CN111554994A - Waste lithium ion battery recovery device and method - Google Patents
Waste lithium ion battery recovery device and method Download PDFInfo
- Publication number
- CN111554994A CN111554994A CN202010496157.3A CN202010496157A CN111554994A CN 111554994 A CN111554994 A CN 111554994A CN 202010496157 A CN202010496157 A CN 202010496157A CN 111554994 A CN111554994 A CN 111554994A
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- ball milling
- ion battery
- tail gas
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 153
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 112
- 239000002699 waste material Substances 0.000 title claims abstract description 106
- 238000011084 recovery Methods 0.000 title claims abstract description 30
- 238000000498 ball milling Methods 0.000 claims abstract description 133
- 239000007789 gas Substances 0.000 claims abstract description 121
- 239000000463 material Substances 0.000 claims abstract description 120
- 239000011261 inert gas Substances 0.000 claims abstract description 43
- 230000008569 process Effects 0.000 claims description 121
- 238000010521 absorption reaction Methods 0.000 claims description 67
- 239000003513 alkali Substances 0.000 claims description 56
- 238000000197 pyrolysis Methods 0.000 claims description 41
- 239000002893 slag Substances 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000001179 sorption measurement Methods 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 26
- 208000028659 discharge Diseases 0.000 claims description 23
- 238000002844 melting Methods 0.000 claims description 21
- 230000008018 melting Effects 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 238000007599 discharging Methods 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 238000010791 quenching Methods 0.000 claims description 14
- 230000000171 quenching effect Effects 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000004064 recycling Methods 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 239000002250 absorbent Substances 0.000 claims description 10
- 230000002745 absorbent Effects 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 238000007711 solidification Methods 0.000 claims description 9
- 238000005188 flotation Methods 0.000 claims description 8
- 230000005484 gravity Effects 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 5
- 238000007885 magnetic separation Methods 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 19
- 238000000354 decomposition reaction Methods 0.000 abstract description 10
- 239000002341 toxic gas Substances 0.000 abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 31
- 229910052731 fluorine Inorganic materials 0.000 description 21
- 229910052698 phosphorus Inorganic materials 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000011575 calcium Substances 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 8
- -1 polypropylene Polymers 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 238000009854 hydrometallurgy Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 238000009853 pyrometallurgy Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000010892 non-toxic waste Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/10—Inorganic absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/02—Gases or liquids enclosed in discarded articles, e.g. aerosol cans or cooling systems of refrigerators
-
- 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
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a waste lithium ion battery recovery device and a waste lithium ion battery recovery method. The device comprises a discharge device, a crushing device, a high-temperature ball milling device, an inert gas supply device and a tail gas treatment device, wherein the discharge device is provided with a waste lithium ion battery inlet and a discharge lithium ion battery outlet; the crushing device is provided with a discharge lithium ion battery inlet, a crushed material outlet, a first inert gas inlet and a first tail gas outlet, wherein the discharge lithium ion battery inlet is connected with the discharge lithium ion battery outlet; the high-temperature ball milling device is provided with a crushed material inlet, a ball milling material outlet, a second inert gas inlet and a second tail gas outlet, wherein the crushed material inlet is connected with the crushed material outlet; the inert gas supply device is respectively connected with the first inert gas inlet and the second inert gas inlet; the tail gas treatment device is respectively connected with the first tail gas outlet and the second tail gas outlet. The device can more effectively treat the toxic gas generated by volatilization and decomposition of the electrolyte in the recovery process of the waste lithium ion battery.
Description
Technical Field
The invention relates to the technical field of waste lithium ion battery recovery, in particular to a waste lithium ion battery recovery device and a waste lithium ion battery recovery method.
Background
The lithium ion battery has the advantages of high voltage, small volume, high specific energy, small self-discharge, high safety and the like, and is widely applied to the fields of consumer electronics, electric vehicles, industrial energy storage and the like. Research shows that the charging cycle of the lithium ion battery is about 500 times, the service life is generally 3-5 years, and the quantity of the waste lithium ion batteries is more and more huge along with the rapid increase of the production quantity and the use quantity of the lithium ion batteries. The lithium ion battery mainly comprises a positive electrode, a negative electrode, a diaphragm, electrolyte and an outer package, wherein the positive electrode material component of the ternary lithium ion battery is LiNi1-x-yCoxMnyO2. The waste ternary lithium ion battery contains rich valuable metal elements such as Li, Ni, Co, Mn, Cu, Al and the like, wherein the content of Co and Ni is far higher than the grade of primary cobalt ore and primary nickel ore. In recent years, the resource recycling of waste ternary lithium ion batteries is receiving more and more attention from people at home and abroad.
At present, the treatment and recovery process of the anode and cathode materials of the waste lithium ion battery is relatively perfect, and valuable metal elements in the anode and cathode materials can be recovered through a hydrometallurgy process or a pyrometallurgy process. Before hydrometallurgical or pyrometallurgical treatment, the waste lithium ion batteries need to be subjected to discharging and crushing treatment. The waste batteries are often subjected to the following two problems in the crushing process: 1. the electrolyte can volatilize and decompose, especially the organic solvent in the electrolyte and electrolysisMass LiPF6Volatile organic gases (VOCs) and HF gases having toxicity are easily generated; 2. the fire phenomenon occurs when the waste battery is crushed. In the actual industrial production process, the discharged waste lithium ion battery still may have a trace voltage (less than 0.1V), and a large amount of heat is emitted after the short circuit of the positive electrode and the negative electrode is contacted in the crushing process, so that the crushed materials of the battery are ignited in the crushing process. In addition, sparks are generated when the lithium ion battery shell and metal parts of the crusher rub in the crushing process, and a small amount of sparks can ignite a plastic diaphragm (the diaphragm component is polypropylene (PP) or Polyethylene (PE)) in the lithium ion battery, so that the fire is generated. At present, the existing crushing pretreatment process does not effectively solve the problems of toxic gas generated in the crushing process and the fire phenomenon.
Patent CN104009269A chooses to adopt mechanical system to carry out the breakage with the battery under nitrogen protection atmosphere, and the emergence of phenomenon can be prevented to the broken in-process nitrogen gas to fire, but can not prevent the volatilization and the decomposition of electrolyte, and the toxic gas of mixing in the nitrogen gas is not handled well. Patent CN103943911A firstly carries out discharge treatment on the waste lithium ion battery, and then breaks the waste lithium ion battery in a closed shear type breaker by a spraying method. Although the spraying can effectively prevent the occurrence of fire, the spraying liquid can corrode the crushing device after adsorbing the lithium hexafluorophosphate. Patent CN105390764A discloses a high-pressure liquid cutting system, which is to perform crushing and cutting treatment on waste lithium ion batteries under high-pressure liquid environment, and needs to be matched with a waste liquid recovery device, and the high-pressure liquid cannot be reused. Patent CN1070087929A discloses a method for roasting and sorting waste lithium ion batteries. The method comprises the steps of mixing the waste lithium ion battery and calcium-containing powder medicament ingredients, roasting at a high temperature, or spraying a calcium-containing medicament reacting with fluoride ions in the roasting process of the waste lithium ion battery, wherein the fluoride ions and the calcium-containing medicament generate an insoluble solid phase in the roasting process, and finally crushing and sorting the obtained roasted product to remove fluorine-containing solids. However, this process has the following problems: (1) for LiPF in electrolyte only6Adsorbing without treating the organic solvent in the electrolyte, and calciningVOCs gas generated in the process cannot be treated; (2) crushing treatment is not carried out before roasting, the defluorination effect is poor in the roasting process, and fluorine-containing substances are entrained in materials and are difficult to volatilize; (3) the fluorine-containing waste residue is directly buried, thus polluting the environment.
Therefore, there is a need to provide a more effective pretreatment process for waste lithium ion batteries to better treat toxic gases generated by volatilization and decomposition of electrolytes during recovery of the waste lithium ion batteries, and to solve the problems that materials are prone to fire in the crushing process and the like.
Disclosure of Invention
The invention mainly aims to provide a waste lithium ion battery recovery device and a waste lithium ion battery recovery method, and aims to solve the problems that toxic gas generated by volatilization and decomposition of electrolyte in the waste lithium ion battery recovery process cannot be effectively treated in the prior art, and materials are prone to fire in the crushing process.
In order to achieve the above object, according to one aspect of the present invention, there is provided a used lithium ion battery recycling apparatus, comprising: the discharging device is provided with a waste lithium ion battery inlet and a discharging lithium ion battery outlet and is used for discharging the waste lithium ion battery; the crushing device is provided with a discharge lithium ion battery inlet, a crushed material outlet, a first inert gas inlet and a first tail gas outlet, wherein the discharge lithium ion battery inlet is connected with the discharge lithium ion battery outlet; the high-temperature ball milling device is provided with a crushed material inlet, a ball milling material outlet, a second inert gas inlet and a second tail gas outlet, the crushed material inlet is connected with the crushed material outlet, and the high-temperature ball milling device is used for simultaneously pyrolyzing and ball milling the crushed material discharged by the crushing device; the inert gas supply device is respectively connected with the first inert gas inlet and the second inert gas inlet; and the tail gas treatment device is respectively connected with the first tail gas outlet and the second tail gas outlet.
Further, the high temperature ball milling apparatus comprises: a housing having a second inert gas inlet and a second tail gas outlet; the ball milling tank is positioned in the shell and provided with a crushed material inlet and a ball milling material outlet, and the ball milling tank is also provided with air holes; and the heating unit is positioned inside the shell and used for heating the ball milling tank.
Further, a plurality of ball milling pots and a plurality of heating units are disposed inside the housing.
Further, the plurality of heating units are divided into a first group and a second group, wherein the first group of heating units is located at the center of the housing, the plurality of ball milling pots are planetary-distributed around the first group of heating units, and the second group of heating units is located at the periphery of the ball milling pots.
Further, the tail gas treatment device comprises: the physical adsorption unit is provided with a tail gas inlet and an adsorption residual gas outlet, and the tail gas inlet is respectively connected with the first tail gas outlet and the second tail gas outlet; the alkali liquor absorption unit is provided with an adsorption residual gas inlet, a purified gas outlet and an alkali absorption waste residue outlet, and the adsorption residual gas inlet is connected with the adsorption residual gas outlet.
Further, the tail gas treatment device also comprises a melting and solidifying unit, wherein the melting and solidifying unit is provided with an alkali absorption waste residue inlet which is connected with an alkali absorption waste residue outlet.
Furthermore, old and useless lithium ion battery recovery unit still includes sorting unit, and sorting unit is provided with the ball-milling material import, and the ball-milling material import links to each other with the export of ball-milling material, and sorting unit is used for sorting the ball-milling material of high temperature ball-milling device exhaust.
According to another aspect of the present invention, there is provided a method for recovering a waste lithium ion battery, comprising the following steps: carrying out discharge treatment on the waste lithium ion battery to obtain a discharged lithium ion battery; crushing the discharged lithium ion battery to obtain a crushed material; performing high-temperature ball milling treatment on the crushed materials to simultaneously perform pyrolysis and ball milling on the crushed materials to obtain ball-milled materials; wherein the crushing treatment process and the high-temperature ball milling treatment process are carried out under the protection of inert gas; and collecting tail gas generated in the crushing treatment process and the high-temperature ball milling treatment process, and carrying out tail gas treatment on the tail gas.
Further, in the crushing process, the discharge lithium ion battery is crushed until the particle size is less than 2 cm.
Further, the ball milling temperature in the high-temperature ball milling treatment process is 500-700 ℃, and the ball milling time is 1-5 hours; preferably, the mass ratio of the ball materials in the high-temperature ball milling treatment process is 1-10: 1, and the ball milling rotating speed is 100-800 r/min.
Further, the tail gas treatment process comprises a physical adsorption process and an alkali liquor absorption process which are sequentially carried out; preferably, the physical adsorption process uses activated carbon as an adsorbent; preferably, the absorbent adopted in the alkali liquor absorption process is Ca (OH)2、NaOH、KOH、NaHCO3And KHCO3More preferably, the concentration of the absorbent is 1-10 mol/L.
Further, the alkali liquor absorption process adopts a spray absorption mode or a static absorption mode.
Further, alkali absorption waste residues generated in the alkali liquor absorption process, and the tail gas treatment process also comprises the step of carrying out melting and solidifying treatment on the alkali absorption waste residues; preferably, the melt-solidification process comprises: preserving the heat of the alkali absorption waste residue for 1-4 hours at the temperature of 1100-1400 ℃ to obtain a molten mass; preferably, adding silicon dioxide into the alkali absorption waste residues, controlling the ratio of the total mole number of Ca, Na and K elements in the alkali absorption waste residues in the form of oxides to the mole number of the silicon dioxide to be 0.5-1.5: 1, and then preserving heat at the temperature of 1100-1400 ℃ for 1-4 hours to obtain a molten mass; and water quenching the molten mass to obtain solid slag.
Further, the waste lithium ion battery recovery method also comprises the step of sorting ball-milled materials; preferably, the sorting mode is one or more of gravity separation, flotation, magnetic separation and chemical beneficiation.
The invention provides a waste lithium ion battery recovery device, which is used for treating waste lithium ion batteries and discharging the batteries in a discharging device. And then, the obtained discharge lithium ion battery enters a crushing device and is crushed under the protection of inert gas, so that the fire phenomenon in the crushing process is effectively inhibited. And the obtained crushed material enters a high-temperature ball milling device to be subjected to high-temperature ball milling under the protection of inert gas. In the high-temperature ball milling process, the crushed materials can be pyrolyzed while being ball milled. In the common pyrolysis process, due to the serious agglomeration phenomenon of materials, organic matters, electrolyte and the like are mixed in the metal pellets and are difficult to effectively decompose, so that F, P and organic matters in the waste lithium ion battery are difficult to effectively remove. Different from the common pyrolysis process, the high-temperature ball milling device is adopted to process the crushed materials, the ball milling crushing can be carried out while the pyrolysis is carried out, the ball milling can effectively improve the pyrolysis efficiency, the materials are prevented from being agglomerated in the pyrolysis process, and the decomposition and volatilization of organic matters are facilitated, so that F, P and the organic matters in the waste lithium ion battery can be removed more fully and more quickly. And tail gas generated by volatilization and pyrolysis in the crushing process and the high-temperature ball milling process enters a tail gas treatment device to be subjected to aftertreatment under the carrying of inert gas. In addition, the invention combines the crushing and high-temperature ball milling processes, can shorten the flow of multistage crushing, and can correspondingly reduce the operation difficulty of the subsequent metal recovery process after organic matters and the like in the battery are fully removed.
In a word, the device provided by the invention can be used for more effectively treating toxic gas generated by volatilization and decomposition of the electrolyte in the recovery process of the waste lithium ion battery and effectively solving the problem that materials are easy to catch fire in the crushing process.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows a block diagram of a waste lithium ion battery recycling apparatus according to an embodiment of the present invention;
fig. 2 shows a schematic diagram of a high-temperature ball milling device in a waste lithium ion battery recycling device according to an embodiment of the invention;
fig. 3 shows a schematic flow diagram of a waste lithium ion battery recycling method according to an embodiment of the present invention;
FIG. 4 shows an XRD pattern of an amorphous glass frit obtained from the melting and solidifying step in example 1 of the present invention.
Wherein the figures include the following reference numerals:
10. a discharge device; 20. a crushing device; 30. a high temperature ball milling device; 31. a housing; 32. a ball milling tank; 33. a heating unit; 40. an inert gas supply device; 50. a tail gas treatment device; 51. a physical adsorption unit; 52. an alkali liquor absorption unit; 53. a melt-solidification unit; 60. a sorting device.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As described in the background art, the prior art cannot effectively treat toxic gas generated by volatilization and decomposition of electrolyte in the recovery process of waste lithium ion batteries, and also has the problem that materials are easy to catch fire in the crushing process.
In order to solve the above problems, the present invention provides a waste lithium ion battery recycling device, as shown in fig. 1, the device includes a discharging device 10, a crushing device 20, a high temperature ball milling device 30, an inert gas supply device 40, and a tail gas treatment device 50, the discharging device 10 has a waste lithium ion battery inlet and a discharged lithium ion battery outlet, and the discharging device 10 is used for performing discharge treatment on the waste lithium ion battery; the crushing device 20 is provided with a discharge lithium ion battery inlet, a crushed material outlet, a first inert gas inlet and a first tail gas outlet, wherein the discharge lithium ion battery inlet is connected with the discharge lithium ion battery outlet; the high-temperature ball milling device 30 is provided with a crushed material inlet, a ball milling material outlet, a second inert gas inlet and a second tail gas outlet, the crushed material inlet is connected with the crushed material outlet, and the high-temperature ball milling device 30 is used for simultaneously pyrolyzing and ball milling the crushed material discharged by the crushing device 20; the inert gas supply device 40 is respectively connected with the first inert gas inlet and the second inert gas inlet; the tail gas treatment device 50 is connected with the first tail gas outlet and the second tail gas outlet respectively.
When the above-mentioned device is used for treating waste lithium ion battery, the battery is firstly fed into the discharge device 10 to implement discharge. Then, the obtained discharge lithium ion battery enters the crushing device 20 to be crushed under the protection of inert gas, so that the fire phenomenon in the crushing process is effectively inhibited. The obtained crushed material enters a high-temperature ball milling device 30 to be ball milled at high temperature under the protection of inert gas. In the high-temperature ball milling process, the crushed materials can be pyrolyzed while being ball milled. In the common pyrolysis process, due to the serious agglomeration phenomenon of materials, organic matters, electrolyte and the like are mixed in the metal pellets and are difficult to effectively decompose, so that F, P and organic matters in the waste lithium ion battery are difficult to effectively remove. Different from the common pyrolysis process, the high-temperature ball milling device is adopted to process the crushed materials, the ball milling crushing can be carried out while the pyrolysis is carried out, the ball milling can effectively improve the pyrolysis efficiency, the materials are prevented from being agglomerated in the pyrolysis process, and the decomposition and volatilization of organic matters are facilitated, so that F, P and the organic matters in the waste lithium ion battery can be removed more fully and more quickly. And tail gas generated by volatilization and pyrolysis in the crushing process and the high-temperature ball milling process enters the tail gas treatment device 50 to be subjected to aftertreatment under the carrying of inert gas. In addition, the invention combines the crushing and high-temperature ball milling processes, can also shorten the flow of multistage crushing (only high-temperature ball milling and one-stage crushing are needed), and can correspondingly reduce the operation difficulty of the subsequent metal recovery process after organic matters and the like in the battery are fully removed.
In a word, the device provided by the invention can be used for more effectively treating toxic gas generated by volatilization and decomposition of the electrolyte in the recovery process of the waste lithium ion battery and effectively solving the problem that materials are easy to catch fire in the crushing process.
In a preferred embodiment, as shown in fig. 2, the high temperature ball milling apparatus 30 comprises a housing 31, a ball milling pot 32 and a heating unit 33, the housing 31 having a second inert gas inlet and a second off-gas outlet; the ball milling tank 32 is positioned inside the shell 31, the ball milling tank 32 is provided with a crushing material inlet and a ball milling material outlet, and the ball milling tank 32 is also provided with air holes; a heating unit 33 is located inside the housing 31, and the heating unit 33 is used to heat the ball milling pot 32. Thus, inert gas enters the shell 31 through the second inert gas inlet and then enters the ball milling tank 32 through the air holes, an inert environment is provided for the ball milling process, tail gas generated in the pyrolysis process is taken out, and the tail gas enters the tail gas treatment stage after being discharged through the second tail gas outlet.
More preferably, as shown in fig. 2, the housing 31 is internally provided with a plurality of ball milling pots 32 and a plurality of heating units 33. This can improve the throughput of crushed material. It is further preferable that the plurality of heating units 33 are divided into a first group and a second group, wherein the first group of heating units 33 is located at the center of the housing 31, the plurality of ball milling pots 32 are planetary-distributed around the first group of heating units 33, and the second group of heating units 33 is located at the periphery of the ball milling pots 32. By the arrangement, the thermal decomposition environment in the ball milling tank is more stable, the heating efficiency is higher, the heat distribution is more uniform, and the thermal decomposition efficiency and the stability of organic matters and electrolyte in the high-temperature ball milling process are improved.
The grinding balls in the ball mill pot are preferably ceramic balls such as stainless steel balls or zirconia balls.
Preferably, the crushing device is a roller crusher, a hammer crusher, a jaw crusher, or the like. In the actual operation process, the discharged lithium ion battery is preferably crushed to the particle size of less than 2 cm.
The inert gas may be an inert gas commonly used in the art, and preferably, the inert gas supply device is a nitrogen gas supply device, an argon gas supply device, or a helium gas supply device.
The discharge device 10 may be of a type commonly used in the art, such as a physical discharge device or a chemical discharge device, and accordingly, a physical discharge or a chemical discharge may be used.
In a preferred embodiment, as shown in fig. 1, the tail gas treatment device 50 comprises a physical adsorption unit 51 and an alkali liquor absorption unit 52, the physical adsorption unit 51 has a tail gas inlet and an adsorption residual gas outlet, and the tail gas inlet is respectively connected with the first tail gas outlet and the second tail gas outlet; the alkali liquor absorption unit 52 is provided with an adsorption residual gas inlet, a purified gas outlet and an alkali absorption waste residue outlet, and the adsorption residual gas inlet is connected with the adsorption residual gas outlet. Therefore, tail gas generated in the crushing and high-temperature ball milling pyrolysis processes can enter the physical adsorption unit 51 for physical adsorption, then enters the alkali liquor absorption unit 52 for alkali liquor absorption, and can be discharged after reaching the standard. Preferably in the lye absorption units 52The alkali liquor is Ca (OH)2、NaOH、KOH、NaHCO3And KHCO3One or more of them. In addition, the specific lye absorption units 52 preferably adopt a spray type lye absorption device or a static type lye absorption device.
In order to further reduce the influence of the alkali absorption slag on the environment, F, P, etc. in the tail gas can be converted into alkali absorption slag to be precipitated, in a preferred embodiment, the tail gas treatment device 50 further includes a melting and solidifying unit 53, and the melting and solidifying unit 53 has an alkali absorption slag inlet connected to the alkali absorption slag outlet. Therefore, the alkali absorption waste residues can be melted and solidified through the melting and solidifying unit 53, and then converted from dangerous waste residues into nontoxic waste residues, and finally buried. Preferably, the melting and solidifying unit 53 includes a melting unit and a water quenching unit connected in series, so that the alkali absorption slag is subjected to high-temperature melting treatment in the melting unit and then enters the water quenching unit for water quenching. Amorphous nontoxic waste residue can be obtained by cooling in a water quenching mode, and F, P and the like have better solidification effect.
In a preferred embodiment, the waste lithium ion battery recycling device further comprises a sorting device 60, the sorting device 60 is provided with a ball milling material inlet, the ball milling material inlet is connected with a ball milling material outlet, and the sorting device 60 is used for sorting the ball milling materials discharged from the high temperature ball milling device 30. Therefore, after the organic matters, the electrolyte and the like are fully pyrolyzed in the high-temperature ball milling process, the rest ball milling materials can directly enter a separation stage to further recover copper, aluminum, iron and the like in the ball milling materials. The specific sorting device 60 may adopt one or more of a gravity separation device, a flotation device, a magnetic separation device and a chemical method mineral separation device. The black powder obtained by sorting can be further used for recovering valuable metal elements such as lithium, nickel, cobalt, manganese and the like by a hydrometallurgy or pyrometallurgy method.
According to another aspect of the present invention, there is also provided a method for recovering a used lithium ion battery, as shown in fig. 3, the method comprising the following steps: carrying out discharge treatment on the waste lithium ion battery to obtain a discharged lithium ion battery; crushing the discharged lithium ion battery to obtain a crushed material; performing high-temperature ball milling treatment on the crushed materials to simultaneously perform pyrolysis and ball milling on the crushed materials to obtain ball-milled materials; wherein the crushing treatment process and the high-temperature ball milling treatment process are carried out under the protection of inert gas; and collecting tail gas generated in the crushing treatment process and the high-temperature ball milling treatment process, and carrying out tail gas treatment on the tail gas.
The crushing is carried out under the protection of inert gas, so that the fire phenomenon in the crushing process can be effectively inhibited. And carrying out high-temperature ball milling on the obtained crushed material under the protection of inert gas. In the high-temperature ball milling process, the crushed materials can be pyrolyzed while being ball milled. In the common pyrolysis process, due to the serious agglomeration phenomenon of materials, organic matters, electrolyte and the like are mixed in the metal pellets and are difficult to effectively decompose, so that F, P and organic matters in the waste lithium ion battery are difficult to effectively remove. Different from the common pyrolysis process, the high-temperature ball milling treatment is adopted to crush the materials, the ball milling can be carried out while the pyrolysis is carried out, the ball milling can effectively improve the pyrolysis efficiency, the materials are prevented from being agglomerated in the pyrolysis process, and the decomposition and volatilization of organic matters are facilitated, so that F, P and the organic matters in the waste lithium ion battery can be removed more fully and more quickly. And tail gas generated by volatilization and pyrolysis in the crushing process and the high-temperature ball milling process is carried by inert gas and enters a tail gas treatment stage for post-treatment. In addition, the invention combines the crushing and high-temperature ball milling processes, can also shorten the flow of multistage crushing (only high-temperature ball milling and one-stage crushing are needed), and can correspondingly reduce the operation difficulty of the subsequent metal recovery process after organic matters and the like in the battery are fully removed.
In order to more fully pyrolyze the electrolyte, organic matters and the like carried in the crushed materials into gas, in a preferred embodiment, in the crushing process, the discharge lithium ion battery is crushed to the particle size of less than 2 cm.
In a preferred embodiment, the ball milling temperature in the high-temperature ball milling treatment process is 500-700 ℃, and the ball milling time is 1-5 h. Under the conditions of temperature and time, the electrolyte and the organic matters can be more fully pyrolyzed. More preferably, the mass ratio of the ball materials in the high-temperature ball milling treatment process is 1-10: 1, and the ball milling rotating speed is 100-800 r/min. Therefore, the problem of mutual adhesion between materials in the ball milling process can be further relieved, and the pyrolysis reaction is more sufficient.
In a preferred embodiment, the tail gas treatment process comprises a physical adsorption process and a lye absorption process which are sequentially carried out. Therefore, tail gas generated in the crushing and high-temperature ball milling pyrolysis processes can be physically adsorbed firstly, and then is absorbed by alkali liquor, and can be discharged after reaching the standard. Preferably, the physical adsorption process uses activated carbon as an adsorbent; preferably, the absorbent adopted in the alkali liquor absorption process is Ca (OH)2、NaOH、KOH、NaHCO3And KHCO3More preferably, the concentration of the absorbent is 1-10 mol/L.
In a preferred embodiment, the lye absorption process is a spray absorption process or a static absorption process.
In a preferred embodiment, the alkali absorption waste residue generated in the alkali liquor absorption process, and the tail gas treatment process further comprises the step of performing melting solidification treatment on the alkali absorption waste residue. Therefore, the alkali absorption waste residues can be converted from dangerous waste residues into nontoxic waste residues through melting and solidification, and finally, the waste residues are subjected to landfill treatment. Preferably, the melt-solidification process comprises: preserving the heat of the alkali absorption waste residue for 1-4 hours at the temperature of 1100-1400 ℃ to obtain a molten mass; and water quenching the molten mass to obtain solid slag. Therefore, the alkali absorption waste residue is subjected to high-temperature melting treatment by the melting unit and then enters the water quenching unit for water quenching. Amorphous nontoxic waste residue can be obtained by cooling in a water quenching mode, and F, P and the like have better solidification effect. Preferably, silicon dioxide is added into the alkali absorption waste residue, and Ca, Na and K elements in the alkali absorption waste residue are controlled to be in oxide form (namely, CaO and Na are used2O and K2The total mole number of O) and the mole number of silicon dioxide are 0.5-1.5: 1, and then the temperature is kept for 1-4 hours under the condition of 1100-1400 ℃ to obtain the molten mass. The silica is added to form the quaternary slag system "CaO (Na)2O or K2O)-SiO2-CaF2-P2O5", the quaternary slag system is 110Can be melted at high temperature within the range of 0-1400 ℃. Control of CaO (Na)2O or K2O)/SiO2＝0.5～1.5。
In a preferred embodiment, the waste lithium ion battery recovery method further comprises the step of sorting the ball-milled materials; preferably, the sorting mode is one or more of gravity separation, flotation, magnetic separation and chemical beneficiation.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
And (3) discharging the waste ternary lithium ion battery in a NaCl solution for 24 hours, and taking out the battery and drying the battery after discharging. The battery after will airing is thrown into and is broken to the roll crusher, adopts nitrogen protection in the crushing process, and the phenomenon of catching fire does not have during this period, and the material particle diameter after the breakage is less than 2 cm. Adding the stainless steel balls and the materials into a high-temperature ball milling device shown in figure 2 according to the mass ratio of 2:1, heating to 550 ℃, keeping the rotation speed at 300 r/min, and keeping the temperature for 1 h. After ball milling, the granularity of the material is less than 5mm, the content of F in the material is reduced to 0.85% from 8.02% before pyrolysis, the content of P in the material is reduced to 0.15% from 1.75% before crushing, and the content of organic carbon in the material is reduced to 0.09% from 5.7% before pyrolysis.
Introducing nitrogen as shielding gas during operation of the ball mill, sequentially introducing generated tail gas (nitrogen, VOCs gas, F-containing gas, P-containing gas, etc.) and tail gas generated in the crushing process into an activated carbon adsorption device and an alkali liquor absorption device, wherein an absorbent in the alkali liquor absorption device is Ca (OH)2The concentration of the solution is 5 mol/L.
Recovering F, P-containing waste residue generated in the tail gas treatment process, and adding SiO2CaO/SiO in the slag2Maintaining at 1200 deg.c for 1 hr to form CaO-CaF2-SiO2-P2O5And (3) slag system, wherein the molten slag is subjected to water quenching treatment to obtain amorphous glass slag (the XRD pattern of the amorphous glass slag is shown in figure 4), and the amorphous glass slag is detected not to be hazardous waste (the detection result is shown in table 1) and can be directly subjected to landfill treatment. The materials after high-temperature ball milling can be separated by common gravity,And (4) separating by flotation, chemical method mineral separation and other processes to obtain copper, iron, aluminum and black powder. The black powder can be further recycled by valuable metals such as lithium, nickel, cobalt, manganese and the like through hydrometallurgy or pyrometallurgy.
TABLE 1 detection results of glass slag
Example 2
The method comprises the steps of physically discharging the waste ternary lithium ion battery, putting the discharged battery into a hammer crusher for crushing, wherein nitrogen protection is adopted in the crushing process, the fire phenomenon does not occur in the period, and the particle size of the crushed material is smaller than 2 cm. Adding the stainless steel balls and the materials into a high-temperature ball milling device shown in figure 2 according to the mass ratio of 4:1, heating to 600 ℃, keeping the rotation speed at 500 r/min, and keeping the temperature for 2 h. After ball milling, the granularity of the material is less than 3mm, the content of F in the material is reduced to 0.55% from 8.02% before pyrolysis, the content of P in the material is reduced to 0.07% from 1.75% before crushing, and the content of organic carbon in the material is reduced to 0.05% from 5.7% before pyrolysis.
Introducing nitrogen as shielding gas during operation of the ball mill, sequentially introducing generated tail gas (nitrogen, VOCs gas, F-containing gas, P-containing gas, etc.) and tail gas generated in the crushing process into an activated carbon adsorption device and an alkali liquor absorption device, wherein an absorbent in the alkali liquor absorption device is Ca (OH)2The concentration of the solution is 3 mol/L.
Recovering F, P-containing waste residue generated in the tail gas treatment process, and adding SiO2So as to lead CaO/SiO in the slag2Maintaining at 1300 deg.c for 1 hr to form CaO-CaF2-SiO2-P2O5Slag system, the water quenching treatment is carried out on the melting slag to obtain amorphous glass slag, the harmless treatment of fluorine and phosphorus is realized, and the glass slag can be directly buried. The materials after high-temperature ball milling can be separated by common processes such as gravity separation, flotation, chemical method mineral separation and the like to obtain copper, iron, aluminum and black powder. The black powder can be further recycled by valuable metals such as lithium, nickel, cobalt, manganese and the like through hydrometallurgy or pyrometallurgy.
Example 3
The method comprises the steps of physically discharging the waste ternary lithium ion battery, putting the discharged battery into a hammer crusher for crushing, wherein nitrogen protection is adopted in the crushing process, the fire phenomenon does not occur in the period, and the particle size of the crushed material is smaller than 2 cm. Adding the stainless steel balls and the materials into a high-temperature ball milling device shown in figure 2 according to the mass ratio of 10:1, heating to 700 ℃, keeping the rotating speed at 800 r/min, and keeping the temperature for 5 h. After ball milling, the granularity of the material is less than 1mm, the content of F in the material is reduced to 0.15% from 8.02% before pyrolysis, the content of P in the material is reduced to 0.03% from 1.75% before crushing, and the content of organic carbon in the material is reduced to 0.01% from 5.7% before pyrolysis.
Introducing nitrogen as shielding gas during operation of the ball mill, sequentially introducing generated tail gas (nitrogen, VOCs gas, F-containing gas, P-containing gas, etc.) and tail gas generated in the crushing process into an activated carbon adsorption device and an alkali liquor absorption device, wherein an absorbent in the alkali liquor absorption device is Ca (OH)2The concentration of the solution is 10 mol/L.
Recovering F, P-containing waste residue generated in the tail gas treatment process, and adding SiO2So as to lead CaO/SiO in the slag2Keeping the temperature at 1400 ℃ for 1h to form CaO-CaF ═ 0.52-SiO2-P2O5Slag system, the water quenching treatment is carried out on the melting slag to obtain amorphous glass slag, the harmless treatment of fluorine and phosphorus is realized, and the glass slag can be directly buried. The materials after high-temperature ball milling can be separated by common processes such as gravity separation, flotation, chemical method mineral separation and the like to obtain copper, iron, aluminum and black powder. The black powder can be further recycled by valuable metals such as lithium, nickel, cobalt, manganese and the like through hydrometallurgy or pyrometallurgy.
Example 4
The method comprises the steps of physically discharging the waste ternary lithium ion battery, putting the discharged battery into a hammer crusher for crushing, wherein nitrogen protection is adopted in the crushing process, the fire phenomenon does not occur in the period, and the particle size of the crushed material is smaller than 2 cm. Adding the stainless steel balls and the materials into a high-temperature ball milling device shown in figure 2 according to the mass ratio of 1:1, heating to 500 ℃, keeping the rotating speed at 100 r/min, and keeping the temperature for 1 h. After ball milling, the granularity of the material is less than 8mm, the content of F in the material is reduced to 1.43% from 8.02% before pyrolysis, the content of P in the material is reduced to 0.25% from 1.75% before crushing, and the content of organic carbon in the material is reduced to 0.87% from 5.7% before pyrolysis.
Introducing nitrogen as shielding gas during operation of the ball mill, sequentially introducing generated tail gas (nitrogen, VOCs gas, F-containing gas, P-containing gas, etc.) and tail gas generated in the crushing process into an activated carbon adsorption device and an alkali liquor absorption device, wherein an absorbent in the alkali liquor absorption device is Ca (OH)2The concentration of the solution is 1 mol/L.
Recovering F, P-containing waste residue generated in the tail gas treatment process, and adding SiO2So as to lead CaO/SiO in the slag2Maintaining at 1400 deg.c for 1 hr to form CaO-CaF2-SiO2-P2O5Slag system, the water quenching treatment is carried out on the melting slag to obtain amorphous glass slag, the harmless treatment of fluorine and phosphorus is realized, and the glass slag can be directly buried. The materials after high-temperature ball milling can be separated by common processes such as gravity separation, flotation, chemical method mineral separation and the like to obtain copper, iron, aluminum and black powder. The black powder can be further recycled by valuable metals such as lithium, nickel, cobalt, manganese and the like through hydrometallurgy or pyrometallurgy.
Comparative example 1
The method comprises the following steps of physically discharging the waste ternary lithium ion battery, putting the discharged battery into a multistage crushing device for crushing, adopting nitrogen protection in the crushing process, avoiding the fire phenomenon in the period, and enabling the particle size of the crushed material to be less than 5 mm. And performing ordinary pyrolysis on the crushed materials, wherein the pyrolysis temperature is 650 ℃, and the heat preservation time is 2 hours. After pyrolysis treatment, the content of F in the material is reduced to 3.95% from 8.02% before pyrolysis, the content of P in the material is reduced to 0.85% from 1.75% before crushing, and the content of organic carbon in the material is reduced to 0.97% from 5.7% before pyrolysis.
By comparison, although the material can be crushed to 5mm or less by multi-stage crushing, agglomeration phenomenon occurs in the pyrolysis process, and volatilization of F, P elements and pyrolysis of organic matters are affected. The high-temperature ball milling treatment can effectively improve the volatilization of F, P elements and the pyrolysis of organic matters.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. The utility model provides a waste lithium ion battery recovery unit which characterized in that includes:
the discharging device (10) is provided with a waste lithium ion battery inlet and a discharging lithium ion battery outlet, and the discharging device (10) is used for discharging the waste lithium ion battery;
the crushing device (20) is provided with a discharge lithium ion battery inlet, a crushed material outlet, a first inert gas inlet and a first tail gas outlet, wherein the discharge lithium ion battery inlet is connected with the discharge lithium ion battery outlet;
the high-temperature ball milling device (30) is provided with a crushed material inlet, a ball milling material outlet, a second inert gas inlet and a second tail gas outlet, the crushed material inlet is connected with the crushed material outlet, and the high-temperature ball milling device (30) is used for simultaneously pyrolyzing and ball milling the crushed material discharged by the crushing device (20);
an inert gas supply device (40) connected to the first inert gas inlet and the second inert gas inlet, respectively;
and the tail gas treatment device (50) is respectively connected with the first tail gas outlet and the second tail gas outlet.
2. The recovery device of spent lithium ion batteries according to claim 1, characterized in that said high temperature ball milling device (30) comprises:
a housing (31) having the second inert gas inlet and the second off-gas outlet;
the ball milling tank (32) is positioned inside the shell (31), the ball milling tank (32) is provided with the crushed material inlet and the ball milling material outlet, and the ball milling tank (32) is also provided with air vents;
a heating unit (33) located inside the housing (31), the heating unit (33) being used for heating the ball milling pot (32).
3. The recycling apparatus of waste lithium ion batteries according to claim 2, characterized in that a plurality of ball milling pots (32) and a plurality of heating units (33) are arranged inside the housing (31).
4. The waste lithium ion battery recycling device according to claim 3, wherein the plurality of heating units (33) are divided into a first group and a second group, wherein the first group of heating units (33) is located at the center of the housing (31), the plurality of ball mill pots (32) are planetary-distributed around the first group of heating units (33), and the second group of heating units (33) is located at the periphery of the ball mill pots (32).
5. The recovery plant of spent lithium ion batteries according to any one of claims 1 to 4, characterized in that said tail gas treatment plant (50) comprises:
the physical adsorption unit (51) is provided with a tail gas inlet and an adsorption residual gas outlet, and the tail gas inlet is respectively connected with the first tail gas outlet and the second tail gas outlet;
and the alkali liquor absorption unit (52) is provided with an adsorption residual gas inlet, a purified gas outlet and an alkali absorption waste residue outlet, and the adsorption residual gas inlet is connected with the adsorption residual gas outlet.
6. The waste lithium ion battery recycling device according to claim 5, wherein the tail gas treatment device (50) further comprises a melting and solidifying unit (53), and the melting and solidifying unit (53) is provided with an alkali absorption waste residue inlet which is connected with the alkali absorption waste residue outlet.
7. The waste lithium ion battery recovery device according to any one of claims 1 to 4, further comprising a sorting device (60), wherein the sorting device (60) is provided with a ball milling material inlet, the ball milling material inlet is connected with the ball milling material outlet, and the sorting device (60) is used for sorting the ball milling material discharged from the high temperature ball milling device (30).
8. A method for recovering waste lithium ion batteries is characterized by comprising the following steps:
carrying out discharge treatment on the waste lithium ion battery to obtain a discharged lithium ion battery;
crushing the discharge lithium ion battery to obtain a crushed material; performing high-temperature ball milling treatment on the crushed materials to simultaneously perform pyrolysis and ball milling on the crushed materials to obtain ball-milled materials; wherein the crushing treatment process and the high-temperature ball milling treatment process are both carried out under the protection of inert gas;
and collecting tail gas generated in the crushing treatment process and the high-temperature ball milling treatment process, and carrying out tail gas treatment on the tail gas.
9. The method for recycling the waste lithium ion batteries according to claim 8, wherein in the crushing process, the discharged lithium ion batteries are crushed to have a particle size of less than 2 cm.
10. The recovery method of the waste lithium ion batteries according to claim 8 or 9, wherein the ball milling temperature in the high-temperature ball milling treatment process is 500-700 ℃, and the ball milling time is 1-5 hours; preferably, the mass ratio of the ball materials in the high-temperature ball milling treatment process is 1-10: 1, and the ball milling rotating speed is 100-800 r/min.
11. The method for recovering the waste lithium ion batteries according to claim 8 or 9, wherein the tail gas treatment process comprises a physical adsorption process and an alkali liquor absorption process which are sequentially carried out;
preferably, the physical adsorption process uses activated carbon as an adsorbent;
preferably, the first and second electrodes are formed of a metal,the absorbent adopted in the alkali liquor absorption process is Ca (OH)2、NaOH、KOH、NaHCO3And KHCO3More preferably, the concentration of the absorbent is 1-10 mol/L.
12. The method for recycling the waste lithium ion batteries according to claim 11, wherein the lye absorption process adopts a spray absorption mode or a static absorption mode.
13. The method for recycling the waste lithium ion batteries according to claim 11, wherein the alkali absorption waste residues generated in the alkali liquor absorption process, and the tail gas treatment process further comprises a step of performing melting and solidification treatment on the alkali absorption waste residues; preferably, the melt-solidification process includes:
preserving the heat of the alkali absorption waste residue for 1-4 hours at the temperature of 1100-1400 ℃ to obtain a molten mass; preferably, adding silicon dioxide into the alkali absorption waste residues, controlling the ratio of the total mole number of Ca, Na and K elements in the alkali absorption waste residues in the form of oxides to the mole number of the silicon dioxide to be 0.5-1.5: 1, and then preserving heat at the temperature of 1100-1400 ℃ for 1-4 hours to obtain the molten mass;
and performing water quenching on the molten mass to obtain solid slag.
14. The waste lithium ion battery recovery method according to claim 8 or 9, further comprising the step of sorting the ball-milled material;
preferably, the sorting mode is one or more of gravity separation, flotation, magnetic separation and chemical method ore dressing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010496157.3A CN111554994A (en) | 2020-06-03 | 2020-06-03 | Waste lithium ion battery recovery device and method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010496157.3A CN111554994A (en) | 2020-06-03 | 2020-06-03 | Waste lithium ion battery recovery device and method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111554994A true CN111554994A (en) | 2020-08-18 |
Family
ID=72003252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010496157.3A Pending CN111554994A (en) | 2020-06-03 | 2020-06-03 | Waste lithium ion battery recovery device and method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111554994A (en) |
-
2020
- 2020-06-03 CN CN202010496157.3A patent/CN111554994A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Makuza et al. | Pyrometallurgical options for recycling spent lithium-ion batteries: A comprehensive review | |
| Yu et al. | Pretreatment options for the recycling of spent lithium-ion batteries: A comprehensive review | |
| CN111392750B (en) | Method for removing impurities and recovering lithium from waste lithium ion batteries | |
| CN110931909A (en) | Recovery method of waste lithium ion battery | |
| CN110071342A (en) | Waste and old lithium ion battery recovery method and device | |
| EP4207434A1 (en) | Wet separation process for waste lithium batteries and use thereof | |
| US20210384562A1 (en) | Process for physically separating and recovering various components from spent lithium ion batteries | |
| CN109888370A (en) | Waste and old lithium ion battery method for pyrolysis and system | |
| Dobó et al. | A review on recycling of spent lithium-ion batteries | |
| CN112779421B (en) | Method for recycling anode material of waste lithium ion battery | |
| CN109449525A (en) | The innoxious recovery and treatment method and device of waste lithium cell electrolyte | |
| JP7271833B2 (en) | Lithium recovery method | |
| CN114151802A (en) | Method for recycling all components of waste lithium battery | |
| Tanong et al. | Metal recycling technologies for battery waste | |
| JP2021031760A (en) | Process for recovering valuable metal | |
| CN112909370A (en) | Method for repairing ternary cathode material in waste lithium battery | |
| JP7363207B2 (en) | How to recover valuable metals | |
| CN211980826U (en) | Waste lithium ion battery recovery device | |
| Shi et al. | A comprehensive review of full recycling and utilization of cathode and anode as well as electrolyte from spent lithium-ion batteries | |
| CN209526183U (en) | Waste and old lithium ion battery recyclable device | |
| CN105742747B (en) | Utilize the method for useless cobalt acid lithium purification relieving haperacidity tail gas and Call Provision lithium | |
| CN112827337A (en) | Fluorine removal device, waste lithium battery treatment system, treatment method and application thereof | |
| CN111554994A (en) | Waste lithium ion battery recovery device and method | |
| CN112820970B (en) | Harmless treatment method for waste lithium battery electrolyte | |
| CN209526167U (en) | Waste and old lithium ion battery pyrolysis system |
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 |