CN109234524A - A kind of method and system of the comprehensively recovering valuable metal from waste and old ternary lithium battery - Google Patents
A kind of method and system of the comprehensively recovering valuable metal from waste and old ternary lithium battery Download PDFInfo
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- CN109234524A CN109234524A CN201811093703.8A CN201811093703A CN109234524A CN 109234524 A CN109234524 A CN 109234524A CN 201811093703 A CN201811093703 A CN 201811093703A CN 109234524 A CN109234524 A CN 109234524A
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- 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
- 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
- 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
- C22B47/00—Obtaining manganese
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a kind of method and system of comprehensively recovering valuable metal from waste and old ternary lithium battery.The described method includes: disassembling out positive plate from waste and old ternary 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；Using Nanofiltration-membrane technique, the other cation separations that will be acidified the lithium ion in leachate be different from lithium ion obtain lithium-containing solution and the solution containing other cations, then carry out enrichment method respectively using reverse osmosis technology；And the lithium ion Precipitation in lithium-containing solution is made using lithium precipitating reagent, and nickel ion, cobalt ions and manganese ion Precipitation in the solution containing other cations are made using alkaline matter, realize the recycling of valuable metal.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 method and corresponding system of the present invention relates to a kind of from waste and old ternary lithium battery comprehensively recovering valuable metal, belong to
In lithium battery 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.
The yield of Chinese lithium battery in 2016 reaches 78.42 hundred million, increases by 40% on a year-on-year basis, wherein power battery yield reaches
29.39GWh becomes maximum consumption terminal more than 3C battery production.With the promotion and popularization of pure electric automobile, lithium-ion electric
Pond market will continue to keep rapid growth, and Chinese lithium electricity market scale in 2017 reaches 82GWh, and next three years compound growth rate will
It is 25%.With the raising that country requires power battery energy density, power battery gradually turns to nickel from ferric phosphate lithium cell
Cobalt-manganese ternary battery, type several typical case's nickel-cobalt-manganese ternary lithium batteries such as including 111/523/622/811, it is contemplated that the five-year
Ternary power battery will become mainstream.
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 and old ternary lithium
The valuable metals such as synthetical recovery nickel cobalt manganese lithium in battery, 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 or presoma.Although solvent extraction extracts
High-efficient, obtained product purity is high, but organic solvent it is more or less there is molten damage and volatile pollution environment, cause
Secondary pollution, other extraction higher cost, there is limitations in the industrial production.For another example since nickel, cobalt equipotential are close, electricity
Nickel cobalt can generate synchronous deposition in deposition technique, form cobalt-nickel alloy, influence subsequent purifying, constrain the application of extension.
Furthermore prior art precipitating or extraction nickel cobalt manganese, then purify lithium-containing solution.The process is especially cumbersome, needs a point 4-5 stage
PH value is adjusted, a large amount of soda acids is consumed and technique is tediously long, be not easy accurately to control.
Such as Chinese patent CN103199230A obtains the powder of positive electrode using pretreatment, then sour molten removal of impurities obtains
Nickeliferous manganese mixed solution, makees complexing agent using acetate, new to add nickel source or manganese source, then makes nickel manganese in electrolytic cell Inner electrolysis
It is deposited in titanium simultaneously, the nickel manganese mixture of deposition is added into lithium source in proportion and is sintered, nickel ion doped is obtained.The method is thought
Road is fine, but does not purify out lithium salts, so that valuable lithium resource waste.Chinese patent CN10871048A uses alkali soluble solution
Aluminium foil, the then valuable metal element of Ore Leaching positive electrode, then adjust pH value after removing the impurity such as ferro-aluminum, using P204 or
P507 extraction manganese cobalt nickel obtains the products such as manganese sulfate, cobaltous sulfate, nickel sulfate, and further high-temperature calcination prepares cobalt oxide, nickel oxide
Equal products.Also without the recycling of clear lithium in this method, and the method for using organic solvent extraction, it be easy to cause organic matter
Volatilization and organic liquid waste processing be also problem.In addition Chinese patent CN106785167A is recycled using the method for high-temperature calcination
Ternary nickel cobalt manganese material, first high-temperature calcination 3-7min, then crushing, screening wait until positive electrode, then ball milling, water logging, solid-liquid
Separation, obtains lithium-containing solution.The method technique is more environmentally friendly, but lithium recycling yield is relatively low, and there is no return well for other metallic elements
It receives and utilizes.
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 methods of comprehensively recovering valuable metal from waste and old ternary lithium battery
And system, to overcome deficiency in the prior art.
For achieving the above object, present invention employs following technical solutions:
The embodiment of the invention provides a kind of method of comprehensively recovering valuable metal from waste and old ternary lithium battery, packets
It includes:
Positive plate is disassembled out from waste and old ternary 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 nickel ion, cobalt ions and manganese ion；
And the lithium ion Precipitation in the lithium-containing solution is made using lithium precipitating reagent, and institute is made using alkaline matter
Nickel ion, cobalt ions and the manganese ion Precipitation in the solution containing other cations are stated, realizes the recycling of valuable metal.
In some embodiments, the method for recycling lithium and cobalt from waste and old ternary lithium battery specifically includes:
(1) it discharged waste and old ternary 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 nickel
Cobalt manganese co-precipitate.
The embodiment of the invention also provides a kind of system of comprehensively recovering valuable metal from waste and old ternary lithium battery, packets
It includes:
Detachment means can disassemble waste and old ternary 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；
Nickel cobalt manganese is co-precipitated mechanism, is at least used to make nickel ion, cobalt ions and manganese ion precipitating in other cations
It is precipitated.
Compared with the prior art, the beneficial effects of the present invention are:
1) the method valuable metal of the comprehensively recovering valuable metal provided by the invention from waste and old ternary lithium battery separates skill
Art is advanced, good separating effect, using ultrafiltration-nanofiltration-it is reverse osmosis associated with mode preferentially make lithium ion and other bivalent cations
Separation, simplification of flowsheet, and the process are physical process, will not introduce organic matter or foreign ion, two kinds of ions of nickel cobalt
Single-stage rejection effect reach 90% or more, manganese ion single-stage rejection effect reaches 85% or more；
2) the method separating-purifying theory of the comprehensively recovering valuable metal provided by the invention from waste and old ternary lithium battery is new,
Remaining organic macromolecule is preferentially removed using ultrafiltration pretreatment acidification leachate, reduces pollution and blocking to nanofiltration membrane, then
Separating Li and other bivalent metal ions in acidification leachate, then reprocessing contains lithium and nickel and cobalt containing manganese mixed solution respectively,
Removal of impurities is concentrated to get product, substantially reduces process flow, reduces entrainment loss of the lithium ion in cumbersome dedoping step, greatly
The rate of recovery of width raising lithium；
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 is 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 the method for the comprehensively recovering valuable metal from waste and old ternary lithium battery in a typical embodiments of the invention
Flow diagram.
Specific embodiment
In view of existing waste and old ternary lithium battery recovery efficiency is low, technique is tediously long, to environment, there are the deficiencies of secondary pollution, originally
Case inventor is studied for a long period of time and is largely practiced, and is able to propose technical solution of the present invention, is mainly included battery dismantling, divides
Class, positive plate are broken, heat treatment, Ore Leaching, ultrafiltration membrane-nanofiltration membrane-reverse osmosis separation concentration of valuable metals ion, removal of impurities, sink
The processing steps such as shallow lake utilize ultrafiltration pretreatment acidification leachate to remove remaining organic macromolecule, reduce the pollution to nanofiltration membrane
And blocking, the metal ions such as lithium and nickel cobalt manganese, reverse osmosis enrichment method lithium ion and nickel respectively are efficiently separated using Nanofiltering membrane
Then the metal ions such as cobalt manganese are settled out lithium carbonate and nickel-cobalt-manganese ternary presoma respectively again.As follows will to the technical solution, its
Implementation process and principle etc. are further explained.
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 the elements such as nickel cobalt manganese.The process is greatly reduced the usage amount of soda acid and avoids to be extracted using organic solvent
The technical process such as nickel cobalt manganese are taken, in combination with reverse osmosis concentration technology, solution concentration and evaporation energy consumption is reduced, can quickly realize
Valuable metal ions have the characteristics that environmentally protective, low energy consumption, recovery efficiency are high to separation and purification, and technological operation is simple,
It is easy to amplify realization industrialization.
As the one aspect of technical solution of the present invention, involved in be a kind of to be integrated back from waste and old ternary lithium battery
The method for receiving valuable metal comprising:
Positive plate is disassembled out from waste and old ternary 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 nickel ion, cobalt ions and manganese ion；
And the lithium ion Precipitation in the lithium-containing solution is made using lithium precipitating reagent, and institute is made using alkaline matter
Nickel ion, cobalt ions and the manganese ion Precipitation in the solution containing other cations are stated, realizes the recycling of valuable metal.
In some embodiments, the method for the comprehensively recovering valuable metal from waste and old ternary lithium battery specifically includes:
(1) it discharged waste and old ternary 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 nickel
Cobalt manganese co-precipitate.
In some embodiments, the waste and old ternary lithium battery includes nickel-cobalt-manganese ternary waste lithium cell, main Types with
For typical ternary battery nickel cobalt manganese molar ratio, mainly there are 111,523,622,811 etc. four kinds of typical types and lithium batteries
The discarded positive plate etc. that production process generates, 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
It is 2~10, the lithium-containing solution after being finally concentrated and the solution containing other cations.Ultrafiltration-the nanofiltration-is reverse osmosis
Technology, which refers to, removes remaining organic macromolecule using ultrafiltration pretreatment acidification leachate, reduces pollution and blocking to nanofiltration membrane,
Using nanofiltration membrane separating Li and other metal ions, it is mainly used for monovalence and divalent ion separation i.e. lithium and cobalt, nickel, manganese divide
From using reverse osmosis membrane enrichment method lithium-containing solution, reduction concentration and evaporation amount 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, nickel cobalt
The single-stage rejection effect of two kinds of ions reaches 90% or more, and manganese ion single-stage rejection effect reaches 85% or more, then in conjunction with anti-
Lithium-containing solution is concentrated in infiltration once again, and lithium concentration is made to reach 3-10%.The combination process is in such a way that serial or parallel connection combines
It carries out, 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 nickel cobalt manganese co-precipitate.
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 nickel cobalt manganese co-precipitate is the hydroxide or carbonate of nickel cobalt manganese, can also be nickel oxide
Perhaps oxalic acid nickel cobalt manganese is precipitated using calcining or conversion process using sodium oxalate cobalt manganese according to the actual situation.
Wherein, shown in Figure 1 as more specifically one of case study on implementation of the invention, it is described from waste and old ternary lithium
The method of comprehensively recovering valuable metal may particularly include following steps in battery:
It (is generated including the types such as 111,523,622,811 and lithium battery production process useless with waste and old ternary lithium battery
Abandon positive plate) it is raw material, it discharged, cracked, removed, sieved, obtain positive plate, high-temperature process removes binder, through the molten leaching of acid
Filtrate is passed through ultrafiltration membrane-nanofiltration membrane-reverse osmosis treatment, respectively obtains lithium-containing solution and other ions by valuable metal element out
Mixed 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
The isolated nickel and cobalt containing manganese mixed solution of nanofiltration membrane is added decoppering agent and removes copper ion, and adjusting pH value is 3-5, and precipitating removes
The impurity such as ferro-aluminum, are then added the mixed precipitation that alkali is co-precipitated out nickel cobalt manganese, can be used as ternary precursor through detection, realize
To the synthetical recovery of lithium, nickel, cobalt, manganese in waste and old ternary battery.Concentrated mother liquor, which can be used, recycles not outlet, fits in the circulating cycle
When addition deionized water dilution, the lithium product that lithium carbonate product obtains after recrystallization, washing, drying has reached LITHIUM BATTERY
Requirement, can direct reuse.
The mixed slurry is after above-mentioned steps are handled, and the main content of lithium carbonate is greater than 99.5%, and aluminium content is less than
0.001%, iron content is less than 0.001%, and sodium content is less than 0.025%, and content of magnesium is less than 0.008%.Nickel cobalt manganese co-precipitate
Quality meets the requirement of the lithium battery quality of production.
The other side of the embodiment of the present invention additionally provides one kind valuable gold of synthetical recovery from waste and old ternary lithium battery
The system of category comprising:
Detachment means can disassemble waste and old ternary 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；
Nickel cobalt manganese is co-precipitated mechanism, is at least used to make nickel ion, cobalt ions and manganese ion precipitating in other cations
It is precipitated.
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 nickel cobalt manganese element separate and concentration.The process
The usage amount of soda acid is greatly reduced and avoids using technical process such as organic solvent extraction nickel cobalt manganeses, in combination with reverse osmosis
Saturating concentration technique reduces solution concentration and evaporation energy consumption, can quickly realize that valuable metal ions to separation and purification, have green
The high feature of colour circle guarantor, 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 ternary lithium battery as raw material.Old and useless battery electric discharge, dismantling, screening are obtained waste and old three first
First positive electrode.Weigh waste and old tertiary cathode material 1kg at 500 DEG C in Muffle furnace handle 1h after, remove binder, water quenching
And 30min is handled in ultrasonic vibration, remove positive electrode and aluminium foil.Separation aluminium foil, aluminium foil warp are removed using big net sieve pore
Flushing processing can be directly used for aluminium smelting.Sulfuric acid treatment of the obtained black slag fine crushing through 4mol/L, while being added 30% pair
Oxygen water, control solid-to-liquid ratio are 80g/L, and temperature control is at 80 DEG C and is stirred continuously 4h, and the leaching of valuable metal is then obtained by filtration
Liquid.Acid leaching residue 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 1 below:
Chemical component (unit: g/L) in 1 leachate of table
| Classification | Aluminium | Cobalt | Lithium | Manganese | Nickel | Iron | SO4 2- |
| Content | 2.84 | 16.71 | 9.25 | 18.48 | 23.53 | 0.006 | 142.57 |
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 1MPa, and the pressure of nanofiltration membrane is 3.5MPa, concentrated stream
Speed is 3.0L/min, and nickel cobalt manganese plasma is rejected by, and in concentrated water lateral enrichment, lithium ion then enters in fresh water, is detected respectively
To lithium-containing solution and other Ar ion mixing solution, wherein nickel ion single-stage rejection reaches 91.5%, cobalt ions single-stage rejection
95.7%, manganese ion rejection 85.2%.Lithium ion is enriched in fresh water, and the lithium-containing solution of enrichment is further evaporated, lithium is made
Concentration reaches 25g/L, and the sodium carbonate that saturation is added under the conditions of 85 DEG C is settled out lithium carbonate, and washed-recrystallization-washing-is dry
Dry equal processing obtain battery-level lithium carbonate, testing result such as the following table 2:
2 battery-level lithium carbonate testing result of table
Nickel and cobalt containing manganese mixed solution goes copper removal, iron, aluminium etc. miscellaneous respectively through iron replacement, sodium hydroxide control pH value to 5.0
After matter, solution nickel cobalt manganese content is detected, calculates nickel cobalt manganese mole, and adds suitable cobaltous sulfate and uses 5.0mol/L sodium carbonate heavy again
Shallow lake nickel cobalt manganese, obtains Ni0.33Co0.33Mn0.33CO3Ternary precursor, can be directly used for the synthesis of lithium battery.The process flow
Short, environmentally protective, preferential separating Li is co-precipitated out nickel-cobalt-manganese ternary presoma, easy to operate, is easy to be mass produced, carbonic acid
Lithium and ternary precursor product reach downstream battery enterprise to the quality requirement of raw material.
Embodiment 2
Using certain enterprise's ternary lithium anode leftover pieces as raw material.Discarded tertiary cathode leftover pieces 500g is weighed to get down from horse at 450 DEG C
After not handling 2h in furnace, binder is removed, water quenching simultaneously handles 60min in ultrasonic vibration, removes positive electrode and aluminium foil.
Separation aluminium foil is removed using big net sieve pore, aluminium foil can be directly used for aluminium through flushing processing and smelt.Obtained black slag warp fine crushing
The sulfuric acid treatment of 2mol/L, while 30% hydrogen peroxide is added, control solid-to-liquid ratio is 95g/L, and temperature control is at 85 DEG C and constantly stirs
3h is mixed, the leachate of valuable metal is then obtained by filtration.Acid leaching residue is mainly the acid non-soluble substances such as carbon dust.Through in detection leachate
Chemical component, as a result as shown in table 3 below:
Chemical component (unit: g/L) in 3 leachate of table
| Classification | Aluminium | Cobalt | Lithium | Manganese | Nickel | Iron | SO4 2- |
| Content | 1.12 | 18.47 | 10.36 | 18.48 | 19.45 | 0.004 | 121.22 |
Acid leaching liquor pH value is adjusted to 3.0 or so with alkali, is diluted with deionized water and is adjusted yin-yang total ion concentration, control is arrived
62g/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 4.0L/min, and nickel cobalt manganese plasma is rejected by, and in concentrated water lateral enrichment, lithium ion then enters in fresh water,
Detection obtains lithium-containing solution and other Ar ion mixing solution respectively, and wherein nickel ion single-stage rejection reaches 92.5%, cobalt ions
Single-stage rejection 97.7%, manganese ion rejection 86.7%.Lithium ion is enriched in fresh water, and the lithium-containing solution of enrichment is further
Evaporation, makes lithium concentration reach 30g/L, the sodium carbonate that saturation is added under the conditions of 85 DEG C is settled out lithium carbonate, washed-to tie again
The processing such as crystalline substance-washing-drying obtain battery-level lithium carbonate, testing result such as the following table 4:
4 battery-level lithium carbonate testing result of table
Nickel and cobalt containing manganese mixed solution removes the impurity such as copper removal, iron, aluminium to 4 through iron replacement, sodium hydroxide control pH value respectively
Afterwards, solution nickel cobalt manganese content is detected, nickel cobalt manganese mole is calculated, and adds suitable cobaltous sulfate and 6.0mol/L sodium carbonate is used to precipitate again
Nickel cobalt manganese obtains Ni0.5Co0.2Mn0.3CO3Ternary precursor, can be directly used for the synthesis of lithium battery.The process flow is short, green
Colour circle is protected, and preferential separating Li is co-precipitated out nickel-cobalt-manganese ternary presoma, easy to operate, is easy to be mass produced, lithium carbonate and three
First presoma product reaches downstream battery enterprise to the quality requirement of raw material.
Embodiment 3
Using some type of waste and old ternary lithium battery as raw material.Old and useless battery electric discharge, dismantling, screening are obtained waste and old three first
First positive electrode.Weigh waste and old tertiary cathode material 1.2kg at 550 DEG C in Muffle furnace handle 2h after, remove binder, water quenching
It is cold and 45min is handled in ultrasonic vibration, remove positive electrode and aluminium foil.Separation aluminium foil, aluminium foil are removed using big net sieve pore
It can be directly used for aluminium through flushing processing to smelt.HCl treatment of the obtained black slag fine crushing through 3mol/L, while being added 30%
Hydrogen peroxide, control solid-to-liquid ratio are 75g/L, and temperature control is at 85 DEG C and is stirred continuously 6h, and the leaching of valuable metal is then obtained by filtration
Liquid out.Acid leaching residue 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 5 below:
Chemical component (unit: g/L) in 5 leachate of table
| Classification | Aluminium | Cobalt | Lithium | Manganese | Nickel | Iron | Cl- |
| Content | 2.23 | 19.71 | 10.47 | 22.58 | 28.53 | 0.07 | 101.53 |
Acid leaching liquor pH value is adjusted to 3.0 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 0.8MPa, and the pressure of nanofiltration membrane is 3.5MPa, concentrated water
Flow velocity is 3.0L/min, and nickel cobalt manganese plasma is rejected by, and in concentrated water lateral enrichment, lithium ion then enters in fresh water, is detected respectively
Lithium-containing solution and other Ar ion mixing solution are obtained, wherein nickel ion single-stage rejection reaches 94.8%, the retention of cobalt ions single-stage
Rate 98.9%, manganese ion rejection 89.4%.Lithium ion is enriched in fresh water, and the lithium-containing solution of enrichment is further evaporated, is made
Lithium concentration reaches 28g/l, and the sodium carbonate that saturation is added under the conditions of 80 DEG C is settled out lithium carbonate, washed-recrystallization-washing-
The processing such as dry obtain battery-level lithium carbonate, testing result such as the following table 6:
6 battery-level lithium carbonate testing result of table
Nickel and cobalt containing manganese mixed solution is after vulcanized sodium copper removal, sodium hydroxide control pH value to the impurity such as 5 difference iron, aluminium, inspection
Solution nickel cobalt manganese content is surveyed, nickel cobalt manganese mole is calculated, and adds suitable nickel chloride and 0.5mol/L sodium carbonate is used to precipitate nickel cobalt again
Manganese obtains Ni0.6Co0.2Mn0.2CO3Ternary precursor, can be directly used for the synthesis of lithium battery.The process flow is short, green ring
It protects, preferential separating Li is co-precipitated out nickel-cobalt-manganese ternary presoma, and it is easy to operate, it is easy to be mass produced, before lithium carbonate and ternary
It drives body product and reaches downstream battery enterprise to the quality requirement of raw material.
Embodiment 4
Using some type of waste and old ternary lithium battery as raw material.Old and useless battery electric discharge, dismantling, screening are obtained waste and old three first
First positive electrode.Weigh waste and old tertiary cathode material 1.8kg at 600 DEG C in Muffle furnace handle 2h after, remove binder, water quenching
It is cold and 60min is handled in ultrasonic vibration, remove positive electrode and aluminium foil.Separation aluminium foil, aluminium foil are removed using big net sieve pore
It can be directly used for aluminium through flushing processing to smelt.Sulfuric acid treatment of the obtained black slag fine crushing through 3mol/L, while being added 30%
Hydrogen peroxide, control solid-to-liquid ratio are 60g/L, and temperature control is at 80 DEG C and is stirred continuously 6h, and the leaching of valuable metal is then obtained by filtration
Liquid out.Acid leaching residue 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 7 below:
Chemical component (unit: g/L) in 7 leachate of table
| Classification | Aluminium | Cobalt | Lithium | Manganese | Nickel | Iron | SO4 2- |
| Content | 3.15 | 17.71 | 9.58 | 19.39 | 25.52 | 0.016 | 138.96 |
Acid leaching liquor pH value is adjusted to 3.5 or so with alkali, and is diluted and adjusted yin-yang total ion concentration, 60g/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, nickel cobalt manganese plasma are rejected by, and in concentrated water lateral enrichment, lithium ion then enters in fresh water, and detection obtains respectively
Lithium-containing solution and other Ar ion mixing solution, wherein nickel ion single-stage rejection reaches 90.8%, cobalt ions single-stage rejection
92.3%, manganese ion rejection 86.1%.Lithium ion is enriched in fresh water, and the lithium-containing solution of enrichment is further evaporated, lithium is made
Concentration reaches 30g/l, be added under the conditions of 80 DEG C saturation sodium carbonate be settled out lithium carbonate it is washed-recrystallization-washing-drying
Equal processing obtain battery-level lithium carbonate, testing result such as the following table 8:
8 battery-level lithium carbonate testing result of table
Nickel and cobalt containing manganese mixed solution goes copper removal, iron, aluminium etc. miscellaneous respectively through iron replacement, sodium hydroxide control pH value to 3.0
After matter, solution nickel cobalt manganese content is detected, calculates nickel cobalt manganese mole, and adds suitable cobaltous sulfate and uses 8.0mol/L sodium carbonate heavy again
Shallow lake nickel cobalt manganese, obtains Ni0.33Co0.33Mn0.33CO3Ternary precursor, can be directly used for the synthesis of lithium battery.The process flow
Short, environmentally protective, preferential separating Li is co-precipitated out nickel-cobalt-manganese ternary presoma, easy to operate, is easy to be mass produced, carbonic acid
Lithium and ternary precursor product reach downstream battery enterprise to the quality requirement of raw material.
Embodiment 5
Using some type of waste and old ternary lithium battery as raw material.Old and useless battery electric discharge, dismantling, screening are obtained waste and old three first
First positive electrode.Weigh waste and old tertiary cathode material 1.2kg at 300 DEG C in Muffle furnace handle 6h after, remove binder, water quenching
It is cold and 45min is handled in ultrasonic vibration, remove positive electrode and aluminium foil.Separation aluminium foil, aluminium foil are removed using big net sieve pore
It can be directly used for aluminium through flushing processing to smelt.HCl treatment of the obtained black slag fine crushing through 10mol/L, while being added 30%
Hydrogen peroxide, control solid-to-liquid ratio are 120g/L, and temperature control is at 90 DEG C and is stirred continuously 6h, and the leaching of valuable metal is then obtained by filtration
Liquid out.Acid leaching residue is mainly the acid non-soluble substances such as carbon dust.
Acid leaching liquor pH value is adjusted to 10.0 or so with alkali, and is diluted and adjusted yin-yang total ion concentration, 120g/L is arrived in control,
Into ultrafiltration-nanofiltration-ro treatment technology, the pressure for controlling ultrafiltration membrane is 0.1MPa, and the pressure of nanofiltration membrane is 0.1MPa, dense
Water flow velocity is 0.1L/min, and nickel cobalt manganese plasma is rejected by, and in concentrated water lateral enrichment, lithium ion then enters in fresh water, is examined respectively
Lithium-containing solution and other Ar ion mixing solution are measured, wherein nickel ion single-stage rejection reaches 94.8%, and cobalt ions single-stage is cut
Stay rate 98.9%, manganese ion rejection 89.4%.Lithium ion is enriched in fresh water, and the lithium-containing solution of enrichment is further evaporated,
Lithium concentration is set to reach 30g/l, the sodium carbonate that saturation is added under the conditions of 80 DEG C is settled out lithium carbonate, and washed-recrystallization-washes
It the processing such as washs-dries and obtain battery-level lithium carbonate.
Nickel and cobalt containing manganese mixed solution after vulcanized sodium copper removal, sodium hydroxide control pH value to 4.5 difference iron, the impurity such as aluminium,
Solution nickel cobalt manganese content is detected, calculates nickel cobalt manganese mole, and add suitable nickel chloride and use 0.5mol/L sodium carbonate coprecipitated nickel hydroxide again
Cobalt manganese, obtains Ni0.6Co0.2Mn0.2CO3Ternary precursor, can be directly used for the synthesis of lithium battery.The process flow is short, green
Environmental protection, preferential separating Li are co-precipitated out nickel-cobalt-manganese ternary presoma, easy to operate, are easy to be mass produced, lithium carbonate and ternary
Presoma product reaches downstream battery enterprise to the quality requirement of raw material.
Embodiment 6
Using some type of waste and old ternary lithium battery as raw material.Old and useless battery electric discharge, dismantling, screening are obtained waste and old three first
First positive electrode.Weigh waste and old tertiary cathode material 1.2kg at 800 DEG C in Muffle furnace handle 0.5h after, remove binder, water
Quenching simultaneously handles 45min in ultrasonic vibration, removes positive electrode and aluminium foil.Separation aluminium foil, aluminium are removed using big net sieve pore
Foil can be directly used for aluminium through flushing processing and smelt.HCl treatment of the obtained black slag fine crushing through 1mol/L, is added simultaneously
30% hydrogen peroxide, control solid-to-liquid ratio are 40g/L, and temperature control is at 30 DEG C and is stirred continuously 6h, and valuable metal is then obtained by filtration
Leachate.Acid leaching residue is mainly the acid non-soluble substances such as carbon dust.
Acid leaching liquor pH value is adjusted to 1.0 or so with alkali, and is diluted and adjusted yin-yang total ion concentration, 120g/L is arrived in control,
Into ultrafiltration-nanofiltration-ro treatment technology, the pressure for controlling ultrafiltration membrane is 1.5MPa, and the pressure of nanofiltration membrane is 6MPa, concentrated water
Flow velocity is 5L/min, and nickel cobalt manganese plasma is rejected by, and in concentrated water lateral enrichment, lithium ion then enters in fresh water, is detected respectively
To lithium-containing solution and other Ar ion mixing solution, wherein nickel ion single-stage rejection reaches 94.8%, cobalt ions single-stage rejection
98.9%, manganese ion rejection 89.4%.Lithium ion is enriched in fresh water, and the lithium-containing solution of enrichment is further evaporated, lithium is made
Concentration reaches 35g/l, and the sodium carbonate that saturation is added under the conditions of 80 DEG C is settled out lithium carbonate, and washed-recrystallization-washing-is dry
Dry equal processing obtain battery-level lithium carbonate.
Nickel and cobalt containing manganese mixed solution after vulcanized sodium copper removal, sodium hydroxide control pH value to 4.0 difference iron, the impurity such as aluminium,
Solution nickel cobalt manganese content is detected, nickel cobalt manganese mole is calculated, and adds suitable nickel chloride and 8mol/L sodium carbonate is used to precipitate nickel cobalt again
Manganese obtains Ni0.6Co0.2Mn0.2CO3Ternary precursor, can be directly used for the synthesis of lithium battery.The process flow is short, green ring
It protects, preferential separating Li is co-precipitated out nickel-cobalt-manganese ternary presoma, and it is easy to operate, it is easy to be mass produced, before lithium carbonate and ternary
It drives body product and reaches 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 nickel cobalt manganese from waste and old ternary lithium battery, obtained the battery of high quality
Level lithium carbonate and nickel-cobalt-manganese ternary presoma 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 of the comprehensively recovering valuable metal from waste and old ternary lithium battery, characterized by comprising:
Positive plate is disassembled out from waste and old ternary 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 nickel ion, cobalt ions and manganese ion；
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 are nickel ion, cobalt ions and the manganese ion Precipitation in the solution of other cations, realizes the recycling of valuable metal.
2. the method for the comprehensively recovering valuable metal according to claim 1 from waste and old ternary lithium battery, it is characterised in that
It specifically includes:
(1) it discharged waste and old ternary 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 nickel cobalt manganese
Co-precipitate.
3. the method for the comprehensively recovering valuable metal according to claim 1 or 2 from waste and old ternary lithium battery, feature exist
In: the waste and old ternary lithium battery includes nickel-cobalt-manganese ternary waste lithium cell, the type of the nickel-cobalt-manganese ternary waste lithium cell
Including 111,523,622 or 811 types.
4. the method for the comprehensively recovering valuable metal according to claim 2 from waste and old ternary lithium battery, which is characterized in that
Step (2) specifically includes: calcining to the positive plate, carries 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 for the comprehensively recovering valuable metal according to claim 2 from waste and old ternary lithium battery, which is characterized in that
Step (3) specifically includes: the positive plate leaching through high-temperature process being placed in acidic materials, while hydrogen peroxide is added, controls solid-liquid
It than for 40~120g/L, and is stirred in 30~90 DEG C, makes the valuable metal Elements Leaching in the positive plate, obtain acidification and leach
Liquid；Preferably, the acidic materials include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, in hydrofluoric acid any one or two
Kind or more combination；Preferably, the concentration of the acidic materials is 1~10mol/L.
6. the method for the comprehensively recovering valuable metal according to claim 2 from waste and old ternary lithium battery, which is characterized in that
Step (4) specifically includes: step (3) being obtained acidification leachate and inputs ultrafiltration membrane, nanofiltration membrane and reverse osmosis membrane respectively, wherein
The aperture of the ultrafiltration membrane isPreferablyOperating pressure is 0.1~1.5MPa, the nanofiltration membrane
Operating pressure is 0.1~6MPa, and monolithic membrane flow velocity is 0.1~5L/min, and working ph values are 2~10, after being finally concentrated
Lithium-containing solution and solution containing other cations；Preferably, the concentration of the lithium-containing solution after concentration is in 15g/L or more；It is preferred that
, the material of the nanofiltration membrane include polyamide, polysulfones, polyvinyl alcohol, sulfonated polysulfone, sulfonated polyether sulfone, in cellulose acetate
Any two or more combination, especially preferably polyamide and polysulfone composite membrane, retaining molecular weight is 50~1000 dongles
?；Preferably, the nanofiltration membrane includes board-like nanofiltration membrane or rolling nanofiltration membrane.
7. the method for the comprehensively recovering valuable metal according to claim 2 from waste and old ternary lithium battery, it is characterised in that:
In step (5), the lithium precipitating reagent includes sodium carbonate, sodium bicarbonate or sodium fluoride；And/or the lithium sediment includes carbonic acid
Lithium 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 for the comprehensively recovering valuable metal according to claim 2 from waste and old ternary lithium battery, which is characterized in that
Step (6) specifically includes: obtained in the solution containing other cations to step (4) and decoppering agent be added, and adjust pH value be 3~
5, alkaline matter is added later, reaction obtains nickel cobalt manganese co-precipitate；Preferably, the decoppering agent include vulcanized sodium, nickel sulfide,
Any one in iron or two or more combinations；Preferably, the alkaline matter includes sodium hydroxide, potassium hydroxide, oxidation
Sodium, potassium oxide, any one or two or more combinations in calcium hydroxide；Preferably, the concentration of the alkaline matter is 0.5
~8mol/L；Preferably, the nickel cobalt manganese co-precipitate is the hydroxide or carbonate of nickel cobalt manganese；
And/or the solution containing other cations includes the mixing of cobalt ions, nickel ion and manganese ion；
And/or the nickel cobalt manganese co-precipitate is the hydroxide or carbonate of nickel cobalt manganese.
9. a kind of system of the comprehensively recovering valuable metal from waste and old ternary lithium battery, characterized by comprising:
Detachment means can disassemble waste and old ternary 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；
Nickel cobalt manganese is co-precipitated mechanism, is at least used to make nickel ion, cobalt ions and the manganese ion Precipitation in other cations.
10. the system of the comprehensively recovering valuable metal according to claim 9 from waste and old ternary lithium battery, it is characterised in that
Further include: high-temperature process mechanism is at least used to carry out high-temperature process to the positive plate, viscous in the positive plate to remove
Tie 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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