CN109004307A - The recyclable device of valuable metal in waste and old nickel cobalt manganese lithium ion battery - Google Patents
The recyclable device of valuable metal in waste and old nickel cobalt manganese lithium ion battery Download PDFInfo
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- CN109004307A CN109004307A CN201810923244.5A CN201810923244A CN109004307A CN 109004307 A CN109004307 A CN 109004307A CN 201810923244 A CN201810923244 A CN 201810923244A CN 109004307 A CN109004307 A CN 109004307A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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
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Abstract
The present invention relates to a kind of recyclable devices of valuable metal in waste and old nickel cobalt manganese lithium ion battery, it is characterised in that it includes the pretreatment unit, heating device, equipment for separating liquid from solid, the 1st reactor, the 1st recyclable device, the 2nd reactor, the 2nd recyclable device and valuable metal cobalt, manganese, zinc and the yttrium separator that are connected by pipeline.
Description
Technical field
The present invention relates to a kind of recyclable devices of valuable metal in waste and old nickel cobalt manganese lithium ion battery.
Background technique
Lithium ion battery is positive electrode using lithium alloy metals oxide, and graphite is negative electrode material.According to statistics, 2000
The consumption figure of year whole world lithium ion battery is 500,000,000, has reached 7,000,000,000 within 2015.Due to the service life of lithium ion battery
Be it is limited, a large amount of waste and old lithium ion battery also generates therewith.By taking China as an example, it is contemplated that the discarded lithium battery in the year two thousand twenty China will
More than 25,000,000,000, gross weight is more than 500,000 tons.Discarded lithium battery, anode contain a large amount of noble metals, and wherein cobalt accounts for 5~20%,
Nickel accounts for 5~12%, and manganese accounts for 7~10%, and lithium accounts for 2~5% and 7% plastics, and contained metal is rare metal mostly, it should reasonable
Recycling and reusing.For example, cobalt as a kind of strategic resource, is widely used in every field, in addition to there are also high temperature for lithium battery
Alloy etc..It can calculate, the yield of noble metal is huge.
Mainly there are pyrometallurgy recycling and hydrometallurgical recovery now for the recovery method of discarded lithium battery.Two methods
Respectively have advantage and disadvantage: Wet-process metallurgy method can recycle most of metal, but it requires pole to the Classification Management of lithium ion battery
Height is needed battery according to cathode and anode and dielectric material classification processing, and another exterior-applied liquid medicine is more, needs mating sewage treatment unit.Fire
Method metallurgy mode consumes energy greatly, needs to melt out cobalt, copper, nickel, iron by being up to 1200 DEG C or more high temperature, and lithium, aluminium etc. do not return generally
It receives, the filler material of building building cement is used for as slag phase.Its advantages are low to cell classification requirement, it might even be possible to not require to disassemble
Deng pretreatment.Therefore pyrometallurgy recycling lithium battery is widely used, but the lithium in pyrometallurgical processes in battery enters
It is difficult to recycle in clinker.
Application No. is 201710744391.1 patent of invention disclose it is valuable in a kind of waste and old nickel cobalt manganese lithium ion battery
The recovery method of metal includes the following steps: (1) waste and old nickel cobalt manganese lithium ion battery dismantling, electric discharge, broken slabbing；(2) it shells
From and leach: broken old and useless battery piece, which is placed in acid solution, to be impregnated, gentle agitation add reducing agent carry out battery positive/negative plate
The leaching of nickel, cobalt, manganese, lithium valuable metal in removing and battery material；(3) slag-liquid separation is carried out after leaching, obtains filtrate, filter residue,
Filtrate is nickeliferous, the soluble ion of cobalt, manganese, lithium, copper, aluminium, and filter residue contains copper foil, aluminium foil and graphite, residue washing, drying, grinding,
Sieve to obtain copper powder, aluminium powder and graphite powder；(4) filtrate cleans: iron displacement copper removal, iron oxide, and hydrolysis removes iron, aluminium, and filtering must clean
Nickeliferous, cobalt, manganese, the solution of lithium and copper and iron aluminium slag afterwards；(5) synthetic solvent prepare: after the removal of impurities of step (4) liquid by nickel, cobalt,
Manganese, aluminium presoma desired ratio supplying scarce element salt, total 70~100g/L of metal concentration of solution or so；(6) it synthesizes
Aluminium coats nickel cobalt manganese presoma: the nickel cobalt manganese aluminum solutions of step (5) add lye and ammonium hydroxide to synthesize nickel cobalt manganese forerunner in a kettle
Body, filtering, filter residue are nickel cobalt manganese aluminium presoma, and washing, drying, filtrate is liquid after synthesis, liquid ammonia still process after synthesis；(7) after synthesizing
Liquid concentration: liquid is concentrated by evaporation after the synthesis containing lithium of step (6), if there is sulfate crystal occurs, is centrifugally separating to obtain sulfuric acid
Sodium crystal and mother liquor, crystallizing and washing drying, washing water are combined with mother liquor；(8) lithium carbonate: the concentrate of step (7) is precipitated
Or carbonate or logical carbon dioxide gas precipitating lithium are added in crystalline mother solution, it precipitates filtration washing and obtains lithium carbonate, filtrate is used for two
Secondary recycling lithium.The step (1) dismantles battery pack, is then placed in 1-6% sodium chloride solution and discharges, is broken into after electric discharge
The sheet of 0.5-10cm long.The concentration of acid described in the step (2) is 0.5~2.5mol/L, and liquid-solid ratio 2~4, temperature is
60~80 DEG C, 0~10min of broken waste and old lithium ion battery soaking time, hydrogen peroxide that the reducing agent of addition is 30% or
The sodium sulfite solution of person 20~25%, reaction process and the after the reaction was completed pH value of adjustment solution are at 0.5~2.0, reaction
Between 30~100min.The suction filtration of slag-liquid separation described in the step (3), filters pressing or centrifuge separation, pure water；Filter residue dries
It is dry.Filtrate described in the step (4) adds the sodium hydroxide solution of 150-400g/L to adjust solution ph 1.5-2.5, heating
To 80-90 DEG C, the reduced iron powder of 1~10 times of amount is added, reacts 10~30min, stops heating, oxidant hydrogen peroxide or secondary is added
Sodium chlorate, additional amount are 1.0~2.0 times, 10~30min of reaction time of theoretical amount, and the sodium hydroxide of 150~400g/L is added
Solution adjusts the pH value of solution to 3.8~4.0, and 0.5~3h of reaction time, Buchner funnel or filter press filtering, filtering gained are filtered
Twice of slag pulping and washing, filter residue drying.The ratio of nickel cobalt manganese in the step (5) is 5:2:3,1:1:1,8:1:1 or other
Ratio, according to the content of aluminium in solution, amount as required is added aluminium, and the salt of the scarce element of institute is sulfate, chloride or nitric acid
One of salt, aluminium salt are aluminum nitrate.Nickel cobalt manganese aluminium ternary forerunner's reaction kettle described in the step (6) adds certain volume
For pure water as bottom liquid, bottom liquid is pure water, is heated to 50-90 DEG C, 30% ammonia is added in 150~300g/L of concentration of lye, every 100g alkali
5~20mL of water controls the pH value 10.0~11.0 of reaction system, and 30~300h of reaction time is filtered after the reaction was completed, and filtrate is standby
With filter residue drying.Liquid ammonia still process after synthesis described in the step (6), solution are heated to 60-100 DEG C, and the ammonia evaporated is with water
Or sulfuric acid absorption recycles.Liquid is concentrated by evaporation according to the lithium concentration in solution after synthesis in the step (7), if gone out
Existing sulfate crystal, low temperature -5~10 DEG C crystallization, is centrifugated, washing, the lithium concentration after concentration in liquid or crystalline mother solution
Reach 10~15g/L, sulfate crystal drying.The temperature of precipitating lithium carbonate is 93-100 DEG C in the step (8), and addition is sunk
Shallow lake agent is sodium carbonate, ammonium carbonate, i.e. salting liquid or carbon dioxide gas containing carbonate, additional amount be theoretical amount 1.1~
2.0 times, residue washing, washing water and mother liquor are combined circulation and stress, lithium carbonate drying.
Method of the invention, using waste and old nickel cobalt manganese systems lithium ion battery as raw material, various waste and old lithium ion batteries are disassembled,
Artificial or Mechanical Crushing, broken material are soaked into pure water or certain density sulfuric acid solution after electric discharge, and reducing agent is added
While adjust solution acidity removed and leached.Valuable metal nickel, cobalt in battery, manganese, lithium enter in leachate, copper
Foil, aluminium foil, graphite, which enter in slag, to be recycled.Solution after removal of impurities is synthetically prepared aluminium cladding nickel-cobalt-manganese ternary presoma, in solution
Lithium carbonate recycling is precipitated into after lithium ion is concentrated.
The medicine have the advantages that method copper foil, aluminium foil and active material of the invention is completely separated, applying waste lithium ionic electricity
Valuable metal nickel, cobalt, manganese, lithium leaching rate in pond are all larger than 99%, and the concentration of copper, aluminium, iron is less than 1g/L in leachate.It leaches
PH value 4.0 or so in liquid removal of impurities, the main metal loss of dedoping step is few.Solution directly synthesizes aluminium cladding nickel-cobalt-manganese ternary presoma,
Method and process process of the invention is short, and the rate of recovery of nickel cobalt manganese reaches 96% or more, and 90% or more the overall recovery of lithium reaches useless
Valuable metal nickel in old nickel cobalt manganese lithium ion battery, cobalt, manganese, the simple and effective recycling of lithium purpose.After this law is handled, copper foil aluminium
Foil is stripped clean thoroughly, and removal process process is short, and easy to operate, strong operability, equipment is simple, is invested small, it is easy to accomplish work
Industry metaplasia produces.
The inventors discovered that the above method is due to more than operation quantity and complicated, so the processing cost is high, therefore commercially
Using relatively difficult.
Summary of the invention
The purpose of the present invention is to provide a kind of recyclable devices of valuable metal in waste and old nickel cobalt manganese lithium ion battery.
Technical scheme is as follows: the recyclable device of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery,
It is characterized in that, including pretreatment unit, heating device, equipment for separating liquid from solid, the 1st reactor, the 1st recycling connected by pipeline
Device, the 2nd reactor, the 2nd recyclable device and valuable metal cobalt, manganese, zinc and yttrium separator；
The pretreatment unit includes dismantling, electric discharge and fragmentation cell, disassembled for waste and old nickel cobalt manganese lithium ion battery,
Electric discharge is crushed, and therefrom roughing goes out positive electrode and negative electrode material, crushes the positive electrode and negative electrode material；Sieving, obtains powder
Last particle；
The pretreatment unit further includes cleaning unit, for removing water-soluble potassium and sodium etc. in the powder particle
Water-soluble alkali metal salts are added water and are stirred in the powder particle, stir to get cleaning solution slurry, finally will be described
Cleaning solution slurry is sent into the equipment for separating liquid from solid, is separated by solid-liquid separation the cleaning solution slurry, obtained powder particle is solid
Valuable metal recovery raw material；The solid valuable metal recovery raw material is sent into the 1st reactor；
Sulfuric acid solution is added in the 1st reactor, is mixed；When detecting hydrogen in the 1st reactor
When incrementss are lower than threshold values, the sulfuric acid solution is sent to the heating devices heat to sending the described 1st back to after 60 DEG C~80 DEG C
Reactor, the sulfate of rare earth element is added into the 1st reactor, and stirring and dissolving obtains de- earth solution and leaches residual
The mixture of the sulfate mixed precipitation of slag and rare earth element；
The sulfate mixed precipitation of de- earth solution and leaching residue and rare earth element that the step (3) is obtained
Mixture is sent into the equipment for separating liquid from solid and carries out the 2nd separation of solid and liquid, obtains filtrate, filter residue, contains nickel, cobalt etc. in the filtrate
Valuable metal, the filter residue include the mixture and nickel, cobalt and rare earth element of the sulfuric acid double salt mixed precipitation of rare earth element；
The filter residue is output to the 1st recyclable device, is recycled as iron nickel production of raw material for use；
The filtrate is transported to the 2nd reactor, middle addition oxidant carries out at oxidation in the 2nd reactor
Reason, obtains the 2nd mixed slurry；
2nd mixed slurry is sent to the heating devices heat to sending the 2nd reactor back to after 60 DEG C~80 DEG C,
Neutralizer is added into the 2nd mixed slurry, is neutralized, obtains the 3rd mixed slurry；
3rd mixed slurry is sent into the equipment for separating liquid from solid filtering, obtains leaching residue and impurity removal liquid；Institute
Stating and leaching main component in residue is nickel, cobalt and trace iron and aluminium；And impurity removal liquid predominantly contain nickel sulfate and
The mixed aqueous solution of cobaltous sulfate；
The leaching residue is sent to the 2nd recyclable device；
By the impurity removal liquid send back to the 2nd reactor carry out extraction and extraction process, use phosphoric acid extraction agent as
Organic extractant separates nickel and cobalt from nickeliferous and cobalt solution, using nickel as sulphur by solvent extraction processing and extraction process
Sour nickel aqueous solution recycling, obtains the raffinate of the extracting solution containing cobalt, manganese, zinc and yttrium and nickel；
By the extracting solution containing cobalt, manganese, zinc and yttrium be sent to the valuable metal cobalt, manganese, zinc and yttrium separator into
It is recycled after row separation.
Further, in the 2nd reactor, the condition of reaction includes: that oxidation-reduction potential is 800mV (Ag/AgCl electricity
Pole benchmark) more than, pH value is 1.5~2.5.
The reason is that, the pH of de- earth solution is less than 1 or in the case where being greater than 2.5, manganese and iron etc. are difficult to precipitate, under
In the dealuminzation process of one step, the usage amount of neutralizer increases.On the other hand, when the pH of de- earth solution is more than 2.5, nickel and cobalt
Etc. may precipitate.The result shows that manganese, as manganese oxide (MnO2), iron is precipitated as water iron oxide (III) (Fe (OH) 3), nickel
It with cobalt since ionic forms (Ni2+, Co2+) exist in solution, therefore is filtered, obtains the mixing of nickel sulfate and cobaltous sulfate
Aqueous solution, referred to as the 2nd mixed slurry.
Further, in the 2nd reactor, made using hydrogen peroxide, the powder of lithium nickelate (LiNiO2), sodium peroxydisulfate
For oxidant；Use sulfuric acid, hydrochloric acid, sodium hydroxide, sodium carbonate, calcium hydroxide or calcium carbonate as pH adjusting agent, preferably hydrogen-oxygen
Change sodium or sodium carbonate.
Further, in the 2nd reactor, the oxidation-reduction potential of the 2nd mixed slurry is 300mV (Ag/AgCl
Electrode reference) more than, pH value is 5.0~6.
Experiment shows that, when pH is less than 5.0, iron is unable to precipitation and separation.On the other hand, when pH is more than 6.0, nickel and iron one
Play precipitating；Use sodium hydroxide, sodium carbonate, calcium hydroxide or calcium carbonate as neutralizer, preferably sodium hydroxide or sodium carbonate.
Further, in the 2nd reactor, the liquid temperature of the 2nd mixed slurry is 60 DEG C~80 DEG C；Concentration is 50g/
L~300g/L.
Further, filter device used in the separation of solid and liquid, including revolving filter, whizzer, pressure filtration
Device, vacuum filter or cross-flow filter, preferably revolving filter.
Further, in the 2nd reactor, use phosphate acidic extractant as phosphate acidic extractant, it is excellent
Select two -2- ethylhexyl phosphoric acids (D2EHPA).
Further, the extraction stage of the extraction processing of the 2nd reactor, the pH value of solution are preferably 3.0~7.
The beneficial effects of the present invention are: the leaching process by nickel, cobalt, manganese, lithium valuable metal of the invention with
And the Crystallization Procedure of rare earth element is arranged in same reactor, is reacted according to the sequence crystallized afterwards is first leached,
It not only can simplify reaction process and consersion unit, what is obtained after reaction leaches the sulfuric acid of residue and rare earth element
Salt mixed precipitation mixture can be utilized directly as the raw material of iron nickel manufacturing engineering.That is, by above-mentioned process and
The simplification of equipment can reduce the equipment costs such as reaction unit, equipment for separating liquid from solid and attaching device, can also save water power
Etc. expenses.
Detailed description of the invention
Fig. 1 is the structural diagram of the present invention
Specific embodiment
It elaborates below in conjunction with drawings and examples to technical solution of the present invention.A kind of waste and old nickel cobalt manganese lithium ion
The recyclable device of valuable metal in battery, which is characterized in that including the pretreatment unit, heating device, solid connected by pipeline
Liquid separating apparatus, the 1st reactor, the 1st recyclable device, the 2nd reactor, the 2nd recyclable device and valuable metal cobalt, manganese, zinc and yttrium
Separator；
The pretreatment unit includes dismantling, electric discharge and fragmentation cell, disassembled for waste and old nickel cobalt manganese lithium ion battery,
Electric discharge is crushed, and therefrom roughing goes out positive electrode and negative electrode material, crushes the positive electrode and negative electrode material；Sieving, obtains powder
Last particle；
The pretreatment unit further includes cleaning unit, for removing water-soluble potassium and sodium etc. in the powder particle
Water-soluble alkali metal salts are added water and are stirred in the powder particle, stir to get cleaning solution slurry, finally will be described
Cleaning solution slurry is sent into the equipment for separating liquid from solid, is separated by solid-liquid separation the cleaning solution slurry, obtained powder particle is solid
Valuable metal recovery raw material；The solid valuable metal recovery raw material is sent into the 1st reactor；
Sulfuric acid solution is added in the 1st reactor, is mixed；When detecting hydrogen in the 1st reactor
When incrementss are lower than threshold values, the sulfuric acid solution is sent to the heating devices heat to sending the described 1st back to after 60 DEG C~80 DEG C
Reactor, the sulfate of rare earth element is added into the 1st reactor, and stirring and dissolving obtains de- earth solution and leaches residual
The mixture of the sulfate mixed precipitation of slag and rare earth element；
The sulfate mixed precipitation of de- earth solution and leaching residue and rare earth element that the step (3) is obtained
Mixture is sent into the equipment for separating liquid from solid and carries out the 2nd separation of solid and liquid, obtains filtrate, filter residue, contains nickel, cobalt etc. in the filtrate
Valuable metal, the filter residue include the mixture and nickel, cobalt and rare earth element of the sulfuric acid double salt mixed precipitation of rare earth element；
The filter residue is output to the 1st recyclable device, is recycled as iron nickel production of raw material for use；
The filtrate is transported to the 2nd reactor, middle addition oxidant carries out at oxidation in the 2nd reactor
Reason, obtains the 2nd mixed slurry；
2nd mixed slurry is sent to the heating devices heat to sending the 2nd reactor back to after 60 DEG C~80 DEG C,
Neutralizer is added into the 2nd mixed slurry, is neutralized, obtains the 3rd mixed slurry；
3rd mixed slurry is sent into the equipment for separating liquid from solid filtering, obtains leaching residue and impurity removal liquid；Institute
Stating and leaching main component in residue is nickel, cobalt and trace iron and aluminium；And impurity removal liquid predominantly contain nickel sulfate and
The mixed aqueous solution of cobaltous sulfate；
The leaching residue is sent to the 2nd recyclable device；
By the impurity removal liquid send back to the 2nd reactor carry out extraction and extraction process, use phosphoric acid extraction agent as
Organic extractant separates nickel and cobalt from nickeliferous and cobalt solution, using nickel as sulphur by solvent extraction processing and extraction process
Sour nickel aqueous solution recycling, obtains the raffinate of the extracting solution containing cobalt, manganese, zinc and yttrium and nickel；
By the extracting solution containing cobalt, manganese, zinc and yttrium be sent to the valuable metal cobalt, manganese, zinc and yttrium separator into
It is recycled after row separation.
Further, in the 2nd reactor, the condition of reaction includes: that oxidation-reduction potential is 800mV (Ag/AgCl electricity
Pole benchmark) more than, pH value is 1.5~2.5.
The reason is that, the pH of de- earth solution is less than 1 or in the case where being greater than 2.5, manganese and iron etc. are difficult to precipitate, under
In the dealuminzation process of one step, the usage amount of neutralizer increases.On the other hand, when the pH of de- earth solution is more than 2.5, nickel and cobalt
Etc. may precipitate.The result shows that manganese, as manganese oxide (MnO2), iron is precipitated as water iron oxide (III) (Fe (OH) 3), nickel
It with cobalt since ionic forms (Ni2+, Co2+) exist in solution, therefore is filtered, obtains the mixing of nickel sulfate and cobaltous sulfate
Aqueous solution, referred to as the 2nd mixed slurry.
Further, in the 2nd reactor, made using hydrogen peroxide, the powder of lithium nickelate (LiNiO2), sodium peroxydisulfate
For oxidant；Use sulfuric acid, hydrochloric acid, sodium hydroxide, sodium carbonate, calcium hydroxide or calcium carbonate as pH adjusting agent, preferably hydrogen-oxygen
Change sodium or sodium carbonate.
Further, in the 2nd reactor, the oxidation-reduction potential of the 2nd mixed slurry is 300mV (Ag/AgCl
Electrode reference) more than, pH value is 5.0~6.
Experiment shows that, when pH is less than 5.0, iron is unable to precipitation and separation.On the other hand, when pH is more than 6.0, nickel and iron one
Play precipitating；Use sodium hydroxide, sodium carbonate, calcium hydroxide or calcium carbonate as neutralizer, preferably sodium hydroxide or sodium carbonate.
Further, in the 2nd reactor, the liquid temperature of the 2nd mixed slurry is 60 DEG C~80 DEG C；Concentration is 50g/
L~300g/L.
Further, filter device used in the separation of solid and liquid, including revolving filter, whizzer, pressure filtration
Device, vacuum filter or cross-flow filter, preferably revolving filter.
Further, in the 2nd reactor, use phosphate acidic extractant as phosphate acidic extractant, it is excellent
Select two -2- ethylhexyl phosphoric acids (D2EHPA).
Further, the extraction stage of the extraction processing of the 2nd reactor, the pH value of solution are preferably 3.0~7.
Above description merely relates to certain specific embodiments of the invention, and any those skilled in the art is based on this
The replacement or improvement that the spirit of invention is done should be protection scope of the present invention and covered, protection scope of the present invention Ying Yiquan
Subject to sharp claim.
Claims (8)
1. the recyclable device of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery, which is characterized in that including being connected by pipeline
Pretreatment unit, heating device, equipment for separating liquid from solid, the 1st reactor, the 1st recyclable device, the 2nd reactor, the 2nd recycling connect
Device and valuable metal cobalt, manganese, zinc and yttrium separator；
The pretreatment unit includes dismantling, electric discharge and fragmentation cell, disassemble, discharge for waste and old nickel cobalt manganese lithium ion battery,
Broken, therefrom roughing goes out positive electrode and negative electrode material, crushes the positive electrode and negative electrode material；Sieving, obtains powder
Grain；
The pretreatment unit further includes cleaning unit, water-soluble for removing water-soluble potassium and sodium etc. in the powder particle
Property alkali metal salt, be added and water and be stirred in the powder particle, cleaning solution slurry is stirred to get, finally by the cleaning
Slurry material is sent into the equipment for separating liquid from solid, is separated by solid-liquid separation the cleaning solution slurry, obtained powder particle is that solid is valuable
Metal recovery raw material；The solid valuable metal recovery raw material is sent into the 1st reactor；
Sulfuric acid solution is added in the 1st reactor, is mixed；When the increase for detecting hydrogen in the 1st reactor
When amount is lower than threshold values, the sulfuric acid solution is sent to the heating devices heat to sending the 1st reaction back to after 60 DEG C~80 DEG C
Device, is added the sulfate of rare earth element into the 1st reactor, stirring and dissolving, obtain de- earth solution and leach residue with
And the mixture of the sulfate mixed precipitation of rare earth element；
The mixing of the sulfate mixed precipitation of de- earth solution and leaching residue and rare earth element that the step (3) is obtained
Object is sent into the equipment for separating liquid from solid and carries out the 2nd separation of solid and liquid, obtains filtrate, filter residue, and it is valuable to contain nickel, cobalt etc. in the filtrate
Metal, the filter residue include the mixture and nickel, cobalt and rare earth element of the sulfuric acid double salt mixed precipitation of rare earth element；
The filter residue is output to the 1st recyclable device, is recycled as iron nickel production of raw material for use；
The filtrate is transported to the 2nd reactor, middle addition oxidant carries out oxidation processes in the 2nd reactor,
Obtain the 2nd mixed slurry；
2nd mixed slurry is sent to the heating devices heat to the 2nd reactor is sent back to after 60 DEG C~80 DEG C, to institute
It states in the 2nd mixed slurry and neutralizer is added, be neutralized, obtain the 3rd mixed slurry；
3rd mixed slurry is sent into the equipment for separating liquid from solid filtering, obtains leaching residue and impurity removal liquid；The leaching
Main component is nickel, cobalt and trace iron and aluminium in residue out；And the impurity removal liquid predominantly contains nickel sulfate and sulfuric acid
The mixed aqueous solution of cobalt；
The leaching residue is sent to the 2nd recyclable device；
It sends impurity removal liquid back to the 2nd reactor and carries out extraction and extraction process, use phosphoric acid extraction agent as organic
Extractant separates nickel and cobalt from nickeliferous and cobalt solution, using nickel as nickel sulfate by solvent extraction processing and extraction process
Aqueous solution recycling, obtains the raffinate of the extracting solution containing cobalt, manganese, zinc and yttrium and nickel；
The extracting solution containing cobalt, manganese, zinc and yttrium is sent to the valuable metal cobalt, manganese, zinc and yttrium separator to be divided
From rear recycling.
2. the recyclable device of valuable metal in waste and old nickel cobalt manganese lithium ion battery according to claim 1, which is characterized in that
In 2nd reactor, the condition of reaction includes: that oxidation-reduction potential is 800mV or more, and pH value is 1.5~2.5.
3. the recyclable device of valuable metal, feature exist in waste and old nickel cobalt manganese lithium ion battery according to claim 1 or 2
In using hydrogen peroxide, the powder of lithium nickelate (LiNiO2), sodium peroxydisulfate as oxidant in the 2nd reactor；It uses
Sulfuric acid, hydrochloric acid, sodium hydroxide, sodium carbonate, calcium hydroxide or calcium carbonate are as pH adjusting agent, preferably sodium hydroxide or sodium carbonate.
4. the recyclable device of valuable metal in waste and old nickel cobalt manganese lithium ion battery according to claim 3, which is characterized in that
In 2nd reactor, the oxidation-reduction potential of the 2nd mixed slurry is 300mV or more, and pH value is 5.0~6.
5. the recyclable device of valuable metal in waste and old nickel cobalt manganese lithium ion battery according to claim 4, which is characterized in that
In 2nd reactor, the liquid temperature of the 2nd mixed slurry is 60 DEG C~80 DEG C；Concentration is 50g/L~300g/L.
6. the recyclable device of valuable metal, feature exist in waste and old nickel cobalt manganese lithium ion battery according to claim 1 or 2
In, filter device used in the separation of solid and liquid, including revolving filter, whizzer, pressure filter, vacuum filter,
Or cross-flow filter, preferred revolving filter.
7. the recyclable device of valuable metal in waste and old nickel cobalt manganese lithium ion battery according to claim 5, which is characterized in that
In 2nd reactor, use phosphate acidic extractant as phosphate acidic extractant, preferably two -2- ethylhexyl phosphorus
Sour (D2EHPA).
8. the recyclable device of valuable metal in waste and old nickel cobalt manganese lithium ion battery according to claim 7, which is characterized in that
The extraction stage of the extraction processing of 2nd reactor, the pH value of solution are preferably 3.0~7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810923244.5A CN109004307A (en) | 2018-08-14 | 2018-08-14 | The recyclable device of valuable metal in waste and old nickel cobalt manganese lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810923244.5A CN109004307A (en) | 2018-08-14 | 2018-08-14 | The recyclable device of valuable metal in waste and old nickel cobalt manganese lithium ion battery |
Publications (1)
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| CN109504859A (en) * | 2018-12-29 | 2019-03-22 | 启东市北新无机化工有限公司 | A method of the Call Provision nickel from waste and old lithium ion battery |
| CN110767954A (en) * | 2019-09-16 | 2020-02-07 | 天齐锂业（江苏）有限公司 | Method for carrying out distillation defluorination on lithium ion battery powder by mixed acid and synergistic valuable metal leaching |
| CN115058594A (en) * | 2022-07-14 | 2022-09-16 | 广东佳纳能源科技有限公司 | Method for recovering valuable metal elements from waste lithium ion batteries and leaching device |
| CN115448381A (en) * | 2022-09-08 | 2022-12-09 | 湖南五创循环科技有限公司 | Recycling method and recycling device of waste lithium ion battery anode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109504859A (en) * | 2018-12-29 | 2019-03-22 | 启东市北新无机化工有限公司 | A method of the Call Provision nickel from waste and old lithium ion battery |
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| CN115058594A (en) * | 2022-07-14 | 2022-09-16 | 广东佳纳能源科技有限公司 | Method for recovering valuable metal elements from waste lithium ion batteries and leaching device |
| CN115448381A (en) * | 2022-09-08 | 2022-12-09 | 湖南五创循环科技有限公司 | Recycling method and recycling device of waste lithium ion battery anode material |
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