CN103060567A - Method for processing waste lithium ion battery positive plate to extract valuable metal - Google Patents
Method for processing waste lithium ion battery positive plate to extract valuable metal Download PDFInfo
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- CN103060567A CN103060567A CN2012105622350A CN201210562235A CN103060567A CN 103060567 A CN103060567 A CN 103060567A CN 2012105622350 A CN2012105622350 A CN 2012105622350A CN 201210562235 A CN201210562235 A CN 201210562235A CN 103060567 A CN103060567 A CN 103060567A
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- 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
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- 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
Abstract
A method for processing a waste lithium ion battery positive plate to extract valuable metal is characterized in that chlorine gas is piped in to a failure lithium ion battery positive plate under the existence of reducing agent carbon under the temperature of 450-650 DEG C to carry out chlorination processing, and a mixed product of smoke and condensed state chloride containing the valuable metal is obtained; and undissolved substances insoluble in water and valuable metal chloride solutions soluble in water are obtained through water emersion of the mixed product. The method can efficiently recover high-purification aluminum salt and other valuable metallic compounds in a short process; acid or alkaline or organic solvents are not adopted in the treatment process, and environmental management is easy.
Description
Technical field
The invention belongs to the resource circulation utilization field.Be specifically related to a kind of method of from based lithium-ion battery positive plate, extracting valuable metal.
Background technology
Lithium ion battery is modern advanced chemical power source, the power source that is widely used in consumption electronic product, war products, aeronautical product, instrument and shipping products etc., also be the light high-energy power cell of following electromobile first-selection, have huge market in the whole world.Take mobile communication as example, Global Mobile Phone Users surpasses 3,500,000,000 at present, and Chinese user surpasses 600,000,000, and at increase year after year.As rechargeable cell, after lithium ion battery discharges and recharges through hundreds of times (normal operation 1 ~ 2 year), owing to dilatational strain, capacity loss etc. cause scrapping, then scrap pending lithium ion battery enormous amount every year, and will increase substantially year by year.
Lithium ion battery has the structure similar to other chemical power sources, is made of shell, battery core, electrolytic solution; The positive plate that consists of battery core is that positive electrode material (composite oxide material take non-ferrous metal elements such as Li, Co, Ni, Mn as chief component) is coated on and forms on the aluminium plasma membrane, and negative plate is that negative material (carbon material) is coated on the copper film and forms.Metal content in the common lithium ion battery core body material sees the following form:
Metal content in the common lithium ion battery core body of table 1 material
| Element term | Co(Ni,Mn) | Cu | Al | Li |
| Content/% | 20.0~22.0 | 18.0~20.0 | 6.0~6.4 | 2.2~2.5 |
As seen, anode material for lithium-ion batteries has become one of important applied field of nonferrous materials.A large amount of discarded lithium ion batteries that lost efficacy have become the important secondary resource of Li, Co, Ni, Mn, Cu and Al etc.Wherein copper is the current collector material as battery cathode, and aluminium is the current collector material of anode, and cobalt (nickel, manganese) and lithium are the main components of positive electrode active materials.Therefore, waste and old lithium ion battery is the important secondary resource of copper, aluminium, lithium, cobalt (nickel, manganese) etc., has the content higher than its first resource.
For cobalt most valuable in the battery, lithium and copper, the most convenient the positive and negative electrode separate treatment.Adopt special disintegration separating device, battery can be disintegrated, and positive and negative electrode is separated; From negative plate, reclaim and obtain copper, from positive plate, reclaim cobalt, lithium and aluminium.For present lithium ion battery with graphite cathode material, the recovery of negative pole copper and graphite is relative simple, can reach target with simple high melt.And the processing relative complex of positive plate and have higher economic worth.
In processing the process of positive plate, generally be first the aluminium plasma membrane to be separated with active material, process active material with chemical process again, obtain Co(Ni, Mn through separating, purifying), metal or the compound of Li, Cu and Al etc.; Key wherein is the effective separation of aluminium film and active substance and the high-efficiency dissolution of active substance.
The method of separating aluminium film and active substance has Physical, chemical method, and respectively by different approach: l) the dissolving binding agent destroys contact interface; 2) dissolving collector.In lithium ion battery manufacture process, binding agent PVDF is adjoined pyrrolidone with the NMP(N-methyl) dissolving, with positive active material or negative electrode active material mixing furnishing slurry, be coated in again and make membrane coated electrode on the metal collector
[1]In the research that now has been reported, adopt the organic solvent dissolution aluminium foil base binding agent PVDF on the useless pole piece that films, can conveniently reclaim positive electrode active material and metal A l
[2]Utilize positive electrode active material to be insoluble to the character of alkali, dissolve in advance most of aluminium in the useless pole piece of filming with NaOH, and positive electrode active material is all stayed alkali and soaked in the slag and separated
[3]
In the recovery method of the processing of active substance and valuable metal material; The recovery key of valuable constituent is the dissolving of active substance, adopts efficient reaction reagent that active substance is decomposed, and effective constituent is entered in the solution with ionic species, convenient follow-up the separation in every way and purifying.At present, dissolving method commonly used is acid pasting, and the acid of employing has hydrochloric acid (HCl)
[4], sulfuric acid
[5]And nitric acid
[6]Deng.Comparatively speaking, the sulfuric acid dissolution method is used widely, but does not adopt the simple sulfur acid-soluble method, generally adds H
2O
2 [7], Na
2S
2O
3 [8]Deng reductive agent process is strengthened.
But existing technique comprises in the above technique, often all has many, the long flow path for the treatment of processes operation, and uses number of chemical reagent.At aluminium film and active substance separation phase, the organic solvent kind of PVDF is few, price is high but can dissolve, and limited to the dissolving power of PVDF; Although solvent can be recycled, separate PVDF difficulty and purifies and separates cycle weak point.The aluminium foil alkali solution technique adopts the highly basic operation, increase the molten acid consumption of follow-up acid, and operating environment is poor; Generate Al (OH)
3Particle is tiny, and carries carbon dust particulate and organic binder bond colloid secretly, filters, washs difficulty; The Al that obtains (OH)
3Impurity is high, is difficult to utilize.In active substance acid dissolution phase, the high acidity dissolving of adopting reductive agent to strengthen needs use the alkali neutralizing acid, and acid, alkali, reductive agent consumption are large, and discharge of wastewater is many, and environmental protection pressure is large.
Reference:
1. Wu Yu is flat, Dai Xiaobing, and the horse army flag, etc. lithium ion battery one application and practice [M]. Beijing: Chemical Industry Press, 2004
2. Qin Yi is red, Qi Shen. Treatment of Waste Lithium-ion Batteries by Organic Solvent Partition Process [J]. and non-ferrous metal (Smelting Part), 2006,1:13-16
3. Wu Fang. from spent lithium-ion secondary batteries, reclaim cobalt and lithium [J]. China YouSe Acta Metallurgica Sinica, 2004,14 (4): 697-701
4.Zhang P W, Yokoyama T, Itabash O, etal.Hydrometallurgical proeess for recovey of metal values from spent Li-ion second batteries[J] .Hydromctallurgy, 1998,47 (2 ~ 3): 259 1 271
5.Lain?M?J.Recycling?of?lithium?ion?cells?and?batteries[J].Journal?of?Power?Source,2001,97-98:736~738
6.Churl?K.L.,Kang-In.R.Reductive?leaching?of?cathodic?active?metals?from?lithium?ion?batteries[J].Hydrometallurgy.2003,68(l-3):5~10
7. clock sea cloud, Lee recommends, Chai Liyuan. from lithium ion secondary battery positive electrode waste material-aluminium cobalt film, reclaim the technical study [J] of aluminium. and rare metal and Wimet, 2001,3:1 ~ 4
8. Guo Li duckweed, youngest brother Du, Fang Wei, the top gem of a girdle-pendant .Na of thunder man
2S
2O
3Reduction of dissolved LiCoO
4Reach cobalt, lithium Separation and Recovery [J]. applied chemistry, 2006,23 (10): 1152
Summary of the invention
The object of the present invention is to provide a kind for the treatment of process of disabled lithium ion cell positive plate, flow process is short, but high efficiency separation goes out the high aluminium salt of purity and other valuable metal compounds; And adopt the lower temperature process in the treating processes, energy consumption is low simultaneously.
Technical scheme of the present invention is: the disabled lithium ion cell positive plate in the presence of reductive agent carbon, is passed into chlorine in 450 ~ 650 ℃ of temperature and carries out chloridized, obtain flue dust and contain the muriatic mix products of valency metal condensed state; Described mix products by water logging, is separated and removes insolubles and obtain the valuable metal chloride soln.
Pass into total amount 1.50 ~ 1.65kg in 1.0kg disabled lithium ion cell positive plate material control chlorine.
The described chloridized time is 20 ~ 40min.
The add-on of reductive agent carbon is positive plate raw materials quality 10 ~ 15%.
Described flue dust is sneaked into freezing air and be cooled to 160 ~ 200 ℃, cyclone dust collection obtains flue gas and solid dust, collects solid dust, and flue gas is emptying after water washing, absorption, purification; Dust, washings individual curing.
Cyclone dust collection gets AlF to flue dust
3, Al
2O
3Mixture (can be used for electrolysis of aluminum); Flue gas alkali lye after the cyclone dust collection is that mass percentage content is that 20 ~ 25%NaOH aqueous solution absorbs.Absorb the solution that obtains through alkaline solution and can be used for reclaiming the NaClO product.
The present invention is by the processing to mix products: the condensed state muriate to chlorination process carries out water logging, thereby so that the water-soluble solution that enters of muriate of valuable metal lithium, cobalt, nickel, manganese etc.; And then can adopt the separation methods such as the precipitator method, solvent extration, ion exchange method to process the mixed chloride solution, to the valuable metal compound separate, purifying, make product.Typical treatment process can the precipitator method be combined processing with solvent extration: first Quilonum Retard precipitate cobalt, nickel, manganese get cobalt, nickel, manganese mixed carbonate, precipitate lithium with yellow soda ash again and get Quilonum Retard; Cobalt, nickel, manganese mixed carbonate extract manganese with the P204 extracting and separating after acid is molten, get the purified salt of manganese, cobalt and nickel with P507 extracting and separating cobalt, nickel again.
Based lithium-ion battery positive plate is to be coated on by positive electrode material (composite oxide material take non-ferrous metal elements such as Li, Co, Ni, Mn as chief component) to form on the aluminium plasma membrane, and generally adopting PVDF is matrix material; These materials can produce series of physical chemical transformation and interaction in the treating processes of waste pole piece.The present invention is chlorinated valuable metal and the compound thereof of based lithium-ion battery positive plate by under the certain condition; Particularly aluminium is a kind of relatively active metal, very easily reacts with chlorine; And produce following series reaction by the control of the inventive method, thus realize the effective separation of positive plate of lithium battery:
Al+3/2Cl
2==1/2Al
2Cl
6(g)
Product aluminum chloride volatilizees with dimeric form.
Active substance Li (Co, Ni, Mn) O
2Under reductive agent C existence condition, react with chlorine:
Li(Co,Ni,Mn)O
2+C+3/2Cl
2==LiCl+(Co,Ni,Mn)Cl
2+CO
2(g)
Valuable metal muriate product exists with condensed state.
Binding agent PVDF is fluoropolymer, but thermal degradation:
[-C
2H
2F
2-]
n==2nC+2nHF(g)
Product decomposes the carbon that produces can participate in active substance Li (Co, Ni, Mn) O
2Reaction with chlorine; The hydrogen fluoride gas that produces also gaseous aluminum chloride reaction generates the solid aluminum fluoride:
Al
2Cl
6+6HF==2AlF
3+6HCl
The hydrogenchloride that produces can be used as chlorizating agent and active substance effect:
4Li(Co,Ni,Mn)O
2+C+12HCl==4LiCl+4(Co,Ni,Mn)Cl
2+CO
2(g)+6H
2O(g)
The water that produces can make aluminum chloride be decomposed into aluminum oxide:
Al
2Cl
6+6H
2O==2Al
2O
3+6HCl(g)
Because the existence of binding agent PVDF, the HF that pyrolytic decomposition produces is Al
2Cl
6The catalyzer of hydrolysis impels Al
2Cl
6Be hydrolyzed into Al
2O
3
Significantly, aluminium film volatilizees, then forms water-fast aluminum oxide and aluminum fluoride by chlorination process with aluminum chloride, can reclaim Aluminum Compounds from the reaction flue dust gathers dust or in the water logging slag of condensation product; The condensed state product separates insolubles (as: aluminum oxide, aluminum fluoride, value Mn oxide compound and carbon dust etc.) through water logging with muriates such as solvable lithium, cobalt, nickel and manganese; Aqueous chloride solution behind the separation aluminium can pass through the processes such as separation, purifying and process the compound that reclaims non-ferrous metal lithium, cobalt, nickel and manganese etc.
According to above principle, the technological process of processing the waste lithium ion cell anode sheet can be: material preparation, chlorination, volatile matter processing and condensation product processing etc.; It is most important link that wherein chlorination, volatile matter are processed.
The material set-up procedure: the positive plate of disassembling out from old and useless battery is the long strip type flap, and activity and binding agent are through applying, be compacted at aluminium film surface.In order to make aluminium film obtain larger response capacity, with the carrying out of accelerated reaction, must carry out to material the processing in early stage.The processing main program of lithium ion anode sheet is broken, oven dry and prepares burden with reductive agent.
Chlorination process: the aluminum chloride of generation can volatilize at lower temperature, and the present invention so that metallic aluminium changes into aluminum chloride, after the volatilization, is further converted to again water-fast aluminum fluoride and aluminum oxide by the control chlorination temperature; Simultaneously, other metal active material decomposition and form water-soluble chloride mix of condensed state lithium, cobalt, nickel or manganese;
Dust treatment: metallic aluminium through chloridizing volatilization, then form insoluble aluminum fluoride and aluminum oxide after, change flue dust over to gas-phase product; Flue dust gets solid-state insoluble aluminum compound dust through gas solid separation.There are the complete chlorine of unreacted or product hydrogenchloride in the gas phase simultaneously, recycling, regeneration chlorizating agent.
The processing of condensed matter: active substance is chlorinated the chloride mix of decomposing and forming condensed state lithium, cobalt, nickel or manganese, mixed chloride water soluble; Mixture is after water logging, and valuable metal lithium, cobalt or nickel and manganese etc. enter the aqueous solution with ionic species, and after available precipitation separation, extraction separation method etc. carried out the element separation, purification refine became corresponding compound.
Detailed content of the present invention is as follows:
(1) pre-treatment: the waste lithium ion cell anode sheet is crushed to is less than 5mm; The activated carbon that adds positive plate raw materials quality 10 ~ 15% is mixed together evenly.
(2) chloridized: the mixture in (1) step is entered stove, under the chlorine effect, carry out chloridized; Chlorization condition is: 450 ~ 650 ℃ of temperature; Time 20 ~ 60min; By 1.0kg positive plate control chlorine total amount 1.50 ~ 1.65kg.
(3) dust treatment: flue dust is through sneaking into chilled air cools to 160 ~ 200 ℃, and solid dust is collected in cyclone dust collection, and flue gas is emptying after water washing, absorption, purification; Dust, washings individual curing.
(4) processing of condensed state product: the condensed state product to chlorination process carries out water logging, the water-soluble solution that enters of valuable metal muriate (such as the muriate of lithium, cobalt, nickel, manganese etc.).Can adopt the separation methods such as the precipitator method, solvent extration, ion exchange method to process mixed chloride solution, to the valuable metal compound separate, purifying, make product.Typical treatment process can the precipitator method be combined processing with solvent extration: first Quilonum Retard precipitate cobalt, nickel, manganese get cobalt, nickel, manganese mixed carbonate, precipitate lithium with yellow soda ash again and get Quilonum Retard; Cobalt, nickel, manganese mixed carbonate extract manganese with the P204 extracting and separating after acid is molten, get the purified salt of manganese, cobalt and nickel with P507 extracting and separating cobalt, nickel again.
Method of the present invention can produce following advantage and positively effect:
(1) to take full advantage of the muriate of each metal in the positive electrode material be that fusing point, boiling point difference are carried out effective separation in the present invention; Wherein, aluminum chloride fusing point, the low spot that boils are low, volatile, and cobalt, nickel, manganic compound enter after chlorination in the condensed phase, conveniently separate with unclassified stores.
(2) adopt Quilonum Retard as the precipitation agent of cobalt, nickel and manganese etc., the not additional extraction of bringing impurity into, making things convenient for lithium; Enter the lithium in the solution in the precipitation process, carry in the lithium process at follow-up carbonate deposition and reclaiming, namely Quilonum Retard is the product in the technical process of the present invention, realizes the circulation of Quilonum Retard in the precipitation process.
(3) mixture solution of employing traditional solution extraction art breading cobalt, nickel and manganese, technical maturity, easy and simple to handle makes the present invention be easy to realize processing the industrialization of waste lithium ion cell anode sheet.
(4) adopt the lower temperature process, equipment and not harsh with material, energy consumption is low simultaneously.
Embodiment:
Below in conjunction with implementation the present invention is described further.The discarded based lithium-ion battery positive plate material that adopts contains aluminium 10.4%; Sheet material is crushed to is less than 5mm, dry to water content and be lower than 0.1%, as the spent material among the following embodiment.
Embodiment 1
(actives is LiCoO will to contain the positive plate of aluminium 10.4%
2) be crushed to and be less than 5mm, dry to water content and be lower than 0.1%; Press the 1.0kg sheet stock and add 140 ~ 150g activated carbon, mix.
The material that mixes is directly added the chlorination reaction stove continuously through the tubular type screw feeder, and temperature was 600 ~ 650 ℃ when chlorination reaction was carried out; Chlorine consumption 1.60 ~ 1.65kg by material 1.0kg; Material reaction (stopping in the stove) time 20 ~ 25min; By discharging spiral organ continuous discharge.
The chlorination reaction flue gas is cooled to 190 ~ 200 ℃ through sneaking into freezing air, collects ultra-fine alumina, aluminum fluoride through cyclone; Gas discharging after 22 ~ 25%NaOH liquid spray, two-stage packing tower absorb; The treated recycling of absorption liquid.
The solid product of chlorination reaction filters, purifies through water logging, gets LiCl, CoCl
2The aqueous solution.Get cobaltous carbonate, precipitate to get Quilonum Retard through yellow soda ash again through the Quilonum Retard precipitate cobalt; Mother liquor behind the precipitation Quilonum Retard is used for reclaiming NaCl.
The rate of recovery 91.0% of aluminium; The recovery of Co rate is 98.1%; The direct yield 88.7% of lithium; The cobaltous carbonate product is CoCO
399.6%; Lithium carbonate product is Li
2CO
398.8%.
Embodiment 2
(actives is ternary material Li (Ni, Co, Mn) O will to contain the positive plate of aluminium 10.8%
2) be crushed to and be less than 5mm, dry to water content and be lower than 0.1%; Press the 1.0kg sheet stock and add 130 ~ 140g activated carbon, mix.
The material that mixes is directly added the chlorination reaction stove continuously through the tubular type screw feeder, and temperature was 450 ~ 500 ℃ when chlorination reaction was carried out; Chlorine consumption 1.55 ~ 1.60kg by material 1.0kg; Material reaction (stopping in the stove) time 35 ~ 40min; By discharging spiral organ continuous discharge.
The chlorination reaction flue gas is cooled to 170 ~ 180 ℃ through sneaking into freezing air, collects ultra-fine alumina, aluminum fluoride through cyclone; Gas discharging after 20 ~ 22%NaOH liquid spray, two-stage packing tower absorb; The treated recycling of absorption liquid.
The solid product of chlorination reaction filters, purifies through water logging, gets LiCl, (Ni, Co, Mn) Cl
2The aqueous solution.Must be mixed to get carbonate, precipitate to get Quilonum Retard through yellow soda ash again through Quilonum Retard coprecipitated nickel hydroxide, cobalt, manganese; Mother liquor behind the precipitation Quilonum Retard is used for reclaiming NaCl.
The rate of recovery 91.3% of aluminium; The comprehensive recovery that nickel, cobalt and manganese form mixed carbonate is 97.4%; The direct yield 88.1% of lithium; Impurity is less than 0.7% in the triplex carbonate product; Lithium carbonate product is Li
2CO
398.3%.
Embodiment 3
(actives is LiCoO will to contain the positive plate of aluminium 10.4%
2) be crushed to and be less than 5mm, dry to water content and be lower than 0.1%; Press the 1.0kg sheet stock and add 100 ~ 120g activated carbon, mix.
The material that mixes is directly added the chlorination reaction stove continuously through the tubular type screw feeder, and temperature was 550 ~ 600 ℃ when chlorination reaction was carried out; Chlorine consumption 1.50 ~ 1.55kg by material 1.0kg; Material reaction (stopping in the stove) time 30 ~ 35min; By discharging spiral organ continuous discharge.
The chlorination reaction flue gas is cooled to 180 ~ 190 ℃ through sneaking into freezing air, collects ultra-fine alumina, aluminum fluoride through cyclone; Gas discharging after 20 ~ 22%NaOH liquid spray, two-stage packing tower absorb; The treated recycling of absorption liquid.
The solid product of chlorination reaction filters, purifies through water logging, gets LiCl, CoCl
2The aqueous solution.Get cobaltous carbonate, precipitate to get Quilonum Retard through yellow soda ash again through the Quilonum Retard precipitate cobalt; Mother liquor behind the precipitation Quilonum Retard is used for reclaiming NaCl.
The rate of recovery 92.1% of aluminium; The recovery of Co rate is 97.4%; The direct yield 87.5% of lithium; The cobaltous carbonate product is CoCO
399.2%; Lithium carbonate product is Li
2CO
398.5%.
Claims (7)
1. process the method that the waste lithium ion cell anode sheet extracts valuable metal for one kind, it is characterized in that, with the disabled lithium ion cell positive plate in the presence of reductive agent carbon, pass into chlorine in 450 ~ 650 ℃ of temperature and carry out chloridized, obtain flue dust and contain the muriatic mix products of valency metal condensed state; Described mix products is obtained water-fast insolubles and water-soluble valuable metal chloride soln by water logging.
2. method according to claim 1 is characterized in that, passes into total amount 1.50 ~ 1.65kg in 1.0kg disabled lithium ion cell positive plate material control chlorine.
3. method according to claim 1 and 2 is characterized in that, the described chloridized time is 20 ~ 40min.
4. method according to claim 1 is characterized in that, the add-on of reductive agent carbon is 10 ~ 15% of described positive plate quality.
5. method according to claim 1 is characterized in that, through sneaking into chilled air cools to 160 ~ 200 ℃, solid dust is collected in cyclone dust collection with described flue dust, and flue gas is emptying after water washing, absorption, purification; Dust, washings individual curing.
6. method according to claim 1 is characterized in that, comprises following preparation process:
(1) pre-treatment: the waste lithium ion cell anode sheet is crushed to is less than 5mm; The activated carbon that adds positive plate raw materials quality 10 ~ 15% is mixed together evenly;
(2) chloridized: the mixture in (1) step is entered stove, carry out chloridized under the chlorine effect, treatment condition are: 450 ~ 650 ℃ of temperature; Time 20 ~ 60min; By 1.0kg material control chlorine total amount 1.50 ~ 1.65kg;
(3) dust treatment: flue dust is through sneaking into chilled air cools to 160 ~ 200 ℃, and solid dust is collected in cyclone dust collection, and flue gas is emptying after water washing, absorption, purification.
7. each described method is characterized in that according to claim 1-6, and described valuable metal chloride soln except aluminium, gets lithium, cobalt or nickel, manganese mixed solution through the degree of depth; The muriate mixed solution is further separated: first Quilonum Retard precipitate cobalt, nickel, manganese get cobalt, nickel, manganese mixed carbonate, get Quilonum Retard with yellow soda ash precipitation lithium again; Cobalt, nickel, manganese mixed carbonate extract manganese with the P204 extracting and separating after acid is molten, get the purified salt of manganese, cobalt and nickel with P507 extracting and separating cobalt, nickel again.
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| CN108063295A (en) * | 2017-12-06 | 2018-05-22 | 天齐锂业股份有限公司 | The method that lithium is extracted in the clinker generated from pyrogenic process recycling lithium battery |
| CN108063295B (en) * | 2017-12-06 | 2020-09-22 | 天齐锂业股份有限公司 | Method for extracting lithium from slag generated by pyrogenic recovery of lithium battery |
| CN108910928A (en) * | 2018-09-18 | 2018-11-30 | 新特能源股份有限公司 | The co-production and two kinds of metal chlorides of two kinds of metal chlorides |
| CN112342394A (en) * | 2020-10-29 | 2021-02-09 | 广东邦普循环科技有限公司 | Incomplete-extraction battery recovery method |
| EP4206340A4 (en) * | 2020-10-29 | 2023-09-13 | Guangdong Brunp Recycling Technology Co., Ltd | Non-full extraction battery recovery method |
| US11920213B2 (en) | 2020-10-29 | 2024-03-05 | Guangdong Brunp Recycling Technology Co., Ltd. | Method for recycling battery by incomplete extraction |
| WO2023017910A1 (en) * | 2021-08-09 | 2023-02-16 | Korea Atomic Energy Research Institute | Recycling method of positive electrode material for secondary batteries and device using the same |
| CN114959254A (en) * | 2022-04-24 | 2022-08-30 | 山东大学 | Method for separating and recovering cobalt and lithium in lithium cobaltate |
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