CN109256597A - A kind of method and system recycling lithium and cobalt from waste and old cobalt acid lithium battery - Google Patents
A kind of method and system recycling lithium and cobalt from waste and old cobalt acid lithium battery Download PDFInfo
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- CN109256597A CN109256597A CN201811093717.XA CN201811093717A CN109256597A CN 109256597 A CN109256597 A CN 109256597A CN 201811093717 A CN201811093717 A CN 201811093717A CN 109256597 A CN109256597 A CN 109256597A
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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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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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
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Abstract
The invention discloses a kind of from waste and old cobalt acid lithium battery recycles the method and system of lithium and cobalt.The described method includes: disassembling out positive plate from waste and old cobalt acid lithium battery；The binder in positive plate is removed, then through the molten valuable metal element leached in positive plate of acid, obtains acidification leachate；Hyperfiltration treatment is carried out to acidification leachate using ultrafiltration membrane；Utilize Nanofiltration-membrane technique, the other cation separations that the lithium ion in leachate will be acidified be different from lithium ion, lithium-containing solution and the solution containing other cations are obtained, then enrichment method is carried out using reverse osmosis technology respectively, other cations include cobalt ions；And the lithium ion Precipitation in lithium-containing solution is made using lithium precipitating reagent, and the cobalt ions Precipitation in the solution containing other cations is made using alkaline matter, realize the recycling of lithium and cobalt.The present invention uses the reverse osmosis joint technology of ultrafiltration-nanofiltration-, has the characteristics that simple process environmental protection, soda acid dosage is few, membrane separating effect is good and stablizes.
Description
Technical field
The present invention relates to a kind of from waste and old cobalt acid lithium battery recycles the method and corresponding system of lithium and cobalt, belongs to lithium electricity
Pond recovery technology field.
Background technique
Lithium and its compound are the strategic materials being of great significance in national economy and national defense construction, and raw with people
Closely bound up new green energy material living.Lithium ion battery is as a kind of mechanism of new electrochemical power sources, it has also become 3C electronic product
Main energy sources, occupy the share of 80% or more consumer electronics market.The continuous advancement of lithium power technology in recent years, energy density
It is promoted, is significantly increased in new-energy automobile and accumulation power supply domain requirement, lithium ion battery production and marketing has been driven to increase substantially on year-on-year basis.
It is mentioned using tesla as the pure electric automobile of representative using the lithium battery of the lithium cobaltate cathode material of the high voltage platform of Panasonic's production
For for power.In addition in 3C consumer electronics field, a large amount of lithium batteries for using lithium cobaltate cathode material, it is contemplated that old and useless battery
The recycling of recycling especially lithium cobaltate cathode material will be very important field.
However charge-discharge cycle is at 500-1000 times or so in lithium ion battery actual use, the service life, the time limit was in 3-5.It can be with
It is domestic to scrap peak for welcome waste lithium cell before and after predicting the year two thousand twenty.Although the lithium ion battery scrapped without lead,
The heavy metals such as cadmium, mercury, environmental pollution is relatively small, but contains the valuable metals and lithium hexafluoro phosphate etc. such as cobalt, nickel, manganese, lithium
Poisonous and harmful substance, it is mishandling to easily cause serious pollution and the wasting of resources.Containing a large amount of dilute in waste lithium ion
Noble metal, such as cobalt, nickel, lithium have significant economic benefit.Therefore how science green it is efficient from waste lithium cell
The valuable metals such as middle Call Provision, lithium, it has also become the hot technology of current recycling field.
The recovery technology of waste lithium cell is more, and the recovery technology of early stage is only focused in the highest metal of certain economic values
The purification of element, method is relatively simple, and representative is exactly the cobalt recycled in waste and old cobalt acid lithium, does not have synthetical recovery lithium.
And two hydrometallurgy, pyrometallurgy aspects, these sides currently are focused primarily upon to the recovery technology of old and useless battery valuable metal
Method is all realized recycles valuable metal element or synthesis presoma from waste lithium cell.Most commonly used method is pyrogenic process-
Ore Leaching or alkali soluble-Ore Leaching recycle valuable metal element in conjunction with modes such as precipitating, electrochemistry, extractions.Pyrometallurgy master
High-temperature calcination removal organic matter and binder are used, is then sieved again, magnetic separation, removal of impurities, leaching, purifying obtains target product.
In hydrometallurgical alkali soluble-Ore Leaching-extraction nickel cobalt preparation of manganese technology, mainly then fractional precipitation is used using alkali soluble Ore Leaching
Or extraction recycle valuable metal element, used in alkali mainly have sodium hydroxide, potassium hydroxide；Acid be divided into inorganic acid and
Organic acid, such as common inorganic acid hydrochloric acid, sulfuric acid, nitric acid even phosphoric acid, organic acid have citric acid, malic acid etc., use
Extractant has the organic solvents such as P204, P507, and the product of recycling is mostly sulfate.Although solvent extraction extraction efficiency is high, obtain
The product purity that arrives is high, but organic solvent it is more or less there is molten damage and volatile pollution environment, cause secondary pollution,
In addition extraction higher cost, there is limitations in the industrial production.For another example since nickel, cobalt equipotential are close, electro-deposition techniques
Middle nickel cobalt can generate synchronous deposition, form cobalt-nickel alloy, influence subsequent purifying, constrain the application of extension.Furthermore it is existing
Technology precipitating or extraction nickel cobalt manganese, then purify lithium-containing solution.The process is especially cumbersome, and a point 4-5 stage is needed to adjust pH value,
It consumes a large amount of soda acids and technique is tediously long, be not easy accurately to control.
Such as positive and negative pole material is obtained by disassembling removing in Chinese patent CN106395784A, then obtained by calcining
Lithium cobaltate cathode active material is leached using phosphoric acid and hydrogen peroxide joint, obtains lithium-containing solution and cobalt phosphate by separation of solid and liquid
Precipitating.The method combines extract technology to directly obtain cobalt phosphate and lithium-containing solution using roasting, realizes the separation and recovery of cobalt lithium.?
It uses ammonium sulfate in Chinese patent CN106505270A to roast to obtain reduction roasting slag, screened separation aluminium foil obtains lithium containing cobalt
Reducing slag is leached using dilute sulfuric acid, adjusts pH value precipitate cobalt, cobalt hydroxide is obtained cobalt powder through high-temperature calcination；It is heavy with sinker agent
Shallow lake lithium.The method has recycled cobalt and lithium, but has used high temperature sintering twice, and energy consumption is larger.In addition in Chinese patent
Using organic solvent removing positive electrode and aluminium foil in CN108336442A, cleaned using sulfuric acid acidification recycling and more precipitation,
It has recycled and has obtained cobalt powder and lithium carbonate product.The method has used organic solvent removing, although peeling effect is preferable, organic solvent
At high cost, low efficiency is removed, and organic matter is volatile, be easy to cause environmental pollution, constrains scale application.
Other methods such as ion-exchange, sulfide-oxidizing enzyme leaching etc. all successfully recycle valuable metal element, but this
All there is certain limitations for a little methods, and if ion-exchange operation is more complicated, step is comparatively laborious, is only suitable for a small amount of ion
Separating-purifying；The culture of sulfide-oxidizing enzyme leaching-out technique bacterium, use condition are harsh, it is difficult to which the factors such as industrialization all constrain skill
The application of art.
Summary of the invention
The main purpose of the present invention is to provide a kind of from waste and old cobalt acid lithium battery recycles the method and system of lithium and cobalt,
To overcome deficiency in the prior art.
For achieving the above object, present invention employs following technical solutions:
The method that the embodiment of the invention provides a kind of to recycle lithium and cobalt from waste and old cobalt acid lithium battery comprising:
Positive plate is disassembled out from waste and old cobalt acid lithium battery；
The binder in the positive plate is removed, then through the molten valuable metal element leached in the positive plate of acid, is obtained
It is acidified leachate；
Hyperfiltration treatment is carried out to the acidification leachate using ultrafiltration membrane；
Using Nanofiltration-membrane technique, the other cation separations that the lithium ion in leachate will be acidified be different from lithium ion,
Obtain lithium-containing solution and the solution containing other cations, then using reverse osmosis technology respectively to lithium-containing solution, contain other sun
The solution of ion carries out enrichment method, and other cations include cobalt ions；
And the lithium ion Precipitation in the lithium-containing solution is made using lithium precipitating reagent, and institute is made using alkaline matter
The cobalt ions Precipitation in the solution containing other cations is stated, realizes the recycling of lithium and cobalt.
In some embodiments, the method for recycling lithium and cobalt from waste and old cobalt acid lithium battery specifically includes:
(1) it discharged waste and old cobalt acid lithium battery, disassembled, classified, obtain positive plate；
(2) high-temperature process is carried out to the positive plate, at least for removing the binder in the positive plate；
(3) by positive plate and acidic materials continuous contact through high-temperature process, make the valuable metal member in the positive plate
Element leaches, and obtains acidification leachate；
(4) the acidification leachate is passed through into ultrafiltration membrane, nanofiltration membrane and reverse osmosis membrane respectively, it is molten containing lithium after being concentrated
Liquid and solution containing other cations；
(5) lithium precipitating reagent is added into the lithium-containing solution, reaction obtains lithium sediment；
(6) removal of impurities processing is carried out to the solution containing other cations, alkaline matter is added later, reaction obtains cobalt
Sediment.
The system that the embodiment of the invention also provides a kind of to recycle lithium and cobalt from waste and old cobalt acid lithium battery comprising:
Detachment means can disassemble waste and old cobalt acid lithium battery, be classified, and positive plate is obtained；
Mechanism is leached in acidification, can make the valuable metal Elements Leaching in the positive plate, obtains acidification leachate；
The reverse osmosis combined system of ultrafiltration-nanofiltration-comprising ultrafiltration membrane, nanofiltration membrane and reverse osmosis membrane, at least for that will be acidified
Lithium ion and other cation separations, concentration in leachate；
Lithium precipitates mechanism, is at least used to make lithium ion Precipitation；
Cobalt precipitates mechanism, is at least used to make the cobalt ions Precipitation in other cations.
Compared with the prior art, the beneficial effects of the present invention are:
1) the method valuable metal isolation technics of recycling lithium and cobalt provided by the invention from waste and old cobalt acid lithium battery is advanced,
Good separating effect, using ultrafiltration-nanofiltration-it is reverse osmosis associated with mode separate lithium ion with other bivalent cations, letter
Change process flow, and the process is physical process, will not introduce organic matter or foreign ion, the single-stage rejection effect of cobalt ions
Reach 95% or more；
2) the method separating-purifying theory of recycling lithium and cobalt provided by the invention from waste and old cobalt acid lithium battery is new, preferentially adopts
Remaining organic macromolecule is removed with ultrafiltration pretreatment acidification leachate, reduces pollution and blocking to nanofiltration membrane, then be acidified
Separating Li and other bivalent metal ions in leachate, then reprocessing contains lithium and cobalt-carrying solution respectively, and removal of impurities is concentrated to get production
Product substantially reduce process flow, reduce entrainment loss of the lithium ion in cumbersome dedoping step, greatly improve the recycling of lithium
Rate；
3) present invention is lower using the separation process energy consumption of physics, and concentrating and purifying process carries out at normal temperature, without phase-change,
Without chemical reaction, other impurities are not brought into, soda acid usage amount is greatly decreased in separating-purifying process, using common mineral acid acidified
It leaches, reduces cost, and prevented the use of organic extractant, it is environmentally protective；
4) the lithium carbonate product purity is high that the present invention recycles, the valuable metal ions rate of recovery are high.The nanofiltration membrane technology
Product purity is improved, thoroughly, lithium ion comprehensive recovery is high for foreign ion removal；
5) present invention is equipped with digital display and on-line checking facility, and whole equipment is advanced, easy control of process conditions, operation letter
Just, high degree of automation, and be easy to amplify, it is suitable for industrialized production and application.
6) mother liquor during present invention process can be recycled, not outlet, reduce the secondary pollution to environment.
Detailed description of the invention
Fig. 1 is that the process for the method for recycling lithium and cobalt in a typical embodiments of the invention from waste and old cobalt acid lithium battery is shown
It is intended to.
Specific embodiment
In view of existing cobalt acid lithium waste lithium cell recovery efficiency is low, technique is tediously long, to environment there are the deficiency of secondary pollution,
Inventor is studied for a long period of time and is largely practiced, and is able to propose technical solution of the present invention, mainly include battery dismantling,
Classification, positive plate be broken, heat treatment, Ore Leaching, ultrafiltration membrane-nanofiltration membrane-reverse osmosis separation concentration of valuable metals ion, removal of impurities,
The processing steps such as precipitating remove remaining organic macromolecule using ultrafiltration pretreatment acidification leachate, reduce the dirt to nanofiltration membrane
Dye and blocking efficiently separate lithium and cobalt ions, reverse osmosis difference enrichment method lithium ion and cobalt ions using Nanofiltering membrane, then
It is settled out lithium carbonate and cobalt hydroxide respectively again.It as follows will be further to works such as the technical solution, its implementation process and principles
It illustrates.
The reverse osmosis process integration technology of nanofiltration membrane-has a wide range of applications in sea water desalination processing, biomedicine field.It receives
Filter membrane is composite membrane, table and separating layer is made of polyelectrolyte, have the effect of retention to inorganic salts.Relevant film is through reason
By mainly having, dissolve-diffusion model, hydrogen bond are theoretical, spread pore flow theory, selection absorption pore flow theory.Nanofiltration membrane
The technical process that strainability is also manufactured with the charge of film, film etc. is related.There is different selections saturating solute according to nanofiltration membrane
The property crossed, the feature higher than monovalent ion to bivalent ions rejection utilize the monovalence in Nanofiltration-membrane technique separation leachate
Cation and bivalent cation, then again with it is reverse osmosis be concentrated respectively monovalent ion and bivalent ions solution realize elemental lithium and
The separation and concentration of cobalt element.The process is greatly reduced the usage amount of soda acid and avoids using organic solvent extraction cobalt etc.
Technical process reduces solution concentration and evaporation energy consumption in combination with reverse osmosis concentration technology, can quickly realize valuable metal from
Son has the characteristics that environmentally protective, low energy consumption, recovery efficiency are high to separation and purification, and technological operation is simple, is easy to amplify reality
Now industrialize.
As the one aspect of technical solution of the present invention, involved in be a kind of to recycle lithium from waste and old cobalt acid lithium battery
With the method for cobalt comprising:
Positive plate is disassembled out from waste and old cobalt acid lithium battery；
The binder in the positive plate is removed, then through the molten valuable metal element leached in the positive plate of acid, is obtained
It is acidified leachate；
Hyperfiltration treatment is carried out to the acidification leachate using ultrafiltration membrane, the macromoleculars such as remaining organic matter is removed, reduces
Blocking and pollution to subsequent film；
Using Nanofiltration-membrane technique, the other cation separations that the lithium ion in leachate will be acidified be different from lithium ion,
Obtain lithium-containing solution and the solution containing other cations, then using reverse osmosis technology respectively to lithium-containing solution, contain other sun
The solution of ion carries out enrichment method, and other cations include cobalt ions；
And the lithium ion Precipitation in the lithium-containing solution is made using lithium precipitating reagent, and institute is made using alkaline matter
The cobalt ions Precipitation in the solution containing other cations is stated, realizes the recycling of lithium and cobalt.
In some embodiments, the method for recycling lithium and cobalt from waste and old cobalt acid lithium battery specifically includes:
(1) it discharged waste and old cobalt acid lithium battery, disassembled, classified, obtain positive plate；
(2) high-temperature process is carried out to the positive plate, at least for removing the binder in the positive plate；
(3) by positive plate and acidic materials continuous contact through high-temperature process, make the valuable metal member in the positive plate
Element leaches, and obtains acidification leachate；
(4) the acidification leachate is passed through into ultrafiltration membrane, nanofiltration membrane and reverse osmosis membrane respectively, it is molten containing lithium after being concentrated
Liquid and solution containing other cations；
(5) lithium precipitating reagent is added into the lithium-containing solution, reaction obtains lithium sediment；
(6) removal of impurities processing is carried out to the solution containing other cations, alkaline matter is added later, reaction obtains cobalt
Sediment.
In some embodiments, the waste and old cobalt acid lithium battery is representative mainly using cobalt acid lithium as positive electrode
There are battery of mobile phone, Notebook Battery, digital camera battery and part high voltage cobalt acid lithium power battery etc., but not limited to this.
In some embodiments, step (2) specifically includes: the positive plate is calcined, the high-temperature process is carried out,
To remove binder.
Further, the time of the calcining is 0.5~6h, and calcination temperature is 300~800 DEG C.
In some embodiments, step (3) specifically includes: the positive plate leaching through high-temperature process is placed in acidic materials,
Hydrogen peroxide is added simultaneously, control solid-to-liquid ratio is 40~120g/L, and stirs in 30~90 DEG C, makes the valuable gold in the positive plate
Belong to Elements Leaching, obtains acidification leachate.
Further, the acidic materials include any in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, hydrofluoric acid etc.
One or more kinds of combinations, but not limited to this.The scope of application of the present invention is wide in range, has been applicable in common mineral acid acidified leaching
Out, reduce cost.
Further, the concentration of the acidic materials is 1~10mol/L.
In some embodiments, step (4) specifically includes: by step (3) obtain acidification leachate input respectively ultrafiltration membrane,
Nanofiltration membrane and reverse osmosis membrane, wherein the aperture of the ultrafiltration membrane isPreferablyOperating pressure is 0.1
~1.5MPa, the operating pressure of the nanofiltration membrane are 0.1~6MPa, and monolithic membrane flow velocity is 0.1~5L/min, working ph values 2
~10, the lithium-containing solution after being finally concentrated and solution containing other cations.The reverse osmosis skill of ultrafiltration-nanofiltration-
Art, which refers to, removes remaining organic macromolecule using ultrafiltration pretreatment acidification leachate, reduces pollution and blocking to nanofiltration membrane, adopts
With nanofiltration membrane separating Li and other metal ions, it is mainly used for monovalence and the divalent ion separation i.e. separation of lithium and cobalt, nickel, manganese,
Using reverse osmosis membrane enrichment method lithium-containing solution, concentration and evaporation amount is reduced, improves lithium concentration.
Further, the material of the nanofiltration membrane includes that polyamide (PA), polysulfones (PS), polyvinyl alcohol (PVA), sulfonation are poly-
Any two or more combination in sulfone (SPS), sulfonated polyether sulfone (SPES), cellulose acetate (CA) etc., it is especially preferably poly-
Amide and polysulfone composite membrane.
Further, the nanofiltration membrane includes board-like nanofiltration membrane or rolling nanofiltration membrane.The present invention using two kinds or more than
Membrane fussion it is compound after be assembled into the film groups of the types such as board-like, rolling.
Further, the nanofiltration membrane retaining molecular weight is 50~1000 dalton, has good ion selectivity,
95% or more is reached to bivalent ions rejection.
Further, the concentration of the lithium-containing solution after concentration is in 15g/L or more.
The present invention uses the reverse osmosis combination technology of ultrafiltration-nanofiltration-, realizes that the separation, enrichment, concentration of lithium ion are reduced
Soda acid usage amount.Pretreatment acidification leachate removes remaining organic macromolecule in ultra-filtration process, reduces the dirt to nanofiltration membrane
Dye and blocking, enter lithium ion in fresh water in nanofiltration process, and other divalent and the above ion rejection be in concentrated water, single-stage
Rejection reaches 95% or more, and lithium-containing solution is concentrated once again then in conjunction with reverse osmosis, lithium concentration is made to reach 3-10%.The combination
The mode that Cheng Caiyong serial or parallel connection combines carries out, and improves separation, concentrated effect.
In some embodiments, lithium precipitating reagent described in step (5) includes sodium carbonate, sodium bicarbonate or sodium fluoride etc., but
It is without being limited thereto.
Further, the lithium sediment includes lithium carbonate, lithium fluoride, in addition to lithium carbonate, lithium fluoride are also likely to be chlorination
The intermediate products such as lithium, lithium sulfate product, can be concentrated according to the actual situation, convert.
Further, the content of lithium carbonate or lithium fluoride contains in 99.5wt% or more, aluminium in the lithium sediment of recycling
Amount is less than 0.001wt%, and iron content is less than 0.001wt%, and sodium content is less than 0.025wt%, and content of magnesium is less than 0.008wt%.
In some embodiments, step (6) specifically includes: obtaining in the solution containing other cations and adds to step (4)
Enter decoppering agent, and adjusting pH value is 3~5, and alkaline matter is added later, reaction obtains cobalt sediment.
Further, the decoppering agent includes any one in vulcanized sodium, nickel sulfide, iron powder etc. or two or more groups
It closes, but not limited to this.
Further, the alkaline matter includes in sodium hydroxide, potassium hydroxide, sodium oxide molybdena, potassium oxide, calcium hydroxide etc.
Any one or two or more combinations, but not limited to this.
Further, the concentration of the alkaline matter is 0.5~8mol/L.
Further, the cobalt sediment includes cobalt hydroxide, cobalt carbonate, can also be cobalt oxide or cobaltosic oxide
Powder is converted using high-temperature calcination according to the actual situation.
Further, the bivalent cation includes the mixing of cobalt ions, nickel ion and manganese ion etc..
Further, the cobalt sediment includes nickel cobalt manganese co-precipitate, be nickel cobalt manganese hydroxide or carbonate, but
It is without being limited thereto.
Wherein, shown in Figure 1 as more specifically one of case study on implementation of the invention, it is described from waste and old cobalt acid lithium
Lithium is recycled in battery and the method for cobalt may particularly include following steps:
With waste and old cobalt acid lithium battery (the discarded anode generated including cobalt acid lithium 3C Product and cobalt acid lithium battery production process
Piece) it is raw material, it discharged, cracked, removed, sieved, obtain positive plate, high-temperature process removes binder, valuable through the molten leaching of acid
Filtrate is passed through ultrafiltration membrane-nanofiltration membrane-reverse osmosis treatment, respectively obtains the mixing of lithium-containing solution He other ions by metallic element
Solution.By lithium-containing solution by being concentrated to 15g/L or more, in the lithium precipitating reagent that saturation is added, it is settled out lithium carbonate.Through nanofiltration membrane
Isolated nickel and cobalt containing manganese mixed solution is added decoppering agent and removes copper ion, and adjusting pH value is 3-5, and precipitating removes ferro-aluminum etc.
Then impurity is added alkali precipitation and goes out cobalt, realize to lithium, cobalt separation and recycling.Concentrated mother liquor, which can be used, recycles not outlet,
It is properly added deionized water dilution in the circulating cycle, the lithium product that lithium carbonate product obtains after recrystallization, washing, drying reaches
The requirement of LITHIUM BATTERY has been arrived, it can direct reuse.
The other side of the embodiment of the present invention additionally provide it is a kind of recycle lithium and cobalt from waste and old cobalt acid lithium battery be
System comprising:
Detachment means can disassemble waste and old cobalt acid lithium battery, be classified, and positive plate is obtained；
Mechanism is leached in acidification, can make the valuable metal Elements Leaching in the positive plate, obtains acidification leachate；
The reverse osmosis combined system of ultrafiltration-nanofiltration-comprising ultrafiltration membrane, nanofiltration membrane and reverse osmosis membrane, at least for that will be acidified
Lithium ion and other cation separations, concentration in leachate；
Lithium precipitates mechanism, is at least used to make lithium ion Precipitation；
Cobalt precipitates mechanism, is at least used to make the cobalt ions Precipitation in other cations.
Further, it the system also includes high-temperature process mechanism, is at least used to carry out at high temperature the positive plate
Reason, to remove the binder in the positive plate.
Further, it the system also includes impurity removal mechanism, is at least used for the solution progress containing other cations
Removal of impurities processing.
Further, the system can specifically include pulverizer, acidification slot, the reverse osmosis combination dress of ultrafiltration-nanofiltration-
It sets, Muffle furnace, crystallizer, supercentrifuge, sieve, magnetic separator, drying box etc., but not limited to this.
To sum up, the present invention removes remaining organic macromolecule using ultrafiltration membrane pretreatment acidification leachate, reduces to nanofiltration
The pollution and blocking of film, using the monovalent cation and bivalent cation in Nanofiltration-membrane technique separation leachate, then again with anti-
Infiltration be concentrated respectively monovalent ion and bivalent ions solution realize elemental lithium and cobalt element separate and concentration.The process is substantially
Reduce the usage amount of soda acid and avoids using technical process such as organic solvent extraction cobalts, in combination with reverse osmosis concentration skill
Art reduces solution concentration and evaporation energy consumption, can quickly realize valuable metal ions to separation and purification, have it is environmentally protective,
The high feature of low energy consumption, recovery efficiency, and technological operation is simple, is easy to amplify realization industrialization.
Below with reference to several preferred embodiments and attached drawing, further details of the technical solution of the present invention, it is clear that
Described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the implementation in the present invention
Example, those of ordinary skill in the art's every other embodiment obtained without making creative work, all belongs to
In the scope of protection of the invention.The test method of actual conditions is not specified in the following example, usually according to normal condition.
Embodiment 1
Using some type of waste and old cobalt acid lithium battery as raw material.Old and useless battery electric discharge, dismantling, screening are obtained into positive material first
Material.It weighs after lithium cobaltate cathode material 800g handles 2h in Muffle furnace at 450 DEG C, removes binder, water quenching and in ultrasound
30min is handled in concussion, removes positive electrode and aluminium foil.Separation aluminium foil is removed using big net sieve pore, aluminium foil is handled through flushing
It can be directly used for aluminium smelting.Sulfuric acid treatment of the obtained black slag fine crushing through 4mol/L, while 30% hydrogen peroxide is added, control
Solid-to-liquid ratio is 80g/L, and temperature control is at 80 DEG C and is stirred continuously 4h, and the leachate of valuable metal is then obtained by filtration.Acid leaching residue
The predominantly acid non-soluble substances such as carbon dust.Through the chemical component in detection leachate, as a result as shown in table 1 below:
Chemical component (unit: g/L) in 1 leachate of table
| Classification | Aluminium | Cobalt | Lithium | Iron | SO4 2- |
| Content | 1.05 | 50.53 | 6.25 | 0.024 | 142.52 |
Acid leaching liquor pH value is adjusted to 3.5 or so with alkali, and is diluted and adjusted yin-yang total ion concentration, 50g/L is arrived in control, into
Enter ultrafiltration-nanofiltration-ro treatment technology, the pressure for controlling ultrafiltration membrane is 1MPa, and the pressure of nanofiltration membrane is 3.5MPa, concentrated stream
Speed is 3.0L/min, and cobalt plasma is rejected by, and in concentrated water lateral enrichment, lithium ion then enters in fresh water, and detection is contained respectively
Lithium solution and other Ar ion mixing solution, wherein cobalt ions single-stage rejection reaches 95.5%.Lithium ion is enriched in fresh water, will
The lithium-containing solution of enrichment further evaporates, and lithium concentration is made to reach 30g/L, and the sodium carbonate that saturation is added under the conditions of 85 DEG C is settled out
Lithium carbonate, the processing such as washed-recrystallization-washing-drying obtain battery-level lithium carbonate, testing result such as the following table 2:
2 battery-level lithium carbonate testing result of table
Cobalt-carrying solution is after iron replacement, sodium hydroxide control pH to 5.0 remove the impurity such as copper removal, iron, aluminium respectively, after filtering
Filtrate obtains Co (OH) with 2.0mol/L sodium hydroxide pellets cobalt again2Product.The process flow is short, environmentally protective, preferential to separate
Lithium, it is easy to operate, it is easy to be mass produced, lithium carbonate and cobalt hydroxide product reach downstream battery enterprise and want the quality of raw material
It asks.
Embodiment 2
Using some type of waste and old cobalt acid lithium battery as raw material.Old and useless battery electric discharge, dismantling, screening are obtained into positive material first
Material.It weighs after lithium cobaltate cathode material 600g handles 2h in Muffle furnace at 650 DEG C, removes binder, water quenching and in ultrasound
30min is handled in concussion, removes positive electrode and aluminium foil.Separation aluminium foil is removed using big net sieve pore, aluminium foil is handled through flushing
It can be directly used for aluminium smelting.Sulfuric acid treatment of the obtained black slag fine crushing through 10mol/L, while 30% hydrogen peroxide is added, control
Solid-to-liquid ratio processed is 80g/L, and temperature control is at 30 DEG C and is stirred continuously 4h, and the leachate of valuable metal is then obtained by filtration.Acidleach
Slag is mainly the acid non-soluble substances such as carbon dust.Through the chemical component in detection leachate, as a result as shown in table 3 below:
Chemical component (unit: g/L) in 3 leachate of table
| Classification | Aluminium | Cobalt | Lithium | Iron | SO4 2- |
| Content | 1.55 | 60.57 | 7.48 | 0.028 | 156.25 |
Acid leaching liquor pH value is adjusted to 3.5 or so with alkali, is diluted with deionized water and is adjusted yin-yang total ion concentration, control is arrived
60g/L, into ultrafiltration-nanofiltration-ro treatment technology, the pressure for controlling ultrafiltration membrane is 1.2MPa, and the pressure of nanofiltration membrane is
6MPa, concentrated water flow velocity are 5.0L/min, and cobalt plasma is rejected by, and in concentrated water lateral enrichment, lithium ion then enters in fresh water, respectively
Detection obtains lithium-containing solution and other Ar ion mixing solution, and wherein cobalt ions single-stage rejection reaches 95.1%.Lithium ion is light
It is enriched in water, the lithium-containing solution of enrichment is further evaporated, lithium concentration is made to reach 30g/L, saturation is added under the conditions of 85 DEG C
Sodium carbonate is settled out lithium carbonate, and the processing such as washed-recrystallization-washing-drying obtain battery-level lithium carbonate, and testing result is such as
The following table 4:
4 battery-level lithium carbonate testing result of table
Cobalt-carrying solution is filtered after filtering after iron replacement, sodium hydroxide control pH to 4 remove the impurity such as copper removal, iron, aluminium respectively
Liquid obtains Co (OH) with 6.0mol/L sodium hydroxide pellets cobalt again2Product.The process flow is short, environmentally protective, preferential separating Li,
It is easy to operate, it is easy to be mass produced, lithium carbonate and cobalt hydroxide product reach downstream battery enterprise to the quality requirement of raw material.
Embodiment 3
Using some type of waste and old cobalt acid lithium battery as raw material.Old and useless battery electric discharge, dismantling, screening are obtained into positive material first
Material.It weighs after lithium cobaltate cathode material 1000g handles 1h in Muffle furnace at 500 DEG C, removes binder, water quenching and in ultrasound
60min is handled in concussion, removes positive electrode and aluminium foil.Separation aluminium foil is removed using big net sieve pore, aluminium foil is handled through flushing
It can be directly used for aluminium smelting.Sulfuric acid treatment of the obtained black slag fine crushing through 4mol/L, while 30% hydrogen peroxide is added, control
Solid-to-liquid ratio is 75g/L, and temperature control is at 85 DEG C and is stirred continuously 4h, and the leachate of valuable metal is then obtained by filtration.Acid leaching residue
The predominantly acid non-soluble substances such as carbon dust.Through the chemical component in detection leachate, as a result as shown in table 5 below:
Chemical component (unit: g/L) in 5 leachate of table
| Classification | Aluminium | Cobalt | Lithium | Iron | SO4 2- |
| Content | 2.34 | 57.53 | 6.41 | 0.029 | 168.37 |
Acid leaching liquor pH value is adjusted to 2 or so with alkali, and dilutes and adjusts yin-yang total ion concentration, and 50g/L is arrived in control, is entered
Ultrafiltration-nanofiltration-ro treatment technology, the pressure for controlling ultrafiltration membrane is 0.8MPa, and the pressure of nanofiltration membrane is 3.5MPa, concentrated stream
Speed is 3.0L/min, and cobalt plasma is rejected by, and in concentrated water lateral enrichment, lithium ion then enters in fresh water, and detection is contained respectively
Lithium solution and other Ar ion mixing solution, wherein cobalt ions single-stage rejection reaches 95.0%.Lithium ion is enriched in fresh water, will
The lithium-containing solution of enrichment further evaporates, and lithium concentration is made to reach 30g/L, and the sodium carbonate that saturation is added under the conditions of 85 DEG C is settled out
Lithium carbonate, the processing such as washed-recrystallization-washing-drying obtain battery-level lithium carbonate, testing result such as the following table 6:
6 battery-level lithium carbonate testing result of table
Cobalt-carrying solution is after iron replacement, sodium hydroxide control pH to 5.0 remove the impurity such as copper removal, iron, aluminium respectively, after filtering
Filtrate obtains Co (OH) with 8.0mol/L sodium hydroxide pellets cobalt again2Product.The process flow is short, environmentally protective, preferential to separate
Lithium, it is easy to operate, it is easy to be mass produced, lithium carbonate and cobalt hydroxide product reach downstream battery enterprise and want the quality of raw material
It asks.
Embodiment 4
Using some type of waste and old cobalt acid lithium battery as raw material.Old and useless battery electric discharge, dismantling, screening are obtained into positive material first
Material.It weighs after lithium cobaltate cathode material 1200g handles 2h in Muffle furnace at 550 DEG C, removes binder, water quenching and in ultrasound
75min is handled in concussion, removes positive electrode and aluminium foil.Separation aluminium foil is removed using big net sieve pore, aluminium foil is handled through flushing
It can be directly used for aluminium smelting.HCl treatment of the obtained black slag fine crushing through 4mol/L, while 30% hydrogen peroxide is added, control
Solid-to-liquid ratio is 80g/L, and temperature control is at 80 DEG C and is stirred continuously 4h, and the leachate of valuable metal is then obtained by filtration.Acid leaching residue
The predominantly acid non-soluble substances such as carbon dust.Through the chemical component in detection leachate, as a result as shown in table 7 below:
Chemical component (unit: g/L) in 7 leachate of table
| Classification | Aluminium | Cobalt | Lithium | Iron | Cl- |
| Content | 1.12 | 58.30 | 7.11 | 0.027 | 97.69 |
Acid leaching liquor pH value is adjusted to 3.5 or so with alkali, and is diluted and adjusted yin-yang total ion concentration, 55g/L is arrived in control, into
Enter ultrafiltration-nanofiltration-ro treatment technology, the pressure for controlling ultrafiltration membrane is 0.5MPa, and the pressure of nanofiltration membrane is 4MPa, concentrated stream
Fast 3.0L/min, cobalt plasma are rejected by, and in concentrated water lateral enrichment, lithium ion then enters in fresh water, and detection is obtained containing lithium respectively
Solution and other Ar ion mixing solution, wherein cobalt ions single-stage rejection reaches 95.5%.Lithium ion is enriched in fresh water, will be rich
The lithium-containing solution of collection further evaporates, and lithium concentration is made to reach 30g/L, and the sodium carbonate that saturation is added under the conditions of 85 DEG C is settled out carbon
Sour lithium, the processing such as washed-recrystallization-washing-drying obtain battery-level lithium carbonate, testing result such as the following table 8:
8 battery-level lithium carbonate testing result of table
Cobalt-carrying solution is after iron replacement, sodium hydroxide control pH to 4.5 remove the impurity such as copper removal, iron, aluminium respectively, after filtering
Filtrate obtains Co (OH) with 1.0mol/L sodium hydroxide pellets cobalt again2Product.The process flow is short, environmentally protective, preferential to separate
Lithium, it is easy to operate, it is easy to be mass produced, lithium carbonate and cobalt hydroxide product reach downstream battery enterprise and want the quality of raw material
It asks.
Embodiment 5
Using some type of waste and old cobalt acid lithium battery as raw material.Old and useless battery electric discharge, dismantling, screening are obtained into positive material first
Material.It weighs after lithium cobaltate cathode material 900g handles 0.5h in Muffle furnace at 800 DEG C, removes binder, water quenching is simultaneously super
Middle processing 90min is swung in acoustic shock, removes positive electrode and aluminium foil.Using big net sieve pore remove separation aluminium foil, aluminium foil through flushing at
Reason can be directly used for aluminium smelting.HCl treatment of the obtained black slag fine crushing through 10mol/L, while 30% hydrogen peroxide is added,
Control solid-to-liquid ratio is 120g/L, and temperature control is at 80 DEG C and is stirred continuously 2h, and the leachate of valuable metal is then obtained by filtration.Acid
Phase analysis is mainly the acid non-soluble substances such as carbon dust.Through the chemical component in detection leachate, as a result as shown in table 9 below:
Chemical component (unit: g/L) in 9 leachate of table
| Classification | Aluminium | Cobalt | Lithium | Iron | Cl- |
| Content | 0.96 | 65.30 | 7.82 | 0.057 | 129.35 |
Acid leaching liquor pH value is adjusted to 3.5 or so with alkali, and is diluted and adjusted yin-yang total ion concentration, 40g/L is arrived in control, into
Enter ultrafiltration-nanofiltration-ro treatment technology, the pressure for controlling ultrafiltration membrane is 0.5MPa, and the pressure of nanofiltration membrane is 1.2MPa, concentrated water
Flow velocity 2.0L/min, cobalt plasma are rejected by, and in concentrated water lateral enrichment, lithium ion then enters in fresh water, and detection is contained respectively
Lithium solution and other Ar ion mixing solution, wherein cobalt ions single-stage rejection reaches 95.2%.Lithium ion is enriched in fresh water, will
The lithium-containing solution of enrichment further evaporates, and lithium concentration is made to reach 25g/L, and the sodium carbonate that saturation is added under the conditions of 80 DEG C is settled out
Lithium carbonate, the processing such as washed-recrystallization-washing-drying obtain battery-level lithium carbonate, testing result such as the following table 10:
10 battery-level lithium carbonate testing result of table
Cobalt-carrying solution is after iron replacement, sodium hydroxide control pH to 4.5 remove the impurity such as copper removal, iron, aluminium respectively, after filtering
Filtrate obtains Co (OH) with 8.0mol/L sodium hydroxide pellets cobalt again2Product.The process flow is short, environmentally protective, preferential to separate
Lithium, it is easy to operate, it is easy to be mass produced, lithium carbonate and cobalt hydroxide product reach downstream battery enterprise and want the quality of raw material
It asks.
Embodiment 6
Using some type of waste and old cobalt acid lithium battery as raw material.Old and useless battery electric discharge, dismantling, screening are obtained into positive material first
Material.It weighs after lithium cobaltate cathode material 900g handles 6h in Muffle furnace at 300 DEG C, removes binder, water quenching and in ultrasound
90min is handled in concussion, removes positive electrode and aluminium foil.Separation aluminium foil is removed using big net sieve pore, aluminium foil is handled through flushing
It can be directly used for aluminium smelting.Nitric acid treatment of the obtained black slag fine crushing through 1mol/L, while 30% hydrogen peroxide is added, control
Solid-to-liquid ratio is 40g/L, and temperature control is at 90 DEG C and is stirred continuously 2h, and the leachate of valuable metal is then obtained by filtration.Acid leaching residue
The predominantly acid non-soluble substances such as carbon dust.Through the chemical component in detection leachate, as a result as shown in table 11 below:
Chemical component (unit: g/L) in 11 leachate of table
| Classification | Aluminium | Cobalt | Lithium | Iron |
| Content | 0.56 | 62.25 | 7.16 | 0.059 |
Acid leaching liquor pH value is adjusted to 10 or so with alkali, and is diluted and adjusted yin-yang total ion concentration, 40g/L is arrived in control, into
Enter ultrafiltration-nanofiltration-ro treatment technology, the pressure for controlling ultrafiltration membrane is 0.1MPa, and the pressure of nanofiltration membrane is 0.1MPa, concentrated water
Flow velocity 0.1L/min, cobalt plasma are rejected by, and in concentrated water lateral enrichment, lithium ion then enters in fresh water, and detection is contained respectively
Lithium solution and other Ar ion mixing solution, wherein cobalt ions single-stage rejection reaches 96%.Lithium ion is enriched in fresh water, will be rich
The lithium-containing solution of collection further evaporates, and lithium concentration is made to reach 35g/L, and sodium fluoride is added under the conditions of 80 DEG C and is settled out lithium fluoride,
The processing such as washed-recrystallization-washing-drying obtain battery-grade lithium fluoride.Its testing result such as the following table 12:
12 battery-grade lithium fluoride testing result of table
Cobalt-carrying solution is filtered after filtering after iron replacement, potassium hydroxide control pH to 3 remove the impurity such as copper removal, iron, aluminium respectively
Liquid obtains Co (OH) with 0.5mol/L potassium hydroxide precipitate cobalt again2Product.The process flow is short, environmentally protective, preferential separating Li,
It is easy to operate, it is easy to be mass produced, lithium fluoride and cobalt hydroxide product reach downstream battery enterprise to the quality requirement of raw material.
In conclusion the present invention uses the preferential separating Li of Nanofiltering membrane of physics, and using super by above-mentioned technical proposal
The lithium carbonate purity is high of the reverse osmosis joint technology recycling of filter-nanofiltration-, with simple process, environmentally protective, soda acid dosage is few, film
Good separating effect and stabilization, it is easily operated, be suitable for industrialization continuous production feature.
In addition, inventor also refers to the mode of embodiment 1-6, with the other raw materials and condition listed in this specification
It etc. being tested, and has equally recycled and has recycled lithium and cobalt from waste and old cobalt acid lithium battery, obtained the LITHIUM BATTERY carbon of high quality
Sour lithium and cobalt hydroxide product.
It should be noted that, in this document, under normal circumstances, the element limited by sentence " including ... " is not arranged
Except there is also other identical elements in including the steps that the element, process, method or experimental facilities.
It should be appreciated that the above preferred embodiment is merely to illustrate the contents of the present invention, in addition to this, there are also other by the present invention
Embodiment, as long as those skilled in the art because of technical inspiration involved in the present invention, and use equivalent replacement or equivalent deformation
The technical solution that mode is formed is fallen within the scope of protection of the present invention.
Claims (10)
1. a kind of method for recycling lithium and cobalt from waste and old cobalt acid lithium battery, characterized by comprising:
Positive plate is disassembled out from waste and old cobalt acid lithium battery；
The binder in the positive plate is removed, then through the molten valuable metal element leached in the positive plate of acid, is acidified
Leachate；
Hyperfiltration treatment is carried out to the acidification leachate using ultrafiltration membrane；
Using Nanofiltration-membrane technique, the other cation separations that will be acidified the lithium ion in leachate be different from lithium ion are obtained
Lithium-containing solution and solution containing other cations, then using reverse osmosis technology respectively to lithium-containing solution, contain other cations
Solution carry out enrichment method, it is described it is other cation include cobalt ions；
And the lithium ion Precipitation in the lithium-containing solution is made using lithium precipitating reagent, and described contain is made using alkaline matter
There is the cobalt ions Precipitation in the solution of other cations, realizes the recycling of lithium and cobalt.
2. the method according to claim 1 for recycling lithium and cobalt from waste and old cobalt acid lithium battery, it is characterised in that specific packet
It includes:
(1) it discharged waste and old cobalt acid lithium battery, disassembled, classified, obtain positive plate；
(2) high-temperature process is carried out to the positive plate, at least for removing the binder in the positive plate；
(3) by positive plate and acidic materials continuous contact through high-temperature process, soak the valuable metal element in the positive plate
Out, acidification leachate is obtained；
(4) the acidification leachate is passed through into ultrafiltration membrane, nanofiltration membrane and reverse osmosis membrane respectively, the lithium-containing solution after being concentrated and
Solution containing other cations；
(5) lithium precipitating reagent is added into the lithium-containing solution, reaction obtains lithium sediment；
(6) removal of impurities processing is carried out to the solution containing other cations, alkaline matter is added later, reaction obtains cobalt precipitating
Object.
3. the method according to claim 1 or 2 for recycling lithium and cobalt from waste and old cobalt acid lithium battery, it is characterised in that: institute
Stating waste and old cobalt acid lithium battery includes battery of mobile phone, Notebook Battery, digital camera battery or high voltage cobalt acid lithium power battery.
4. the method according to claim 2 for recycling lithium and cobalt from waste and old cobalt acid lithium battery, which is characterized in that step
(2) it specifically includes: the positive plate is calcined, carry out the high-temperature process；Preferably, the time of the calcining is 0.5
~6h, calcination temperature are 300~800 DEG C.
5. the method according to claim 2 for recycling lithium and cobalt from waste and old cobalt acid lithium battery, which is characterized in that step
(3) it specifically includes: the positive plate leaching through high-temperature process being placed in acidic materials, while hydrogen peroxide is added, control solid-to-liquid ratio is
40~120g/L, and stirred in 30~90 DEG C, make the valuable metal Elements Leaching in the positive plate, obtains acidification leachate；
Preferably, the acidic materials include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, any one or two kinds in hydrofluoric acid
Above combination；Preferably, the concentration of the acidic materials is 1~10mol/L.
6. the method according to claim 2 for recycling lithium and cobalt from waste and old cobalt acid lithium battery, which is characterized in that step
(4) it specifically includes: step (3) being obtained into acidification leachate and inputs ultrafiltration membrane, nanofiltration membrane and reverse osmosis membrane respectively, wherein is described
The aperture of ultrafiltration membrane isPreferablyOperating pressure is 0.1~1.5MPa, the work of the nanofiltration membrane
Pressure is 0.1~6MPa, and monolithic membrane flow velocity is 0.1~5L/min, and working ph values are 2~10, contains lithium after being finally concentrated
Solution and solution containing other cations；Preferably, the concentration of the lithium-containing solution after concentration is in 15g/L or more；Preferably, institute
The material for stating nanofiltration membrane includes polyamide, polysulfones, polyvinyl alcohol, sulfonated polysulfone, sulfonated polyether sulfone, any in cellulose acetate
Two or more combinations, especially preferably polyamide and polysulfone composite membrane, retaining molecular weight are 50~1000 dalton；It is preferred that
, the nanofiltration membrane includes board-like nanofiltration membrane or rolling nanofiltration membrane.
7. the method according to claim 2 for recycling lithium and cobalt from waste and old cobalt acid lithium battery, it is characterised in that: step
(5) in, the lithium precipitating reagent includes sodium carbonate, sodium bicarbonate or sodium fluoride；And/or the lithium sediment include lithium carbonate or
Lithium fluoride；Preferably, the content of lithium carbonate or lithium fluoride is less than in 99.5wt% or more, aluminium content in the lithium sediment
0.001wt%, iron content are less than 0.001wt%, and sodium content is less than 0.025wt%, and content of magnesium is less than 0.008wt%.
8. the method according to claim 2 for recycling lithium and cobalt from waste and old cobalt acid lithium battery, which is characterized in that step
(6) it specifically includes: being obtained in the solution containing other cations to step (4) and decoppering agent is added, and adjusting pH value is 3~5, it
After be added alkaline matter, reaction obtains cobalt sediment；Preferably, the decoppering agent include vulcanized sodium, it is nickel sulfide, any in iron
A combination of one or more；Preferably, the alkaline matter include sodium hydroxide, potassium hydroxide, sodium oxide molybdena, potassium oxide,
Any one in calcium hydroxide or two or more combinations；Preferably, the concentration of the alkaline matter is 0.5~8mol/L；
Preferably, the cobalt sediment includes cobalt hydroxide, cobalt carbonate, cobalt oxide or cobaltosic oxide；
And/or the solution containing other cations includes the mixing of cobalt ions, nickel ion and manganese ion；
And/or the cobalt sediment includes nickel cobalt manganese co-precipitate, the nickel cobalt manganese co-precipitate is the hydroxide of nickel cobalt manganese
Or carbonate.
9. a kind of system for recycling lithium and cobalt from waste and old cobalt acid lithium battery, characterized by comprising:
Detachment means can disassemble waste and old cobalt acid lithium battery, be classified, and positive plate is obtained；
Mechanism is leached in acidification, can make the valuable metal Elements Leaching in the positive plate, obtains acidification leachate；
The reverse osmosis combined system of ultrafiltration-nanofiltration-comprising ultrafiltration membrane, nanofiltration membrane and reverse osmosis membrane, at least for leaching will to be acidified
Lithium ion and other cation separations, concentration in liquid；
Lithium precipitates mechanism, is at least used to make lithium ion Precipitation；
Cobalt precipitates mechanism, is at least used to make the cobalt ions Precipitation in other cations.
10. the system according to claim 9 for recycling lithium and cobalt from waste and old cobalt acid lithium battery, it is characterised in that also wrap
Include: high-temperature process mechanism is at least used to carry out high-temperature process to the positive plate, to remove the bonding in the positive plate
Agent；
And/or the system also includes: impurity removal mechanism is at least used to remove to the solution containing other cations and live together
Reason.
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| CN112410565A (en) * | 2020-11-18 | 2021-02-26 | 上海第二工业大学 | Method for recovering valuable metal elements from waste ternary lithium ion battery positive electrode material |
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| CN112707447A (en) * | 2020-12-25 | 2021-04-27 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Method for recycling and regenerating anode material from waste lithium cobalt oxide battery |
| CN113611876A (en) * | 2021-08-05 | 2021-11-05 | 哈尔滨工业大学 | Method for recycling anode material of waste lithium ion battery as electrocatalyst |
| CN113981226A (en) * | 2021-09-29 | 2022-01-28 | 贵州中伟资源循环产业发展有限公司 | Method for pretreating ternary positive plate to be recycled |
| CN113981226B (en) * | 2021-09-29 | 2023-09-05 | 贵州中伟资源循环产业发展有限公司 | Method for preprocessing ternary positive plate to be recycled |
| CN114134329A (en) * | 2021-11-30 | 2022-03-04 | 中国科学院宁波材料技术与工程研究所 | Method for recovering valuable metals in positive electrode material by utilizing aluminum foil of waste lithium ion battery current collector |
| CN114134329B (en) * | 2021-11-30 | 2023-12-22 | 中国科学院宁波材料技术与工程研究所 | Method for recycling valuable metals in positive electrode material by utilizing aluminum foil of current collector of waste lithium ion battery |
| CN114665182A (en) * | 2022-04-25 | 2022-06-24 | 中国科学院青海盐湖研究所 | Method for separating and recovering current collector and negative electrode material in waste lithium ion battery negative electrode |
| CN114665182B (en) * | 2022-04-25 | 2024-04-30 | 中国科学院青海盐湖研究所 | Method for separating and recycling current collector and negative electrode material in negative electrode of waste lithium ion battery |
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