, the magnesium removing solution inlet is connected with the outlet of the magnesium removing unit, the sulfide inlet is used for introducing sulfide salt and/or hydrogen sulfide, the copper and zinc removing unit is used for removing copper impurities and zinc impurities in the magnesium removing solution so as to obtain a nickel, cobalt and manganese containing solution product, or the impurity removing unit is an extraction impurity removing unit.
Further, the recovery device further comprises a reduction smelting unit, the reduction smelting unit is arranged on a flow path connected with the water leaching unit through a water leaching slag inlet, the reduction smelting unit is further provided with a flux inlet, the reduction smelting unit is used for carrying out reduction smelting on the water leaching slag to obtain nickel-cobalt-manganese alloy, and the acid leaching unit is used for carrying out acid leaching on the nickel-cobalt-manganese alloy to obtain acid leaching liquid.
Further, the pyrometallurgy pretreatment unit is also provided with a first smoke outlet, the reduction smelting unit is also provided with a second smoke outlet, the recovery device further comprises a smoke treatment unit, and the smoke treatment unit is respectively connected with the first smoke outlet and the second smoke outlet.
The invention provides a dressing and smelting combined comprehensive recovery method of a waste lithium ion battery, which can more effectively recover lithium elements in the waste lithium ion battery under a shorter process, comprehensively recover metals such as lithium, nickel, cobalt, manganese, copper, aluminum and the like and graphite in the waste lithium ion battery, and effectively remove phosphorus-containing fluorine-containing diaphragms and plastic parts in the battery by a pyrogenic process.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 shows a flow chart of a dressing and smelting combined comprehensive recovery method of waste lithium ion batteries according to an embodiment of the invention, and
Fig. 2 shows a block diagram of a dressing and smelting combined comprehensive recovery device for waste lithium ion batteries according to an embodiment of the invention.
Wherein the above figures include the following reference numerals:
10. a pyrogenic pretreatment unit; 11, a disassembling and crushing unit, 12, a low-temperature pyrolysis unit, 13, a discharge unit, 20, a washing and classifying unit, 30, a magnetic separation unit, 40, a graphite recovery unit, 41, a slurry mixing unit, 42, a flotation unit, 43, a regulator supply unit, 44, a graphite collector supply unit, 45, a foaming agent supply unit, 50, a reduction roasting unit, 60, a water leaching unit, 70, a lithium recovery unit, 71, a impurity removal agent supply unit, 72, an impurity removal and purification unit, 73, a lithium product preparation unit, 80, an acid leaching unit, 90, an impurity removal unit, 91, a pH adjustment unit, 92, a magnesium removal unit, 93, a copper and zinc removal unit, 100, an inert gas supply unit, 110, a reduction smelting unit, 120 and a flue gas treatment unit.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The application will be described in detail below with reference to the drawings in connection with embodiments.
As described in the background section, the prior art has a problem of low recovery rate as a whole when recovering lithium element in waste lithium ion batteries. In addition, at present, a method for comprehensively recovering metals such as lithium, nickel, cobalt, manganese, copper, aluminum and the like and graphite in waste lithium ion batteries is lacking, and the method is not effective for treating phosphorus-containing fluorine-containing diaphragms and plastic parts in batteries.
The invention provides a dressing and smelting combined comprehensive recovery method of a waste lithium ion battery, which is shown in figure 1 and comprises the following steps of S1, carrying out fire pretreatment on the waste lithium ion battery to obtain a pretreated product, S2, carrying out ore washing and grading treatment on the pretreated product to obtain coarse-grain-grade particles, medium-fine-grade particles, fine-grade particles and a first part of lithium-containing solution, carrying out reduction roasting on the coarse-grain-grade particles with the particle size larger than that of the medium-fine-grade particles, carrying out magnetic separation on the medium-fine-grade particles with the particle size larger than that of the fine-grade particles, S3, respectively carrying out magnetic separation on the coarse-grain-grade particles, the medium-fine-grade particles and the fine-grade particles to obtain magnetic separation concentrates serving as nickel cobalt-manganese intermediate products, taking the magnetic separation tailings of the coarse-grade particles and the medium-fine-grade particles as copper-aluminum products, carrying out slurry mixing and water leaching on the graphite and the black powder products in sequence to obtain a graphite product and a black powder, S4, carrying out reduction roasting on the nickel-cobalt-containing intermediate products and the black powder to obtain a lithium-containing solution, and carrying out water leaching on the second part of lithium-containing solution, and carrying out acid leaching and mixing the second part of lithium-containing solution to obtain a lithium-containing solution, and carrying out acid leaching solution, and mixing the second part of lithium-containing solution, and carrying out acid leaching treatment to obtain a lithium-containing solution, and a second part and a lithium-containing solution, and a lithium-containing solution.
By utilizing the process to treat the waste lithium ion battery, the plastic shell and the phosphorus-containing fluorine-containing diaphragm in the waste lithium ion battery can be effectively decomposed through the fire pretreatment, and meanwhile, nickel, cobalt and manganese can be converted into magnetism from non-magnetism. The lithium ion battery material after the pyrogenic pretreatment mainly comprises nickel cobalt manganese, copper, aluminum, iron and black powder (the black powder comprises graphite which is the original negative electrode material of the battery, carbon generated in the pyrogenic pretreatment process and part of lithium). The pretreatment product is separated into coarse, medium, fine, and fine size particles by wash classification, and a portion of the soluble lithium salt is able to enter the water to form a first portion of the lithium-containing solution. Because the black powder has smaller particle size, the black powder is mainly concentrated in fine-size particles, and the particle size of the rest components is larger, and the black powder is concentrated in coarse-size particles and medium-fine-size particles. The magnetic nickel cobalt manganese in each particle size can be separated through magnetic separation, and part of lithium elements can be entrained in the magnetic separation tailings to obtain a nickel cobalt manganese intermediate product, the main components of the magnetic separation tailings of the coarse particle size particles and the medium fine particle size particles are copper and aluminum, the magnetic separation tailings of the coarse particle size particles and the medium fine particle size particles can be used as copper aluminum products, and the magnetic separation tailings of the fine particle size particles are graphite and black powder products. And (3) sequentially carrying out size mixing and graphite flotation on the graphite and the black powder product, and enriching the graphite to obtain a graphite product, wherein the flotation tailings are the black powder. Secondly, the intermediate product of nickel, cobalt and manganese and the black powder are subjected to reduction roasting, and then water leaching is carried out to extract lithium, and the lithium can be preferentially extracted by virtue of reduction roasting-water leaching due to the different reducibility of lithium, nickel, cobalt and manganese, so that the lithium is enriched, and a second part of lithium-containing solution is formed. Combining the first part of lithium-containing solution and the second part of lithium-containing solution, and then extracting lithium by chemical precipitation, evaporative crystallization and other methods to form a lithium product. And leaching residual water leaching slag after water leaching by acid leaching and removing impurities to obtain a solution product containing nickel, cobalt and manganese.
From the aspect of lithium recovery process, the traditional waste lithium ion battery is a process of recovering nickel, cobalt and manganese and then recovering lithium, the lithium loss is serious (the lithium recovery rate is less than 90% or even lower), the extraction and separation process flow is long, and the material flux is large. According to the invention, according to the difference of reducibility of lithium nickel cobalt manganese, the reduction roasting-leaching is adopted to preferentially extract lithium, so that the recovery rate (more than 98%) of lithium in the waste battery can be effectively improved, the extraction flux is reduced, and the process advantage is obvious. In the whole, the invention adopts the mineral separation-smelting combined process to comprehensively recycle metals such as lithium, nickel, cobalt, manganese, copper, aluminum and the like and graphite in the batteries in the waste lithium ion batteries. Due to the self characteristics of the beneficiation process, valuable components in the waste batteries are separated by the beneficiation process, the comprehensive cost is low, and the separation effect is obvious. In addition, the invention can decompose the plastic shell and the phosphorus-containing fluorine-containing diaphragm in the battery through fire pretreatment, and the obtained flue gas can be subjected to post-treatment.
In a preferred embodiment, in the step S1, the pyrogenic pretreatment process comprises the steps of disassembling and crushing the waste lithium ion batteries to obtain crushed materials, wherein the particle size of the crushed materials is preferably less than 50mm, carrying out low-temperature pyrolysis on the crushed materials in a protective atmosphere at a temperature of 400-700 ℃ to obtain a pretreated product, wherein the low-temperature pyrolysis temperature is preferably 600-650 ℃, more preferably 610-640 ℃, and the low-temperature pyrolysis time is preferably 0.5-6 h. By adopting the process, on one hand, the pyrolysis effect of the plastic shell and the phosphorus-containing fluorine-containing diaphragm can be improved, and on the other hand, nickel, cobalt and manganese can be more fully converted into magnetism, so that the nickel, cobalt and manganese can be more effectively separated in the subsequent magnetic separation process. The specific method for disassembling and crushing is achieved by adopting a common method in the field, preferably, nitrogen is introduced into the disassembling and crushing process to serve as a protective gas, the electric core is prevented from firing in the crushing process, tail gas generated in the crushing process can be treated through a tail gas purifying system, and the tail gas is discharged after reaching standards.
Preferably, before the step of disassembling and crushing the waste lithium ion battery, the step S1 further includes a step of discharging the waste lithium ion battery. When the battery is scrapped, the residual electric quantity has explosion danger in the storage and crushing processes, the explosion danger can be reduced by utilizing the discharging step, and the problems of fire and the like easily caused by the residual electric quantity in the disassembly and crushing processes are avoided.
In a preferred embodiment, in step S2, the coarse fraction particles have a particle size of more than 2mm, the fine fraction particles have a particle size of less than 0.2mm, and the medium fine fraction particles have a particle size between the particle sizes of the coarse fraction particles and the fine fraction particles. The size of each grade of particles is controlled within the range, so that the black powder and metal components (copper, aluminum, nickel cobalt manganese and the like) are more favorably separated, graphite is positioned as fine-fraction particles as possible, and copper, aluminum, nickel cobalt manganese and the like are enriched in coarse-fraction particles and medium-fine-fraction particles.
In order to remove magnetic impurities such as nickel, cobalt, manganese, and the like more sufficiently, in a preferred embodiment, in step S3, the magnetic separation magnetic field strengths of the coarse-size-fraction particles, the medium-size-fraction particles, and the fine-size-fraction particles are 40 to 280ka/m, respectively.
In order to further improve the recovery effect of graphite, in a preferred embodiment, the steps of sequentially carrying out size mixing and graphite floatation on the graphite and black powder products comprise the steps of preparing flotation pulp with the concentration of 5-35 wt% by using water, and sequentially adding a regulator, a graphite collector and a foaming agent into the flotation pulp to carry out graphite floatation to obtain the graphite product and the black powder. Preferably, the graphite collector is a hydrocarbon oil collector, the hydrocarbon oil collector is kerosene and/or diesel oil, preferably, the foaming agent is pine oil and/or methyl isobutyl carbinol, preferably, the regulator is one or more of sodium hydrosulfide, sodium sulfide and ammonium sulfide. The above reagents are selected, and the recovery effect of graphite is better.
Preferably, in step S4, the reducing agent used in the reducing roasting process is the graphite product obtained in step S3, which is favorable for fully utilizing resources. Or the reduction roasting process is carried out under a reducing atmosphere. Preferably, the reducing atmosphere consists of reducing gas and optional inert gas, wherein the reducing gas is one or more of hydrogen, ammonia, methane and sulfur dioxide, the inert gas is nitrogen and/or argon, preferably, the temperature in the reducing roasting process is 400-700 ℃, and the reaction time is 0.5-6 h.
In a preferred embodiment, in step S5, lithium in the combined solution is recovered as lithium hydroxide or lithium carbonate to obtain a lithium product, and in a specific operation, carbon dioxide or soluble carbonate (such as sodium carbonate) may be introduced into the combined solution to precipitate the lithium element as lithium carbonate. Or the lithium hydroxide product can be prepared by an evaporation crystallization mode, so that the recovery rate of lithium is higher, and the treatment efficiency is higher.
In addition, in order to obtain a purer lithium product, the impurity (Al, cu, F, P, etc.) content in the combined solution can be analyzed first, if the impurity content is qualified, lithium hydroxide or lithium carbonate products are prepared from the leaching solution, and if the impurity content is unqualified, the lithium hydroxide or lithium carbonate products are prepared after a purification process, and the purification process can be a chemical precipitation method or an ion exchange resin method for removing impurities.
In a preferred embodiment, in step S6, the water leaching residue is subjected to acid leaching to obtain an acid leaching solution, the impurity removing step comprises the steps of adjusting the pH value of the acid leaching solution to be more than 4.2, removing iron impurities and aluminum impurities to obtain an iron and aluminum removing solution, adding fluoride into the iron and aluminum removing solution to remove magnesium impurities to obtain a magnesium removing solution, preferably, the fluoride is sodium fluoride, adding sulfide salt and/or hydrogen sulfide into the magnesium removing solution to remove copper impurities and zinc impurities to obtain a solution product containing nickel, cobalt and manganese, preferably, the sulfide salt is sodium sulfide, or the impurity removing step comprises the step of extracting the acid leaching solution by an extracting agent to obtain a solution product containing nickel, cobalt and manganese, preferably, the extracting agent is a P204 extracting agent.
In a preferred embodiment, step S6 further comprises a step of reduction smelting the water slag before the step of acid leaching the water slag. Therefore, the reduction smelting process can fully reduce and enrich nickel, cobalt and manganese in the water leaching slag, and the problems of fluorine dispersion and difficult open circuit in the recovery process of the power battery are solved by utilizing the reduction smelting process, so that the smelting slag containing F can be obtained, the partial open circuit of the F element is realized, and the treatment of harmful substances is also considered while the resources are recovered. Preferably, the first flue gas generated in the pyrogenic pretreatment process can be subjected to post-treatment to obtain fluorine-containing gypsum slag, and the fluorine-containing gypsum slag is fed into the reduction smelting process together to be subjected to synergistic treatment, so that the environmental protection of the process is improved. Preferably, the water leaching slag is subjected to reduction smelting for 0.5-5 hours at the temperature of 1200-1600 ℃ to obtain nickel-cobalt-manganese alloy, and then acid leaching and impurity removal are sequentially carried out on the nickel-cobalt-manganese alloy to obtain a solution product containing nickel, cobalt and manganese.
In the actual reduction smelting process, water leaching slag, flux and reducing agent are mixed and then reduced and smelted in a smelting furnace, wherein the specific flux is preferably quartz sand, limestone, dolomite, calcite and the like, and the specific reducing agent is preferably coal, coke, petroleum coke, active carbon and the like. The specific dosage of each reagent can be adjusted according to the actual conditions such as the amount of water leaching slag, and the like, and is not repeated here.
In a preferred embodiment, the first flue gas is obtained in the fire pretreatment step, the second flue gas is obtained in the reduction smelting step, and the recovery method further comprises the steps of secondary combustion, surface cooling, dust removal and tail gas purification on the first flue gas and the second flue gas in sequence, and the tail gas is discharged after reaching the standard. The dust removal process can adopt a high-temperature bag-type dust remover, and the specific tail gas purification step can be one or a combination of more of common waste gas treatment devices such as an alkali absorption device, an active carbon device, a UV photolysis device, a biological filtration purification device and the like.
Preferably, after the solution product containing nickel cobalt manganese is obtained, the nickel cobalt manganese element can be further separated by wet treatment.
The waste lithium ion battery refers to a waste lithium ion battery obtained after safe discharge and/or waste generated in the production process of the lithium ion battery. In a preferred embodiment, the waste lithium ion battery is one or more of a waste lithium cobalt oxide battery, a lithium manganese battery, a nickel-manganese binary composite lithium ion battery, a nickel-cobalt binary composite lithium ion battery, a cobalt-manganese binary composite lithium ion battery, a nickel-cobalt-manganese ternary composite lithium ion battery and a nickel-cobalt-aluminum ternary composite lithium ion battery.
According to another aspect of the present invention, there is also provided a combined recovery device for dressing and smelting a waste lithium ion battery, as shown in fig. 2, the recovery device comprising a fire pretreatment unit 10, a wash classification unit 20, a magnetic separation unit 30, a graphite recovery unit 40, a reduction roasting unit 50, a water leaching unit 60, a lithium recovery unit 70, an acid leaching unit 80, and a impurity removal unit 90, the fire pretreatment unit 10 having a waste lithium ion battery inlet and a pretreatment product outlet, the fire pretreatment unit 10 being used for fire pretreatment of the waste lithium ion battery to obtain a pretreatment product, the wash classification unit 20 having a pretreatment product inlet and a first water inlet, the pretreatment product inlet being connected to the pretreatment product inlet, the wash classification unit 20 being used for subjecting the pretreatment product to a wash classification treatment to obtain coarse fraction particles a, medium fine fraction particles B, medium fine fraction particles C and a first portion of a lithium-containing solution D, and the coarse fraction particles a being larger than the medium fine fraction particles B, the medium fine fraction particles B being larger than the medium fine fraction particles C, the magnetic separation unit being connected to the fine fraction C tailings 30, the fine fraction C being sequentially separated from the fine fraction C and the fine fraction C, and the fine fraction C being subjected to a magnetic separation unit 40, and the magnetic separation unit being sequentially connected to the fine fraction C and the fine fraction C being a magnetic separation unit 40, and the magnetic separation unit being used for obtaining an intermediate fraction concentrate, and a magnetic separation product, the magnetic separation unit being connected to the fine fraction C and the fine fraction 30 being sequentially to be subjected to a magnetic separation unit 41, the slurry mixing unit 41 is used for mixing graphite and black powder products F, the flotation unit 42 is used for carrying out graphite flotation to obtain a graphite product H and black powder J, the reduction roasting unit 50 is respectively connected with the outlet of the magnetic separation unit 30 and the outlet of the flotation unit 42, the reduction roasting unit 50 is used for carrying out reduction roasting on the nickel cobalt manganese intermediate product G and the black powder J to obtain roasting slag, the water leaching unit 60 is provided with a roasting slag inlet and a second water inlet, the roasting slag inlet is connected with the outlet of the reduction roasting unit 50, the water leaching unit 60 is used for leaching lithium from the roasting slag to obtain a second part of lithium-containing solution K and water leaching slag L, the inlet of the lithium recovery unit 70 is respectively connected with the outlet of the water leaching unit 60 and the outlet of the ore washing classification unit 20, the lithium recovery unit 70 is used for carrying out lithium recovery treatment on the combined solution of the first part of lithium-containing solution D and the second part of lithium-containing solution K to obtain a lithium product M, the acid leaching unit 80 is provided with a leaching slag inlet, an acid inlet and an acid leaching outlet, the leaching slag inlet is connected with the outlet of the water leaching unit 60, the acid leaching unit 80 is used for leaching the leaching slag to obtain a second part of lithium-containing solution K, and the impurity removal unit 90 is connected with the nickel-containing solution N to obtain a product.
By utilizing the device to treat the waste lithium ion battery, the plastic shell and the phosphorus-containing fluorine-containing diaphragm in the waste lithium ion battery can be effectively decomposed through the fire pretreatment, and meanwhile, nickel, cobalt and manganese can be converted into magnetism from non-magnetism. The lithium ion battery material after the pyrogenic pretreatment mainly comprises nickel cobalt manganese, copper, aluminum, iron and black powder (the black powder comprises graphite which is the original negative electrode material of the battery, carbon generated in the pyrogenic pretreatment process and part of lithium). The pretreatment product is separated into coarse, medium, fine, and fine size particles by wash classification, and a portion of the soluble lithium salt is able to enter the water to form a first portion of the lithium-containing solution. Because the black powder has smaller particle size, the black powder is mainly concentrated in fine-size particles, and the particle size of the rest components is larger, and the black powder is concentrated in coarse-size particles and medium-fine-size particles. The magnetic nickel cobalt manganese in each particle size can be separated through magnetic separation, and part of lithium elements can be entrained in the magnetic separation tailings to obtain a nickel cobalt manganese intermediate product, the main components of the magnetic separation tailings of the coarse particle size particles and the medium fine particle size particles are copper and aluminum, the magnetic separation tailings of the coarse particle size particles and the medium fine particle size particles can be used as copper aluminum products, and the magnetic separation tailings of the fine particle size particles are graphite and black powder products. And (3) sequentially carrying out size mixing and graphite flotation on the graphite and the black powder product, and enriching the graphite to obtain a graphite product, wherein the flotation tailings are the black powder. Secondly, the intermediate product of nickel, cobalt and manganese and the black powder are subjected to reduction roasting, and then water leaching is carried out to extract lithium, and the lithium can be preferentially extracted by virtue of reduction roasting-water leaching due to the different reducibility of lithium, nickel, cobalt and manganese, so that the lithium is enriched, and a second part of lithium-containing solution is formed. Combining the first portion of the lithium-containing solution and the second portion of the lithium-containing solution, and then extracting lithium by chemical precipitation or evaporative crystallization to form a lithium product. And leaching residual water leaching slag after water leaching by acid leaching and removing impurities to obtain a solution product containing nickel, cobalt and manganese.
From the aspect of lithium recovery process, the traditional waste lithium ion battery is a process of recovering nickel, cobalt and manganese and then recovering lithium, the lithium loss is serious (the lithium recovery rate is less than 90% or even lower), the extraction and separation process flow is long, and the material flux is large. According to the invention, according to the difference of reducibility of lithium nickel cobalt manganese, the reduction roasting-leaching is adopted to preferentially extract lithium, so that the recovery rate (more than 98%) of lithium in the waste battery can be effectively improved, the extraction flux is reduced, and the process advantage is obvious. In the whole, the invention adopts the mineral separation-smelting combined process to comprehensively recycle metals such as lithium, nickel, cobalt, manganese, copper, aluminum and the like and graphite in the batteries in the waste lithium ion batteries. Due to the self characteristics of the beneficiation process, valuable components in the waste batteries are separated by the beneficiation process, the comprehensive cost is low, and the separation effect is obvious. In addition, the invention can decompose the plastic shell and the phosphorus-containing fluorine-containing diaphragm in the battery through fire pretreatment, and the obtained flue gas can be subjected to post-treatment.
In a preferred embodiment, the pyrometallurgical pretreatment unit 10 comprises a disassembly crushing unit 11 and a low-temperature pyrolysis unit 12, wherein the disassembly crushing unit 11 is provided with a waste lithium ion battery inlet and a crushed material outlet, and the low-temperature pyrolysis unit 12 is provided with a crushed material inlet, an inert gas inlet and a pretreated product outlet, and the crushed material inlet is connected with the crushed material outlet. Therefore, the waste lithium ion batteries are disassembled and crushed and then subjected to low-temperature pyrolysis, so that plastic shells and phosphorus-containing fluorine-containing diaphragms in the batteries can be removed by pyrolysis, and preferably, the low-temperature pyrolysis unit 12 is used for performing low-temperature pyrolysis on crushed materials discharged from the disassembly and crushing unit 11 at a temperature of 400-700 ℃ to obtain a pretreatment product.
In a preferred embodiment, the fire pretreatment unit 10 further comprises a discharge unit 13, wherein the discharge unit 13 is located upstream of the disassembly and disruption unit 11 and is connected to the inlet of the waste lithium ion battery, and the discharge unit 13 is used for performing discharge treatment on the waste lithium ion battery. When the battery is scrapped, the residual electric quantity has explosion danger in the storage and crushing processes, the explosion danger can be reduced by utilizing the discharging step, and the problems of fire and the like easily caused by the residual electric quantity in the disassembly and crushing processes are avoided.
In a preferred embodiment, as shown in fig. 1, the graphite recovery unit 40 further includes a regulator supply unit 43, a graphite collector supply unit 44, and a foaming agent supply unit 45, the regulator supply unit 43 being connected to the flotation unit 42 for supplying the graphite regulator thereto, the graphite collector supply unit 44 being connected to the flotation unit 42 for supplying the collector thereto, and the foaming agent supply unit 45 being connected to the flotation unit 42 for supplying the foaming agent thereto. In this way, the graphite product and the black powder after the pulp mixing can be subjected to graphite floatation under the action of the graphite collecting agent, the foaming agent and the regulator, so that the separated graphite can be more fully recovered.
In a preferred embodiment, the reduction roasting unit 50 also has a first reducing agent inlet connected to the outlet of the flotation unit 42 for taking the graphite product obtained in the graphite flotation process as reducing agent in the reduction roasting process, or the reduction roasting unit 50 also has a reducing gas inlet, the recovery device also comprising a reducing gas supply unit connected to the reducing gas inlet. Preferably, the recovery apparatus further includes an inert gas supply unit 100, and the inert gas supply unit 100 is connected to the reducing gas inlet and the inert gas inlet of the low temperature pyrolysis unit 12, respectively. In this way, the inert gas may be introduced into the reduction roasting unit 50 to form a reducing atmosphere together with the first reducing gas, so that the soot and the nickel cobalt manganese intermediate product are subjected to reduction roasting.
In a preferred embodiment, the lithium recovery unit 70 includes a impurity removing agent supply unit 71 for supplying an impurity removing agent, an impurity removing purification unit 72 having inlets respectively connected to an outlet of the water leaching unit 60, an outlet of the ore washing classification unit 20, and the impurity removing agent supply unit 71, the impurity removing purification unit 72 for subjecting a combined solution of the first portion lithium-containing solution and the second portion lithium-containing solution to an impurity removing purification reaction to obtain an impurity removed lithium solution, and a lithium product preparation unit 73 connected to an outlet of the impurity removing purification unit 72, the lithium product preparation unit 73 for subjecting the impurity removed lithium solution to evaporation crystallization or precipitation of lithium carbonate to obtain a lithium product. Preferably, the magnesium removing agent is sodium hydroxide, calcium hydroxide or sodium fluoride, preferably, the calcium removing agent is sodium carbonate or sodium fluoride.
In a preferred embodiment, the impurity removal unit 90 comprises a pH adjustment unit 91 connected with an acid leaching solution outlet, wherein the pH adjustment unit 91 is used for adjusting the pH value of the acid leaching solution to be more than 4.2 so as to obtain an aluminum and iron removal solution, a magnesium removal unit 92 provided with a fluoride inlet and an aluminum and iron removal solution inlet, wherein the aluminum and iron removal solution inlet is connected with the outlet of the pH adjustment unit 91, the magnesium removal unit 92 is used for removing magnesium impurities in the aluminum and iron removal solution so as to obtain a magnesium and nickel removal solution, and a copper and zinc removal unit 93 provided with a magnesium and sulfide inlet, wherein the magnesium and magnesium removal solution inlet is connected with the outlet of the magnesium and/or hydrogen sulfide removal unit 92, and the copper and zinc removal unit 93 is used for removing copper impurities and zinc impurities in the magnesium and nickel-cobalt-manganese containing solution products. Or the impurity removing unit 90 is an extraction impurity removing unit. When an extraction and purification unit is used, the extractant is preferably a P204 extractant.
In a preferred embodiment, the recovery device further comprises a reduction smelting unit 110, the reduction smelting unit 110 being arranged in a flow path with the water leaching residue inlet connected to the water leaching unit 60, and the reduction smelting unit 110 further having a flux inlet, the reduction smelting unit 110 being adapted to perform reduction smelting of the water leaching residue to obtain a nickel cobalt manganese alloy, and the acid leaching unit 80 being adapted to perform acid leaching of the nickel cobalt manganese alloy to obtain a pickling solution. Therefore, the reduction smelting process can fully reduce and enrich nickel, cobalt and manganese in the water leaching slag, and the problems of fluorine dispersion and difficult open circuit in the recovery process of the power battery are solved by utilizing the reduction smelting process, so that the smelting slag containing F can be obtained, the partial open circuit of the F element is realized, and the treatment of harmful substances is also considered while the resources are recovered. Preferably, the first flue gas generated in the pyrogenic pretreatment process can be subjected to post-treatment to obtain fluorine-containing gypsum slag, and the fluorine-containing gypsum slag is fed into the reduction smelting process together to be subjected to synergistic treatment, so that the environmental protection of the process is improved.
More preferably, the reduction smelting unit 110 further has a second reductant inlet for introducing reductant into the reduction smelting unit 110 to complete the reduction smelting of the water-immersed slag.
In order to further increase the innocuity of the process, in a preferred embodiment, the pyrometallurgical pretreatment unit 10 further has a first flue gas outlet, the reduction smelting unit 110 further has a second flue gas outlet, the recovery device further comprises a flue gas treatment unit 120, and the flue gas treatment unit 120 is connected to the first flue gas outlet and the second flue gas outlet, respectively. Preferably, the flue gas treatment unit 120 includes a secondary combustion unit, a surface cooling unit, a dust removal unit, and a tail gas purification unit, which are sequentially connected, and the secondary combustion unit is connected to the first flue gas outlet and the second flue gas outlet, respectively.
The application is described in further detail below in connection with specific examples which are not to be construed as limiting the scope of the application as claimed.
Example 1
The battery adopted in the embodiment is a square ternary lithium ion battery of a certain factory in Hunan.
(1) And (3) treating the waste ternary lithium ion battery by adopting chemical discharge, and carrying out multistage crushing on the discharged battery to be less than 50mm under the nitrogen atmosphere. The crushed battery is subjected to pyrolysis pretreatment for 2 hours in a nitrogen atmosphere at the temperature of 500 ℃ to obtain pyrolysis products, and generated pyrolysis smoke is discharged after secondary combustion, surface cooling, high-temperature cloth bag dust collection and tail gas purification treatment.
(2) Washing and grading the pyrolysis product into three particle sizes of more than 2mm, 0.15-2 mm and less than 0.15mm and lithium-rich solution, and carrying out magnetic separation on the three particle sizes under the condition that the magnetic field strength is 240kA/m to obtain the nickel-cobalt-manganese intermediate product. Magnetic tailings with the particle size of 2mm and the particle size of 0.15-2 mm are used as copper-aluminum products, and the recovery rates are 90.41% and 89.51% respectively. The magnetic tailings with the grain size below 0.15mm are black powder and graphite products, water is used for pulping to form flotation slurry with the concentration of 30wt%, 500g/t of sodium sulfide, 200g/t of diesel oil and 40g/t of pine oil are added into the flotation slurry to carry out graphite flotation, the graphite with the C grade of 91.36% and the recovery rate of 88.59% is obtained through flotation, and the flotation tailings are black powder.
(3) And (3) carrying out reduction roasting on the black powder and the nickel-cobalt-manganese intermediate product for 1h in a hydrogen reducing atmosphere at the temperature of 500 ℃ to obtain reduction roasting slag. And (3) taking water as a leaching agent, leaching roasting slag under the condition of leaching for 1h at the liquid-solid ratio of 3:1 and 80 ℃, and carrying out solid-liquid separation treatment to obtain water leaching slag and lithium-containing leaching liquid. And combining the lithium-containing solution obtained in the beneficiation process and the lithium-containing leaching solution obtained by water leaching, introducing CO 2, and performing evaporative crystallization to obtain a lithium carbonate product, wherein the comprehensive recovery rate of lithium is 98.6%.
(4) The water leaching slag, the flux quartz sand, the limestone and the reducing agent coke are subjected to reduction smelting for 2 hours at 1600 ℃ to obtain nickel-cobalt-manganese alloy and smelting slag, and the smelting slag belongs to harmless slag after high-temperature solidification treatment and can be directly buried. The flue gas generated by reduction smelting is discharged after secondary combustion, a waste heat boiler, surface cooling, high-temperature cloth bag dust collection and tail gas purification and absorption.
(5) The nickel-cobalt-manganese alloy is leached by adopting 5.5mol/L sulfuric acid, the liquid-solid ratio is 5:1, the temperature is 90 ℃ and the condition is 1h, the leaching solution obtained by leaching is subjected to P204 extraction to remove impurities, and the obtained nickel-cobalt-manganese purifying solution can be used as a raw material of a downstream lithium ion battery material production enterprise.
(6) The purity of the obtained product is shown as follows, the recovery rate of copper and aluminum in the copper and aluminum product can reach 90.41 percent, 89.51 percent, the recovery rate of graphite reaches 88.59 percent, the purity of lithium carbonate obtained by wet lithium extraction is 99.7 percent, and the recovery rates of lithium, nickel, cobalt and manganese are respectively 98.6 percent, 99.1 percent, 99.3 percent and 98.7 percent.
Example 2
The battery adopted in the embodiment is a cylindrical 18650 ternary lithium ion battery in Jiangsu certain factory.
(1) And (3) treating the waste ternary lithium ion battery by adopting chemical discharge, and carrying out multistage crushing on the discharged battery to be less than 50mm under the nitrogen atmosphere. The crushed battery is subjected to pyrolysis pretreatment for 3 hours in a nitrogen atmosphere at 600 ℃ to obtain pyrolysis products, and generated pyrolysis smoke is discharged after secondary combustion, surface cooling, high-temperature cloth bag dust collection and tail gas purification treatment.
(2) Washing and grading the pyrolysis product into three particle sizes of more than 3mm, 0.2-3 mm and less than 0.2mm and lithium-rich solution, and carrying out magnetic separation on the three particle sizes respectively under the magnetic field strength of 200kA/m to obtain the nickel-cobalt-manganese intermediate product. Magnetic tailings with the grain sizes of 3mm and 0.2-3 mm are used as copper-aluminum products, and the recovery rates are 89.29% and 90.88% respectively. The magnetic tailings with the grain size below 0.2mm are black powder and graphite products, water is used for pulping to form flotation slurry with the concentration of 15wt%, 400g/t of sodium sulfide, 150g/t of diesel oil and 45g/t of pine oil are added into the flotation slurry to carry out graphite flotation, the graphite with the carbon grade of 92.87% and the recovery rate of 87.46% is obtained through flotation, and the flotation tailings are black powder.
(3) And (3) carrying out reduction roasting on the black powder and the nickel-cobalt-manganese intermediate product for 1.5 hours in a hydrogen reducing atmosphere at the temperature of 450 ℃ to obtain reduction roasting slag. And (3) taking water as a leaching agent, leaching the hydrogen reduction roasting slag under the condition of leaching for 1h at the liquid-solid ratio of 5:1 and 60 ℃, and carrying out solid-liquid separation treatment to obtain water leaching slag and lithium-containing leaching liquid. And combining the lithium-containing solution obtained in the beneficiation process and the lithium-containing leaching solution obtained by water leaching, introducing CO 2, and performing evaporative crystallization to obtain a lithium carbonate product, wherein the comprehensive recovery rate of lithium is 99.6%.
(4) The water leaching slag, the flux quartz sand, the limestone and the reducing agent coal are subjected to reduction smelting for 3 hours at 1500 ℃ to obtain nickel-cobalt alloy and smelting slag, and the smelting slag belongs to harmless slag after high-temperature solidification treatment and can be directly buried. The flue gas generated by reduction smelting is discharged after secondary combustion, a waste heat boiler, surface cooling, high-temperature cloth bag dust collection and tail gas purification and absorption.
(5) The nickel-cobalt alloy is leached by adopting 5mol/L sulfuric acid, the liquid-solid ratio is 6:1, the temperature is 90 ℃ and the condition is 1h, the acid leaching solution obtained by leaching is subjected to P204 extraction to remove impurities, and the obtained nickel-cobalt-manganese purifying solution can be used as a raw material of a downstream lithium ion battery material production enterprise.
(6) The purity of the obtained product is shown as follows, the recovery rate of copper and aluminum in the copper and aluminum product can reach 89.29 percent, 90.88 percent, the recovery rate of graphite reaches 87.46 percent, the purity of lithium carbonate obtained by wet lithium extraction is 99.8 percent, and the recovery rates of lithium, nickel, cobalt and manganese are respectively 99.6 percent, 99.3 percent, 99.4 percent and 98.9 percent.
Example 3
The difference from example 1 is that there is no reduction smelting step, the specific process is as follows,
(1) And (3) treating the waste ternary lithium ion battery by adopting chemical discharge, and carrying out multistage crushing on the discharged battery to be less than 50mm under the nitrogen atmosphere. The crushed battery is subjected to pyrolysis pretreatment for 2 hours in a nitrogen atmosphere at the temperature of 500 ℃ to obtain pyrolysis products, and generated pyrolysis smoke is discharged after secondary combustion, surface cooling, high-temperature cloth bag dust collection and tail gas purification treatment.
(2) Washing and grading the pyrolysis product into three particle sizes of more than 2mm, 0.15-2 mm and less than 0.15mm and lithium-rich solution, and carrying out magnetic separation on the three particle sizes under the condition that the magnetic field strength is 240kA/m to obtain the nickel-cobalt-manganese intermediate product. Magnetic tailings with the particle size of 2mm and the particle size of 0.15-2 mm are used as copper-aluminum products, and the recovery rates are 90.37% and 89.15% respectively. The magnetic tailings with the grain size below 0.15mm are black powder and graphite products, water is used for pulping to form flotation slurry with the concentration of 30wt%, 200g/t of sodium sulfide, 200g/t of diesel oil and 40g/t of pine oil are added into the flotation slurry to carry out graphite flotation, the graphite with the grade C of 91.42% and the recovery rate of 88.93% is obtained through flotation, and the flotation tailings are black powder.
(3) And (3) carrying out reduction roasting on the black powder and the nickel-cobalt-manganese intermediate product for 1h in a hydrogen reducing atmosphere at the temperature of 500 ℃ to obtain reduction roasting slag. And (3) taking water as a leaching agent, leaching roasting slag under the condition of leaching for 1h at the liquid-solid ratio of 3:1 and 80 ℃, and carrying out solid-liquid separation treatment to obtain water leaching slag and lithium-containing leaching liquid. And combining the lithium-containing solution obtained in the beneficiation process and the lithium-containing leaching solution obtained by water leaching, introducing CO 2, and performing evaporative crystallization to obtain a lithium carbonate product, wherein the comprehensive recovery rate of lithium is 98.6%.
(4) Leaching the water leaching slag obtained in the step (3) by using sulfuric acid with the concentration of 4.6mol/L to obtain leaching liquid containing nickel, cobalt and manganese. Neutralizing precipitation to remove iron and aluminum (pH value is 4.4), removing copper and zinc by sodium sulfide, and removing magnesium by sodium fluoride to obtain a purifying liquid, wherein the purifying liquid is a solution product containing nickel, cobalt and manganese.
(5) The purity of the obtained product is shown as follows, the recovery rate of copper and aluminum in the copper and aluminum product can reach 90.37 percent, 89.15 percent, the recovery rate of graphite reaches 88.93 percent, the purity of lithium carbonate obtained by wet lithium extraction is 99.7 percent, and the recovery rates of lithium, nickel, cobalt and manganese are respectively 98.5 percent, 98.9 percent, 98.2 percent and 98.1 percent.
Example 4
The battery adopted in the embodiment is a cylindrical 18650 ternary lithium ion battery in a factory in Zhejiang.
(1) And (3) treating the waste ternary lithium ion battery by adopting chemical discharge, and carrying out multistage crushing on the discharged battery under the nitrogen atmosphere. The crushed battery is subjected to pyrolysis pretreatment for 3 hours in a nitrogen atmosphere at 600 ℃ to obtain pyrolysis products, and generated pyrolysis smoke is discharged after secondary combustion, surface cooling, high-temperature cloth bag dust collection and tail gas purification treatment.
(2) The pyrolyzed product is washed and classified into three particle sizes of more than 5mm, 0.45-5 mm and less than 0.45mm and lithium-rich solution, the three particle sizes are respectively subjected to magnetic separation under the magnetic field intensity of 220kA/m to obtain a nickel cobalt manganese intermediate product, and magnetic separation tailings with the particle sizes of more than 5mm and 0.45-5 mm are used as copper aluminum products, and the recovery rates are 92.47% and 90.37% respectively. The magnetic tailings with the grain size below 0.45mm are black powder and graphite products, water is used for pulping to form flotation slurry with the concentration of 10wt%, 1000g/t of sodium sulfide, 200g/t of diesel oil and 40g/t of pine oil are added into the flotation slurry to carry out graphite flotation, the graphite with the carbon grade of 91.17% and the recovery rate of 88.10% is obtained through flotation, and the flotation tailings are black powder and nickel cobalt manganese intermediate products and enter a subsequent reduction roasting process.
(3) And (3) carrying out reduction roasting on the black powder nickel cobalt manganese intermediate product for 1.5 hours in a hydrogen reducing atmosphere at the temperature of 450 ℃ to obtain reduction roasting slag. And (3) taking water as a leaching agent, leaching the hydrogen reduction roasting slag under the condition of leaching for 1h at the liquid-solid ratio of 4:1 and 80 ℃, and carrying out solid-liquid separation treatment to obtain water leaching slag and lithium-containing leaching liquid. And combining the lithium-rich solution and the lithium-containing leaching solution, introducing CO 2, and performing evaporative crystallization to obtain a lithium carbonate product, wherein the comprehensive recovery rate of lithium is 99.6%.
(4) Leaching the water leaching slag obtained in the step (3) by using sulfuric acid with the concentration of 5mol/L to obtain leaching liquid containing nickel, cobalt and manganese. Neutralizing precipitation to remove iron and aluminum (pH value is 4.6), removing copper and zinc by sodium sulfide, and removing magnesium by sodium fluoride to obtain a purifying liquid, wherein the purifying liquid is a solution product containing nickel, cobalt and manganese.
(5) The purity of the obtained product is shown as follows, the recovery rate of copper and aluminum in the copper and aluminum product can reach 92.47 percent, 90.37 percent, the recovery rate of graphite reaches 88.10 percent, the purity of lithium carbonate obtained by wet lithium extraction is 99.8 percent, and the recovery rates of lithium, nickel, cobalt and manganese are respectively 98.6 percent, 99.3 percent, 99.5 percent and 99.2 percent.
Example 5
The battery adopted in the embodiment is a cylindrical 18650 ternary lithium ion battery in a factory in Zhejiang.
(1) And (3) treating the waste ternary lithium ion battery by adopting chemical discharge, and carrying out multistage crushing on the discharged battery under the nitrogen atmosphere. The crushed battery is subjected to pyrolysis pretreatment for 6 hours in a nitrogen atmosphere at 400 ℃ to obtain pyrolysis products, and generated pyrolysis smoke is discharged after secondary combustion, surface cooling, high-temperature cloth bag dust collection and tail gas purification treatment.
(2) The pyrolyzed product is washed and classified into three particle sizes of more than 5mm, 0.2-5 mm and less than 0.20mm and lithium-rich solution, the three particle sizes are respectively subjected to magnetic separation under the magnetic field intensity of 280kA/m to obtain a nickel cobalt manganese intermediate product, and magnetic separation tailings of more than 20mm and 0.2-5 mm are used as copper aluminum products, and the recovery rates are 93.19% and 91.42% respectively. The magnetic tailings with the grain size below 0.20mm are black powder and graphite products, water is used for pulping to form flotation slurry with the concentration of 5wt%, 1000g/t of sodium sulfide, 200g/t of diesel oil and 40g/t of pine oil are added into the flotation slurry to carry out graphite flotation, the graphite with the carbon grade of 92.82% and the recovery rate of 87.36% is obtained through flotation, and the flotation tailings are black powder and nickel cobalt manganese intermediate products and enter a subsequent reduction roasting process.
(3) And (3) carrying out reduction roasting on the black powder nickel cobalt manganese intermediate product for 1.5 hours in a hydrogen reducing atmosphere at 750 ℃ to obtain reduction roasting slag. And (3) taking water as a leaching agent, leaching the hydrogen reduction roasting slag under the condition of leaching for 1h at the liquid-solid ratio of 4:1 and 80 ℃, and carrying out solid-liquid separation treatment to obtain water leaching slag and lithium-containing leaching liquid. And combining the lithium-rich solution and the lithium-containing leaching solution, introducing CO 2, and performing evaporative crystallization to obtain a lithium carbonate product, wherein the comprehensive recovery rate of lithium is 69.6%.
(4) Leaching the water leaching slag obtained in the step (3) by using sulfuric acid with the concentration of 5mol/L to obtain leaching liquid containing nickel, cobalt and manganese. Neutralizing precipitation to remove iron and aluminum (pH value is 4.6), removing copper and zinc by sodium sulfide, and removing magnesium by sodium fluoride to obtain a purifying liquid, wherein the purifying liquid is a solution product containing nickel, cobalt and manganese.
(5) The purity of the obtained product is shown as follows, the recovery rate of copper and aluminum in the copper and aluminum product can reach 92.47 percent, 90.37 percent, the recovery rate of graphite reaches 88.10 percent, the purity of lithium carbonate obtained by wet lithium extraction is 99.8 percent, and the recovery rates of lithium, nickel, cobalt and manganese are 69.6 percent, 99.3 percent, 99.5 percent and 99.2 percent respectively.
Example 6
The battery adopted in the embodiment is a cylindrical 18650 ternary lithium ion battery in a factory in Zhejiang.
(1) And (3) treating the waste ternary lithium ion battery by adopting chemical discharge, and carrying out multistage crushing on the discharged battery under the nitrogen atmosphere. The crushed battery is subjected to pyrolysis pretreatment for 0.5h in a nitrogen atmosphere at 700 ℃ to obtain pyrolysis products, and generated pyrolysis smoke is discharged after secondary combustion, surface cooling, high-temperature cloth bag dust collection and tail gas purification treatment.
(2) The pyrolyzed product is washed and classified into three particle sizes of more than 3mm, 0.20-3 mm and less than 0.20mm and lithium-rich solution, the three particle sizes are respectively subjected to magnetic separation under the magnetic field intensity of 40kA/m to obtain a nickel cobalt manganese intermediate product, and magnetic separation tailings with the particle sizes of more than 3mm and 0.20-3 mm are used as copper aluminum products, and the recovery rates are 93.98% and 92.13% respectively. The magnetic tailings with the grain size below 0.20mm are black powder and graphite products, water is used for pulping to form flotation slurry with the concentration of 35wt%, 1000g/t of sodium sulfide, 200g/t of diesel oil and 40g/t of pine oil are added into the flotation slurry to carry out graphite flotation, the graphite with the carbon grade of 87.05% and the recovery rate of 87.29% is obtained through flotation, and the flotation tailings are black powder and nickel cobalt manganese intermediate products and enter a subsequent reduction roasting process.
(3) And (3) carrying out reduction roasting on the black powder nickel cobalt manganese intermediate product for 7 hours in a hydrogen reducing atmosphere at the temperature of 650 ℃ to obtain reduction roasting slag. And (3) taking water as a leaching agent, leaching the hydrogen reduction roasting slag under the condition of leaching for 1h at the liquid-solid ratio of 4:1 and 80 ℃, and carrying out solid-liquid separation treatment to obtain water leaching slag and lithium-containing leaching liquid. And combining the lithium-rich solution and the lithium-containing leaching solution, introducing CO 2, and performing evaporative crystallization to obtain a lithium carbonate product, wherein the comprehensive recovery rate of lithium is 77.6%.
(4) Leaching the water leaching slag obtained in the step (3) by using sulfuric acid with the concentration of 5mol/L to obtain leaching liquid containing nickel, cobalt and manganese. Neutralizing precipitation to remove iron and aluminum (pH value is 4.6), removing copper and zinc by sodium sulfide, and removing magnesium by sodium fluoride to obtain a purifying liquid, wherein the purifying liquid is a solution product containing nickel, cobalt and manganese.
(5) The purity of the obtained product is shown as follows, the recovery rate of copper and aluminum in the copper and aluminum product can reach 92.47 percent, 90.37 percent, the recovery rate of graphite reaches 88.10 percent, the purity of lithium carbonate obtained by wet lithium extraction is 98.8 percent, and the recovery rates of lithium, nickel, cobalt and manganese are 77.6 percent, 99.3 percent, 99.5 percent and 99.2 percent respectively.
Example 7
The battery adopted in the embodiment is a cylindrical 18650 ternary lithium ion battery in a factory in Zhejiang.
(1) And (3) treating the waste ternary lithium ion battery by adopting chemical discharge, and carrying out multistage crushing on the discharged battery under the nitrogen atmosphere. The crushed battery is subjected to pyrolysis pretreatment for 2 hours in a nitrogen atmosphere at 640 ℃ to obtain pyrolysis products, and generated pyrolysis smoke is discharged after secondary combustion, surface cooling, high-temperature cloth bag dust collection and tail gas purification treatment.
(2) The pyrolyzed product is washed and graded into three particle sizes of >2mm, 0.15-2 mm and below 0.15mm and lithium-rich solution, the three particle sizes are respectively subjected to magnetic separation under the magnetic field intensity of 180kA/m to obtain a nickel cobalt manganese intermediate product, and magnetic separation tailings of >2mm and 0.15-2 mm are used as copper aluminum products, and the recovery rates are 92.89% and 91.22% respectively. The magnetic tailings with the grain size below 0.15mm are black powder and graphite products, water is used for pulping to form flotation slurry with the concentration of 20wt%, 1000g/t of sodium sulfide, 200g/t of diesel oil and 40g/t of pine oil are added into the flotation slurry to carry out graphite flotation, the graphite with the carbon grade of 90.33% and the recovery rate of 87.11% is obtained through flotation, and the flotation tailings are black powder and nickel cobalt manganese intermediate products and enter a subsequent reduction roasting process.
(3) And (3) carrying out reduction roasting on the black powder nickel cobalt manganese intermediate product for 5 hours in a hydrogen reducing atmosphere at the temperature of 350 ℃ to obtain reduction roasting slag. And (3) taking water as a leaching agent, leaching the hydrogen reduction roasting slag under the condition of leaching for 1h at the liquid-solid ratio of 4:1 and 80 ℃, and carrying out solid-liquid separation treatment to obtain water leaching slag and lithium-containing leaching liquid. And combining the lithium-rich solution and the lithium-containing leaching solution, introducing CO 2, and performing evaporative crystallization to obtain a lithium carbonate product, wherein the comprehensive recovery rate of lithium is 23.5%.
(4) Leaching the water leaching slag obtained in the step (3) by using sulfuric acid with the concentration of 5mol/L to obtain leaching liquid containing nickel, cobalt and manganese. Neutralizing precipitation to remove iron and aluminum (pH value is 4.6), removing copper and zinc by sodium sulfide, and removing magnesium by sodium fluoride to obtain a purifying liquid, wherein the purifying liquid is a solution product containing nickel, cobalt and manganese.
(5) The purity of the obtained product is shown as follows, the recovery rate of copper and aluminum in the copper and aluminum product can reach 92.47 percent, 90.37 percent, the recovery rate of graphite reaches 88.10 percent, the purity of lithium carbonate obtained by wet lithium extraction is 99.8 percent, and the recovery rates of lithium, nickel, cobalt and manganese are 23.5 percent, 99.3 percent, 99.5 percent and 99.2 percent respectively.
Example 8
The battery adopted in the embodiment is a cylindrical 18650 ternary lithium ion battery in a factory in Zhejiang.
(1) And (3) treating the waste ternary lithium ion battery by adopting chemical discharge, and carrying out multistage crushing on the discharged battery under the nitrogen atmosphere. The crushed battery is subjected to pyrolysis pretreatment for 3 hours in a nitrogen atmosphere at the temperature of 610 ℃ to obtain pyrolysis products, and generated pyrolysis smoke is discharged after secondary combustion, surface cooling, high-temperature cloth bag dust collection and tail gas purification treatment.
(2) The pyrolyzed product is washed and classified into three particle sizes of more than 2mm, 0.15-2 mm and less than 0.15mm and lithium-rich solution, the three particle sizes are respectively subjected to magnetic separation under the magnetic field intensity of 180kA/m to obtain a nickel cobalt manganese intermediate product, magnetic separation tailings of more than 2mm and 0.15-2 mm are used as copper aluminum products, and the recovery rates are respectively 89.04% and 89.12%. The magnetic tailings with the grain size below 0.15mm are black powder and graphite products, water is used for pulping to form flotation slurry with the concentration of 15wt%, 1000g/t of sodium sulfide, 200g/t of diesel oil and 40g/t of pine oil are added into the flotation slurry to carry out graphite flotation, the graphite with the carbon grade of 89.59% and the recovery rate of 88.40% is obtained through flotation, and the flotation tailings are black powder and nickel cobalt manganese intermediate products and enter a subsequent reduction roasting process.
(3) And (3) performing reduction roasting on the black powder nickel cobalt manganese intermediate product for 2 hours in a hydrogen reducing atmosphere at 480 ℃ to obtain reduction roasting slag. And (3) taking water as a leaching agent, leaching the hydrogen reduction roasting slag under the condition of leaching for 1h at the liquid-solid ratio of 4.5:1 and 80 ℃, and carrying out solid-liquid separation treatment to obtain water leaching slag and lithium-containing leaching liquid. And combining the lithium-rich solution and the lithium-containing leaching solution, introducing CO 2, and performing evaporative crystallization to obtain a lithium carbonate product, wherein the comprehensive recovery rate of lithium is 99.1%.
(4) The water leaching slag, the flux quartz sand, the limestone and the reducing agent coal are subjected to reduction smelting for 5 hours at 1200 ℃ to obtain nickel-cobalt alloy and smelting slag, and the smelting slag belongs to harmless slag after high-temperature solidification treatment and can be directly buried. The flue gas generated by reduction smelting is discharged after secondary combustion, a waste heat boiler, surface cooling, high-temperature cloth bag dust collection and tail gas purification and absorption.
(5) The purity of the obtained product is shown as follows, the recovery rate of copper and aluminum in the copper and aluminum product can reach 92.47 percent, 90.37 percent, the recovery rate of graphite reaches 88.10 percent, the purity of lithium hydroxide obtained by wet lithium extraction is 99.8 percent, and the recovery rates of lithium, nickel, cobalt and manganese are respectively 99.1 percent, 99.3 percent, 99.5 percent and 99.2 percent.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (23)

1. A dressing and smelting combined comprehensive recovery method of waste lithium ion batteries is characterized by comprising the following steps:
The method comprises the steps of S1, carrying out fire pretreatment on the waste lithium ion batteries to obtain pretreatment products, wherein the fire pretreatment process comprises the steps of disassembling and crushing the waste lithium ion batteries to obtain crushed materials with particle diameters below 50mm, carrying out low-temperature pyrolysis on the crushed materials under the conditions of protective atmosphere and 610-640 ℃ to obtain the pretreatment products;
S2, carrying out ore washing and grading treatment on the pretreated product to obtain coarse-size particles, medium-size and fine-size particles, fine-size particles and a first part of lithium-containing solution, wherein the particle size of the coarse-size particles is larger than that of the medium-size and fine-size particles, and the particle size of the medium-size and fine-size particles is larger than that of the fine-size particles;
s3, respectively carrying out magnetic separation on the coarse-grain-level particles, the medium-fine-grain-level particles and the fine-grain-level particles, wherein the obtained magnetic concentrate is used as a nickel cobalt manganese intermediate product, the magnetic tailings of the coarse-grain-level particles and the medium-fine-grain-level particles are used as copper aluminum products, and the magnetic tailings of the fine-grain-level particles are graphite and black powder products;
S4, carrying out reduction roasting on the nickel-cobalt-manganese intermediate product and the black powder to obtain roasting slag, leaching lithium from the roasting slag by water to obtain a second part of lithium-containing solution and water leaching slag, wherein a reducing agent adopted in the reduction roasting process is the graphite product obtained in the step S3;
S5, combining the first part of lithium-containing solution and the second part of lithium-containing solution to obtain a combined solution;
S6, carrying out acid leaching and impurity removal on the water leaching slag to obtain a solution product containing nickel, cobalt and manganese.
2. The recycling method according to claim 1, wherein in the step S1, the time of the low-temperature pyrolysis is 0.5 to 6 hours.
3. The recycling method according to claim 2, wherein the step S1 further comprises a step of discharging the waste lithium ion battery before the step of disassembling and crushing the waste lithium ion battery.
4. The recovery method according to claim 1, wherein in the step S2, the particle size of the coarse fraction particles is larger than 2mm, the particle size of the fine fraction particles is smaller than 0.2mm, and the particle size of the medium fine fraction particles is between the particle sizes of the coarse fraction particles and the fine fraction particles.
5. The recovery method according to claim 4, wherein in the step S3, magnetic separation magnetic field strengths of the coarse fraction particles, the medium fine fraction particles, and the fine fraction particles are 40 to 280ka/m, respectively.
6. The method of claim 4, wherein the steps of sequentially slurrying the graphite and black powder products and floating the graphite comprise:
Preparing the graphite and black powder products into flotation pulp with the concentration of 5-35 wt% by using water;
and adding a regulator, a graphite collector and a foaming agent into the flotation pulp to carry out graphite flotation, so as to obtain the graphite product and the black powder.
7. The recycling method according to any one of claims 1 to 5, characterized in that in the step S4, the temperature of the reduction roasting process is 400 to 700 ℃ and the reaction time is 0.5 to 6 hours.
8. The method according to any one of claims 1 to 5, wherein in step S5, lithium in the combined solution is evaporated and crystallized as lithium hydroxide, or carbon dioxide is introduced into the combined solution or soluble carbonate is added to precipitate lithium as lithium carbonate, to obtain the lithium product.
9. The recovery method according to claim 8, wherein the step S5 further comprises a step of removing impurity ions in the combined solution using chemical precipitation or ion exchange resin, before the step of preparing the lithium product using the combined solution.
10. The recovery method according to any one of claims 1 to 5, wherein in step S6, the water leaching residue is subjected to acid leaching to obtain an acid leaching solution;
the impurity removal step comprises the following steps:
adjusting the pH value of the pickle liquor to be more than 4.2, and removing iron impurities and aluminum impurities to obtain an iron-aluminum removal solution;
adding fluoride into the iron-aluminum removing solution to remove magnesium impurities to obtain a magnesium removing solution, wherein the fluoride is sodium fluoride;
adding sulfide salt and/or hydrogen sulfide into the magnesium removal solution to remove copper impurities and zinc impurities to obtain a solution product containing nickel, cobalt and manganese, wherein the sulfide salt is sodium sulfide;
or the impurity removal step comprises the following steps:
extracting the pickle liquor by using an extracting agent to obtain the solution product containing nickel, cobalt and manganese, wherein the extracting agent is a P204 extracting agent.
11. The recovery method according to claim 7, wherein before the step of acid leaching the water leaching residue, the step S6 further comprises a step of reduction smelting the water leaching residue.
12. The recovery method according to claim 11, characterized in that the water leaching slag is subjected to reduction smelting at a temperature of 1200-1600 ℃ for 0.5-5 hours to obtain a nickel-cobalt-manganese alloy, and then the nickel-cobalt-manganese alloy is subjected to acid leaching and impurity removal in sequence to obtain the nickel-cobalt-manganese containing solution product.
13. The recovery method according to claim 11, wherein a first flue gas is obtained in the pyrometallurgical pretreatment step, a second flue gas is obtained in the reduction smelting step, and the recovery method further comprises the steps of post-combustion, surface cooling, dust removal, and tail gas purification of the first flue gas and the second flue gas in sequence.
14. The recycling method according to claim 1, wherein the waste lithium ion battery is one or more of a waste lithium cobaltate battery, a lithium manganate battery, a nickel-manganese binary composite lithium ion battery, a nickel-cobalt binary composite lithium ion battery, a cobalt-manganese binary composite lithium ion battery, a nickel-cobalt-manganese ternary composite lithium ion battery, and a nickel-cobalt-aluminum ternary composite lithium ion battery.
15. The utility model provides a dressing and smelting combination comprehensive recovery unit of old and useless lithium ion battery, its characterized in that, recovery unit includes:
The fire pretreatment unit (10) is provided with a waste lithium ion battery inlet and a pretreatment product outlet, and the fire pretreatment unit (10) is used for carrying out fire pretreatment on the waste lithium ion battery to obtain a pretreatment product;
The pyrogenic pretreatment unit (10) further comprises a disassembly and crushing unit (11) provided with a waste lithium ion battery inlet and a crushed material outlet and used for obtaining crushed materials with the particle size of less than 50mm, a low-temperature pyrolysis unit (12) provided with a crushed material inlet, an inert gas inlet and a pretreated product outlet, wherein the crushed material inlet is connected with the crushed material outlet and used for carrying out low-temperature pyrolysis on the crushed materials under the conditions of protective atmosphere and 610-640 ℃ to obtain the pretreated products;
A wash classification unit (20) having a pretreatment product inlet and a first water inlet, the pretreatment product inlet being connected to the pretreatment product inlet, the wash classification unit (20) being configured to perform a wash classification treatment on the pretreatment product to obtain coarse fraction particles, medium fine fraction particles, and a first portion of a lithium-containing solution, and the coarse fraction particles having a particle size larger than that of the medium fine fraction particles, the medium fine fraction particles having a particle size larger than that of the fine fraction particles;
The magnetic separation unit (30) is connected with the outlet of the ore washing grading unit (20), the magnetic separation unit (30) is used for respectively carrying out magnetic separation on the coarse-grain-level particles, the medium-fine-grain-level particles and the fine-grain-level particles to obtain nickel cobalt manganese intermediate products, coarse-grain-level particle magnetic separation tailings, medium-fine-grain-level particle magnetic separation tailings and fine-grain-level particle magnetic separation tailings, the coarse-grain-level particle magnetic separation tailings and the medium-fine-grain-level particle magnetic separation tailings are used as copper aluminum products, and the fine-grain-level particle magnetic separation tailings are graphite and black powder products;
the graphite recovery unit (40) is connected with the outlet of the magnetic separation unit (30), the graphite recovery unit (40) comprises a pulp mixing unit (41) and a flotation unit (42) which are sequentially connected, the pulp mixing unit (41) is used for mixing the graphite and black powder products, and the flotation unit (42) is used for carrying out graphite flotation to obtain the graphite products and the black powder;
The reduction roasting unit (50) is respectively connected with the outlet of the magnetic separation unit (30) and the outlet of the flotation unit (42), and the reduction roasting unit (50) is used for carrying out reduction roasting on the nickel-cobalt-manganese intermediate product and the black powder to obtain roasting slag;
The reduction roasting unit (50) is also provided with a first reducing agent inlet which is connected with the outlet of the flotation unit (42) and is used for taking the graphite product obtained in the graphite flotation process as the reducing agent in the reduction roasting process, a water leaching unit (60) is provided with a roasting slag inlet and a second water inlet, the roasting slag inlet is connected with the outlet of the reduction roasting unit (50), and the water leaching unit (60) is used for leaching lithium from the roasting slag by water to obtain a second part of lithium-containing solution and water leaching slag;
The inlet of the lithium recovery unit (70) is respectively connected with the outlet of the water leaching unit (60) and the outlet of the ore washing grading unit (20), and the lithium recovery unit (70) is used for preparing a lithium product by adopting the combined solution of the first part of lithium-containing solution and the second part of lithium-containing solution;
The acid leaching unit (80) is provided with a water leaching slag inlet, an acid inlet and an acid leaching liquid outlet, wherein the water leaching slag inlet is connected with the outlet of the water leaching unit (60), and the acid leaching unit (80) is used for carrying out acid leaching on the water leaching slag to obtain acid leaching liquid;
And the impurity removing unit (90) is connected with the pickle liquor outlet, and the impurity removing unit (90) is used for removing impurities from the pickle liquor to obtain a solution product containing nickel, cobalt and manganese.
16. The recycling apparatus according to claim 15, characterized in that the pyrometallurgical pretreatment unit (10) further comprises a discharge unit (13), the discharge unit (13) being located upstream of the dismantling and crushing unit (11) and connected to the inlet of the waste lithium ion battery, the discharge unit (13) being adapted to discharge the waste lithium ion battery.
17. The recycling apparatus according to claim 15 or 16, characterized in that the graphite recycling unit (40) further comprises:
A regulator supply unit (43) connected to the flotation unit (42) for supplying a regulator thereto;
a graphite collector supply unit (44) connected to the flotation unit (42) for supplying a graphite collector thereto;
a frother supply unit (45) connected to the flotation unit (42) for supplying frother thereto.
18. The recycling apparatus according to claim 15 or 16, characterized in that,
The reduction roasting unit (50) further has a reducing gas inlet, and the recovery device further includes a reducing gas supply unit connected to the reducing gas inlet.
19. The recovery device according to claim 18, further comprising an inert gas supply unit (100), the inert gas supply unit (100) being connected to the reducing gas inlet and the inert gas inlet of the low temperature pyrolysis unit (12), respectively.
20. The recovery device according to claim 15 or 16, wherein the lithium recovery unit (70) comprises:
a impurity removing agent supply unit (71) for supplying an impurity removing agent;
The inlet of the impurity removal and purification unit (72) is respectively connected with the outlet of the water leaching unit (60), the outlet of the ore washing and grading unit (20) and the impurity removal agent supply unit (71), and the impurity removal and purification unit (72) is used for performing impurity removal reaction on the combined solution of the first part of lithium-containing solution and the second part of lithium-containing solution to obtain an impurity-removed lithium solution;
And the lithium product preparation unit (73) is connected with the outlet of the impurity removal purification unit (72), and the lithium product preparation unit (73) is used for carrying out evaporative crystallization or lithium carbonate precipitation on the impurity removal lithium solution to obtain the lithium product.
21. The recycling apparatus according to claim 15 or 16, characterized in that,
The impurity removal unit (90) includes:
The pH adjusting unit (91) is connected with the pickle liquor outlet, and the pH adjusting unit (91) is used for adjusting the pH value of the pickle liquor to be more than 4.2 so as to obtain iron and aluminum removal solution;
A magnesium removal unit (92) having a fluoride inlet and an iron and aluminum removal solution inlet, the iron and aluminum removal solution inlet being connected to an outlet of the pH adjustment unit (91), the magnesium removal unit (92) being configured to remove magnesium impurities in the iron and aluminum removal solution to obtain a magnesium removal solution;
A copper-zinc removal unit (93) provided with a magnesium removal solution inlet and a sulfide inlet, wherein the magnesium removal solution inlet is connected with an outlet of the magnesium removal unit (92), the sulfide inlet is used for introducing sulfide salt and/or hydrogen sulfide, and the copper-zinc removal unit (93) is used for removing copper impurities and zinc impurities in the magnesium removal solution to obtain a solution product containing nickel, cobalt and manganese;
or the impurity removing unit (90) is an extraction impurity removing unit.
22. The recovery device according to claim 21, characterized in that the recovery device further comprises a reduction smelting unit (110), the reduction smelting unit (110) is arranged on a flow path where the water leaching slag inlet is connected with the water leaching unit (60), the reduction smelting unit (110) further has a flux inlet, the reduction smelting unit (110) is used for carrying out reduction smelting on the water leaching slag to obtain nickel cobalt manganese alloy, and the acid leaching unit (80) is used for carrying out acid leaching on the nickel cobalt manganese alloy to obtain the acid leaching liquid.
23. The recovery device according to claim 22, wherein the pyrometallurgical pretreatment unit (10) further has a first flue gas outlet, the reduction smelting unit (110) further has a second flue gas outlet, the recovery device further comprises a flue gas treatment unit (120), the flue gas treatment unit (120) being connected to the first flue gas outlet and the second flue gas outlet, respectively.
CN202010520232.5A 2020-06-09 2020-06-09 Method and device for comprehensive recovery of waste lithium-ion batteries by metallurgy Active CN111534697B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010520232.5A CN111534697B (en) 2020-06-09 2020-06-09 Method and device for comprehensive recovery of waste lithium-ion batteries by metallurgy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010520232.5A CN111534697B (en) 2020-06-09 2020-06-09 Method and device for comprehensive recovery of waste lithium-ion batteries by metallurgy

Publications (2)

Publication Number Publication Date
CN111534697A CN111534697A (en) 2020-08-14
CN111534697B true CN111534697B (en) 2025-02-25

Family

ID=71974279

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010520232.5A Active CN111534697B (en) 2020-06-09 2020-06-09 Method and device for comprehensive recovery of waste lithium-ion batteries by metallurgy

Country Status (1)

Country Link
CN (1) CN111534697B (en)

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112086703B (en) * 2020-09-10 2021-08-06 中南大学 A resource treatment method for decommissioned battery carbon residue
CN112126786A (en) * 2020-09-27 2020-12-25 中钢集团南京新材料研究院有限公司 Recovery method of waste powder produced in ternary material production
CN112575203B (en) * 2020-12-07 2022-11-04 金川集团股份有限公司 Method for recycling lithium in waste power lithium battery
CN112756104B (en) 2020-12-28 2023-01-13 湖南邦普循环科技有限公司 Wet sorting process for waste lithium batteries and application thereof
CN112993428A (en) * 2021-02-08 2021-06-18 中节能工程技术研究院有限公司 Method for recycling waste ternary lithium battery positive electrode material
CN113120930A (en) * 2021-04-21 2021-07-16 中国科学院过程工程研究所 Method for preparing lithium hydroxide by pyrolyzing waste lithium ion batteries
CN113405367B (en) * 2021-06-22 2023-05-23 四川长虹格润环保科技股份有限公司 Lithium battery recycling powder reduction equipment and ternary lithium battery recycling powder reduction method
CN113764758A (en) * 2021-07-26 2021-12-07 广东邦普循环科技有限公司 Method for recycling, pyrolyzing and controlling temperature of waste lithium battery and application
WO2023034971A1 (en) * 2021-09-03 2023-03-09 Comstock Ip Holdings Llc Lithium battery recycling process, apparatus, and system for the production of black mass
CN113846219B (en) * 2021-09-06 2022-11-15 广东邦普循环科技有限公司 Method for extracting lithium from waste lithium batteries
CN113921926B (en) * 2021-09-17 2025-01-03 中国恩菲工程技术有限公司 Waste ternary power battery processing system and method
CN114256527A (en) * 2021-12-06 2022-03-29 中国矿业大学(北京) A method for removing impurities and separating positive and negative electrodes from mixed materials of waste lithium ion batteries
CN115072747A (en) * 2022-05-31 2022-09-20 湖南力合厚浦科技有限公司 Lithium carbonate recovery method and device
CN115287458A (en) * 2022-07-28 2022-11-04 荆门市格林美新材料有限公司 Method for recovering valuable metals in lithium-containing power battery waste
CN115172925A (en) * 2022-08-26 2022-10-11 赣州天奇循环环保科技有限公司 Multi-component recycling method for waste lithium ion batteries
CN115367732B (en) * 2022-09-20 2023-08-22 中南大学 Industrial sulfate solid waste and waste nickel-cobalt-manganese-lithium battery collaborative recycling method
CN115821061A (en) * 2022-11-18 2023-03-21 宜春天卓新材料有限公司 Roasting lithium slag separation method, device, equipment and medium based on density classification
JP2024079020A (en) * 2022-11-30 2024-06-11 住友金属鉱山株式会社 Methods for producing valuable metals
CN115872400B (en) * 2022-12-30 2025-04-18 贵州中伟兴阳储能科技有限公司 A graphite recovery method based on leached residue from waste lithium batteries
EP4431622A1 (en) * 2023-03-17 2024-09-18 cylib GmbH Targeted leach guide for efficient separation of lithium battery materials
CN116723896A (en) * 2023-04-18 2023-09-08 广东邦普循环科技有限公司 A full-chain integrated method for recycling lithium and graphite in used batteries
CN117121267A (en) * 2023-06-28 2023-11-24 广东邦普循环科技有限公司 Method for integrally treating waste ternary lithium battery through full chain
CN116683082B (en) * 2023-07-13 2023-11-14 山东产研绿洲环境产业技术研究院有限公司 Microwave-assisted pyrogenic process-wet process combined process recovery method for waste lithium batteries
CN117142530A (en) * 2023-07-27 2023-12-01 焦作伴侣纳米材料工程有限公司 A method for recycling valuable metals of lithium manganate material and cathode material
EP4570934A1 (en) * 2023-12-13 2025-06-18 tozero GmbH Lithium and graphite recycled from black mass
EP4575017A1 (en) * 2023-12-22 2025-06-25 Umicore Smelting of pyrolyzed battery
CN120438377B (en) * 2025-07-07 2025-09-12 江西天奇金泰阁钴业有限公司 A waste ternary lithium battery recycling and sorting device and its use method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108400400A (en) * 2018-02-07 2018-08-14 中南大学 A kind of reuse method of applying waste lithium ionic power battery
CN110479478A (en) * 2019-09-02 2019-11-22 赣州金环磁选设备有限公司 A kind of method that green high-efficient recycles valuable metal nickel cobalt manganese in waste lithium cell
CN110828927A (en) * 2019-10-18 2020-02-21 广西银亿新材料有限公司 Method for comprehensively recovering waste lithium ion batteries
CN212925126U (en) * 2020-06-09 2021-04-09 中国恩菲工程技术有限公司 Selection and smelting combined comprehensive recovery device for waste lithium ion batteries

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012229481A (en) * 2011-04-27 2012-11-22 Japan Metals & Chem Co Ltd Method for separating and recovering valuable material from used lithium ion battery
CN111129635A (en) * 2019-12-17 2020-05-08 湖南凯地众能科技有限公司 Method and device for separating anode material and cathode material of waste lithium battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108400400A (en) * 2018-02-07 2018-08-14 中南大学 A kind of reuse method of applying waste lithium ionic power battery
CN110479478A (en) * 2019-09-02 2019-11-22 赣州金环磁选设备有限公司 A kind of method that green high-efficient recycles valuable metal nickel cobalt manganese in waste lithium cell
CN110828927A (en) * 2019-10-18 2020-02-21 广西银亿新材料有限公司 Method for comprehensively recovering waste lithium ion batteries
CN212925126U (en) * 2020-06-09 2021-04-09 中国恩菲工程技术有限公司 Selection and smelting combined comprehensive recovery device for waste lithium ion batteries

Also Published As

Publication number Publication date
CN111534697A (en) 2020-08-14

Similar Documents

Publication Publication Date Title
CN111534697B (en) Method and device for comprehensive recovery of waste lithium-ion batteries by metallurgy
CN113517484B (en) Treatment method and product of waste lithium cobalt oxide battery
CN112079369B (en) Method for preferentially extracting lithium and cooperatively recovering manganese from waste lithium ion battery
Al-Thyabat et al. Adaptation of minerals processing operations for lithium-ion (LiBs) and nickel metal hydride (NiMH) batteries recycling: Critical review
CN111170343B (en) Method for recovering and producing lithium hydroxide from waste lithium ion battery
CN112374511A (en) Method for preparing lithium carbonate and ternary precursor by recycling waste ternary lithium battery
CN107017443A (en) A kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery
CN110079671A (en) A kind of method of waste and old lithium ion battery valuable element synthetical recovery
CN109182732A (en) Waste and old ternary lithium battery stagewise recovery method
CN111254276A (en) Method for selective extraction of valuable metals from waste lithium-ion battery powder based on phase inversion of reductive sodium roasting
JPWO2015162902A1 (en) Method and facility for recovering valuable components from waste dry batteries
CN110028111B (en) Ternary cathode material precursor and preparation method of lithium carbonate
CN212925126U (en) Selection and smelting combined comprehensive recovery device for waste lithium ion batteries
CN107742760A (en) Method for extracting lithium from waste lithium ion battery
He et al. Unveiling the lithium deintercalation mechanisms in spent lithium-ion batteries via sulfation roasting
JP6648674B2 (en) Method for producing metallic manganese
CA3219839A1 (en) Process for recycling battery materials by way of hydrometallurgical treatment
CN115652077A (en) A method for selective separation and recovery of lithium and manganese from waste lithium manganese oxide batteries
CN114959272B (en) Method for selectively recovering lithium from waste lithium ion battery
CN112259821A (en) Method for recovering valuable metals from waste lithium ion batteries
CN117845057A (en) Method for recycling valuable metals from waste lithium ion batteries
CN116676493B (en) Cooperative recovery method of waste lithium ion battery material and high nickel matte
CN115852152B (en) Method for cooperatively treating battery black powder and nickel cobalt hydroxide
CN115595456B (en) Method for extracting lithium from waste lithium cobalt oxide battery anode material through low-temperature vulcanization roasting
CN116706302A (en) Lithium battery recycling method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant