CN100401577C - Method of recovering cobalt from lithium ion battery and cobalt recovering system - Google Patents
Method of recovering cobalt from lithium ion battery and cobalt recovering system Download PDFInfo
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- CN100401577C CN100401577C CNB2003801076239A CN200380107623A CN100401577C CN 100401577 C CN100401577 C CN 100401577C CN B2003801076239 A CNB2003801076239 A CN B2003801076239A CN 200380107623 A CN200380107623 A CN 200380107623A CN 100401577 C CN100401577 C CN 100401577C
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- 239000010941 cobalt Substances 0.000 title claims abstract description 435
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 435
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 72
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 126
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 123
- 239000000284 extract Substances 0.000 claims abstract description 119
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- 238000000605 extraction Methods 0.000 claims abstract description 43
- 239000012535 impurity Substances 0.000 claims abstract description 42
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- 239000007788 liquid Substances 0.000 claims description 109
- 229910052751 metal Inorganic materials 0.000 claims description 90
- 239000002184 metal Substances 0.000 claims description 90
- 238000011084 recovery Methods 0.000 claims description 87
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- 235000014413 iron hydroxide Nutrition 0.000 description 5
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- 238000012856 packing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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- 150000007522 mineralic acids Chemical class 0.000 description 2
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- KGQGQKPCLGRZAZ-UHFFFAOYSA-N oxocobalt;hydrate Chemical compound O.[Co]=O KGQGQKPCLGRZAZ-UHFFFAOYSA-N 0.000 description 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 2
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- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
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- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- 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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Secondary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Method or system comprising the step of not only extracting cobalt from defective positive electrodes with a solvent but also extracting cobalt from extraction residue obtained from defective positive electrodes and magnetized matter obtained from waste lithium ion batteries and runoff batteries (step S100); the step of removing impurities contained in the cobalt extract, thereby obtaining a clean cobalt solution (step S200); the step of forming a cobalt hydroxide cake from the clean cobalt solution (step S300); and the step of electrolyzing an electrolytic solution of cobalt containing the cobalt hydroxide cake as an electrolyte to thereby precipitate metallic cobalt (step S400).
Description
Technical field
The present invention relates to reclaim the method for valuable metal in the rechargeable battery, particularly reclaim the interior cobalt recovery method and the cobalt recovery circuit of lithium ion battery of the cobalt that contains in discarded lithium ion battery and the lithium ion battery substandard products.
Background technology
Below, cobalt recovery method and cobalt recovery circuit in the lithium ion battery are described.
At present, well-known lithium ion battery is the very high rechargeable battery of capacitance of Unit Weight or unit volume.This lithium ion battery, receives much concern as the battery of electronic equipments such as the notebook computer, mobile phone that are used for miniaturization or lightness in recent years, to its needs and consume increase in leap.Therefore, from the efficent use of resources angle, from the used lithium ion battery (discarded lithium ion battery) that market, circulates and to reclaim the valuable metal cobalt from the positive active material that contains the substandard products of battery manufacturers be very important.
Therefore, lithium ion battery have use cobalt acid lithium as positive active material, use the structure of graphite (carbon) as negative electrode active material, stacked each pole plate of multilayer.
And, being the statutory standards of maintenance based on the recycling rate of " the utilization of resources promotion law " implemented April calendar year 2001, the system of the recovery and reuse of the cobalt that contains in the substandard products to this discarded lithium ion battery or production has the tendency of further reinforcement.
At present, discarded lithium ion battery is for removing the resinous principle that contains and bath composition etc. by after the calcining, crushing, sizing in accordance with regulations form metal dust, and, select to distinguish this metal dust by magnetic, thereby reclaim magnetic metal cobalt (with reference to patent documentation 1).
In the recovery method of the cobalt in patent documentation 1 in the used lithium rechargeable battery of record, select the magnetic metal distinguish out at that in electric furnace after the dissolving by magnetic, removing slag also removes metal impurities such as iron, copper, aluminium, concentrate after the cobalt that contains, ooze out the concise contained cobalts of conventional method such as method by acid.
In addition, following method (with reference to patent documentation 2) is also arranged: by in the Treatment Solution that contains oxidizing acids such as sulfuric acid, nitric acid and hydrogen peroxide, flood the electrode active material of above-mentioned discarded lithium ion battery, after the form extraction of the cobalt composition in the electrode active material with inorganic metal salt, this Treatment Solution is sneaked into caustic soda, the sediment of the cobalt hydroxide that obtains is reclaimed as cobalt.
Te Kaiping 7-245126 communique (2-3 page or leaf)
Patent documentation 2
Te Kaiping 11-265736 communique (2-4 page or leaf, 8-9 figure)
But in the substandard products that above-mentioned battery manufacturers is produced, having positive plate and negative plate is the substandard products (the substandard products battery of production) that are installed into external packing shell internal state and the substandard products (anodal substandard products) of positive plate monomer.
But the positive electrode plate monomer of lithium battery has with aluminium strip as supporter, in its surface attachment the structure of cobalt acid lithium is arranged, so for the recovery of the cobalt in the anodal substandard products, need not to carry out calcination processing, crushing is handled, screening is handled situation is more.Thereby, in above-mentioned patent documentation 1, in the cobalt recovery method of record, exist time and labour that cost is consumed in the cobalt recycling in a large number, produce the bad problem of cobalt organic efficiency.
And, the aluminium strip that uses as the supporter of positive plate top electrode active material, because it is to handle with crushing not allow squashy material relatively, so the situation that this aluminium strip and cobalt acid lithium can not be peeled off fully occurs, handle and cobalt acid lithium might be removed with aluminium strip by screening thereafter, thereby cause the problem that the cobalt rate of recovery is low.
In addition, by being immersed in the acid flux material, when the electrode active material of lithium ion battery extracts cobalt, indispensable the 3 valency cobalts that contain usually in this electrode active material are reduced into the reducing agent of the divalent cobalt of separating out easily from acid flux material, can use hydrogen peroxide as this reducing agent.But, in the acid flux material for to make hydrogen peroxide have the function of reducing agent, need with for example coexistence such as nitric acid or hot concentrated sulfuric acid of the acid medicine with potent oxidability, therefore when operation, follow danger, then have the problem of degree of danger when increasing cobalt and reclaiming operation.
And, hydrogen peroxide according to the state of handling solvent, with the object being treated state of contact, the oneself decomposes easily, appearance can not be brought into play the situation of desired reducing agent function.Therefore, its oneself occurs suppressing and decompose, be difficult to the stable more problem of situation that obtains the high-recovery of cobalt.
And, for object being treated, for bringing into play the reduction of hydrogen peroxide fully, and under the oneself who considers this hydrogen peroxide situation of decomposing, need at least hydrogen peroxide more than or equal to 3 times of theoretical values, risk factor when cobalt recovery operation occurring further raises, the problem that the while operating cost also raises.
The purpose of this invention is to provide cobalt recovery method and cobalt recovery circuit in a kind of lithium ion battery, in view of the above problems, can carry out high efficiency cobalt from discarded lithium battery, substandard products battery and anodal substandard products and reclaim, and improve the fail safe of cobalt recovery operation.
Summary of the invention
About the cobalt recovery method in the lithium ion battery of the present invention, comprise following process: to handle the discarded lithium ion battery in the middle of the cobalt recycle object obsolete material obtain in the lithium ion battery and/or the crushing powder of substandard products battery by the crushing after the calcination processing, after sieving below the granularity in accordance with regulations, this crushing powder is selected to distinguish into the magnetic separation operation of magnetic metal and nonmagnetic metal with magnetic; The cobalt that anodal substandard products contained in the middle of the cobalt recycle object obsolete material in the above-mentioned lithium ion battery is extracted the 1st abstraction process that separates with the 1st acid flux material; According to the above-mentioned magnetic operation of selecting, the cobalt with containing in the extraction residue free or precipitation in the cobalt that contains in the magnetic metal of selecting to distinguish out and above-mentioned the 1st acid flux material extracts the 2nd abstraction process of separation with the 2nd acid flux material.
According to the present invention, discarded lithium ion battery and substandard products battery crushing after by calcination processing is treated as the crushing powder, after sieving smaller or equal to designated size, on the one hand resulting crushing powder smaller or equal to designated size is selected to distinguish into magnetic metal and nonmagnetic metal with magnetic, extract after the cobalt that contains in the anodal substandard products with the 1st acid flux material on the other hand, be recovered in extraction residue free or precipitation in above-mentioned the 1st acid flux material; Then, above-mentioned magnetic metal and said extracted residue mixed together are advanced the 2nd acid flux material, extract the cobalt that is contained separately, when from discarded lithium battery, substandard products battery and anodal substandard products, extracting cobalt effectively with high-recovery, fail safe when also having improved operation, and reduced operating cost.
And, about the cobalt recovery method in the lithium ion battery of the present invention, also comprise: separate out contain extract the 1st cobalt extract of the cobalt that separates by above-mentioned the 1st abstraction process and contain extract the metal impurities that dissolve in the 2nd cobalt extract of the cobalt that separates by above-mentioned the 2nd abstraction process after, separation contains the clean liquid operation of the clean liquid residue of the cobalt detergent remover of above-mentioned cobalt and the formation of above-mentioned metal impurities; Above-mentioned clean liquid residue is separated into (the リ パ Le プ) residue of pulp again and the pulp matting again of pulp filtrate again.The filtrate of pulp again that obtains by above-mentioned pulp matting again is mixed into above-mentioned the 1st acid flux material or above-mentioned the 2nd acid flux material.
According to the present invention, separate out and be dissolved in the 1st cobalt extract that contains from the cobalt of anodal substandard products extraction, after the metal impurities of the 2nd extract that contains the cobalt that from the extraction residue that obtains according to above-mentioned the 1st abstraction process and above-mentioned magnetic metal, extracts, when above-mentioned metal impurities separate as clean liquid residue, reclaim the cobalt cleaning fluid on the one hand, above-mentioned clean liquid residue is cleaned in pulp more on the other hand, be separated into again the pulp residue and again after the pulp filtrate, with this again pulp filtrate be mixed into above-mentioned the 1st acid flux material or above-mentioned the 2nd acid flux material, can reclaim efficiently and contain the cobalt cleaning fluid that concentrates cobalt, can also reclaim again attached to the cobalt on the above-mentioned clean liquid residue simultaneously.
And the cobalt recovery method about in the lithium ion battery of the present invention comprises: to above-mentioned cobalt cleaning fluid mixed-alkali reagent and after separating out cobalt hydroxide, carry out processed and generate the caked cobalt hydroxide of cobalt hydroxide and form piece and generate operation; Form cobalt liquor that piece is dissolved in the 3rd acid flux material as electrolyte with above-mentioned cobalt hydroxide, handle the electrowinning operation that reclaims metallic cobalt by electrowinning from this electrolyte; The solid-liquid separation process that will separate with electrolyte after the processing at the electrolysis residue of free in the electrolyte after above-mentioned electrowinning is handled or precipitation.Above-mentioned electrolysis residue is mixed into the 2nd acid flux material.
According to the present invention, concentrate from the cobalt cleaning fluid of discarded lithium ion battery, cobalt that substandard products battery and anodal substandard products are extracted, be mixed into alkaline reagent and separate out after the cobalt hydroxide, generate cobalt hydroxide by dehydration and form piece; And this cobalt hydroxide is formed piece be dissolved in the electrolyte of the 3rd acid flux material as cobalt, this electrolyte is handled the precipitating metal cobalt by electrowinning on the one hand, handle by Separation of Solid and Liquid on the other hand, reclaim after the electrolysis residue that dissociates in this electrolyte or precipitate, be mixed into above-mentioned the 2nd acid flux material; When the cobalt that contains the cobalt cleaning fluid can be formed the piece recovery with cobalt hydroxide, can be to reclaim metallic cobalt the electrolyte solution efficiently from form piece with cobalt hydroxide; And can reclaim the cobalt that contains in this electrolysis residue again.
And, cobalt recovery method about in the lithium ion battery of the present invention is characterized in that, electrolyte mixes above-mentioned cobalt hydroxide and forms piece after the above-mentioned processing, generate the molten slurry of cobalt hydroxide, the molten slurry of this cobalt hydroxide is mixed into the dilute electrolyte that reaches in the electrowinning operation last.
According to the present invention, handle electrolyte after the processing that the electrolysis residue is removed by above-mentioned Separation of Solid and Liquid, with above-mentioned cobalt hydroxide form piece mixes form the molten slurry of cobalt hydroxide after, be mixed into the dilute electrolyte in the above-mentioned electrowinning processing; When suppressing the electrolyte ph reduction of above-mentioned electrowinning processing, replenish cobalt (Co to this electrolyte
2+); Suppress the reduction of the current efficiency of above-mentioned electrowinning processing.
And, about the cobalt recovery method in the lithium ion battery of the present invention, it is characterized in that, when the above-mentioned the 1st and the 2nd acid flux material is the sulfuric acid solvent, above-mentioned matting is: behind the above-mentioned the 1st and the 2nd cobalt extract mixed calcium hydroxide, carry out the processing of separating out as the iron of above-mentioned metal impurities or aluminium.
According to the present invention, when stating the 1st and the 2nd acid flux material and being the sulfuric acid solvent, the above-mentioned the 1st and the 2nd cobalt extract is: at first, add calcium hydroxide after, add alkaline reagent again, separate out iron or aluminium as above-mentioned metal impurities; Suppress separating out of saltcake that the chemical reaction of this sulfuric acid and this alkaline reagent generates, can separate above-mentioned clean liquid residue efficiently.
And, about the cobalt recovery circuit in the lithium ion battery of the present invention, it is characterized in that, comprise: handle the discarded lithium ion battery in the middle of the cobalt recycle object obsolete material in the lithium ion battery obtain and/or the crushing powder of substandard products battery by the crushing after the calcination processing, after it being sieved, the magnetic that this crushing powder magnetic is selected to distinguish into magnetic metal and nonmagnetic metal is selected the difference device smaller or equal to designated size; The cobalt that contains on the anodal substandard products in the middle of the cobalt recycle object obsolete material in the above-mentioned lithium ion battery is extracted the 1st of separation with the 1st acid flux material extract separator; Select the cobalt in the magnetic metal that the difference device selects to distinguish out and be contained in cobalt in the extraction residue of free or precipitation in the treatment fluid of above-mentioned the 1st extraction element being contained in, extract the 2nd extraction element of separation with the 2nd acid flux material according to above-mentioned magnetic.
According to the present invention, cobalt recovery circuit is by constituting with the lower part: will carry out calcination processing successively to discarded lithium ion battery and substandard products battery, crush and handle, sieve the magnetic selection difference device that the crushing powder smaller or equal to designated size of handling and obtaining selects to distinguish into magnetic metal and nonmagnetic metal; Extract the 1st extraction element of the cobalt that contains in the anodal substandard products; Extract free or the extraction residue of precipitation and the 2nd extraction element of the cobalt in the above-mentioned magnetic metal in the acid flux material that is contained in above-mentioned the 1st extraction element simultaneously.When extracting cobalt with high-recovery from discarded lithium ion battery, substandard products battery and anodal substandard products, the fail safe in the time of can also improving operation, and reduce operating cost.
And, about the cobalt recovery circuit in the lithium ion battery of the present invention, comprise: separate out contain extract the 1st cobalt extract of the cobalt that separates by above-mentioned the 1st extraction element and contain extract the metal impurities that dissolve in the 2nd cobalt extract of the cobalt that separates by above-mentioned the 2nd extraction element after, be separated into the clean liquid device of the clean liquid residue of the cobalt cleaning fluid that contains above-mentioned cobalt and the formation of above-mentioned metal impurities; Above-mentioned clean liquid residue is separated into the pulp residue and the cleaning device of pulp again of pulp filtrate more again.The above-mentioned filtrate of pulp again is mixed at the 1st acid flux material of above-mentioned the 1st extraction element or at the 2nd acid flux material of above-mentioned the 2nd extraction element.
According to the present invention, cobalt recovery circuit comprises: when the metal impurities that will be dissolved in above-mentioned the 1st cobalt extract and above-mentioned the 2nd cobalt extract separate as clean liquid residue, reclaim the clean liquid device of cobalt cleaning fluid; And, clean after this clean liquid residue, be separated into again on the one hand pulp residue and pulp filtrate again, on the other hand with this again pulp filtrate be mixed into the cleaning device of pulp again of the 2nd acid flux material of the 1st acid flux material of above-mentioned the 1st extraction element or above-mentioned the 2nd extraction element.Can reclaim the cobalt cleaning fluid that contains the cobalt that is concentrated efficiently, can reclaim again attached to the cobalt in this clean liquid residue simultaneously.
And the cobalt recovery circuit about in the lithium ion battery of the present invention comprises: to above-mentioned cobalt cleaning fluid mixed-alkali reagent, separate out cobalt hydroxide after, carry out processed and generate the caked cobalt hydroxide of cobalt hydroxide forming the piece generating apparatus; Above-mentioned cobalt hydroxide is formed cobalt liquor that piece is dissolved in the 3rd acid flux material as electrolyte, handle the electrowinning device that reclaims metallic cobalt from this electrolyte according to electrowinning; Be separated into free or the electrolysis residue of precipitation and the equipment for separating liquid from solid of processing back electrolyte in the electrolyte after above-mentioned electrowinning is handled.Above-mentioned electrolysis residue is mixed into above-mentioned the 2nd acid flux material at the 2nd extraction element.
According to the present invention, cobalt recovery circuit comprises: add alkaline reagent to the cobalt cleaning fluid that concentrates the cobalt that extracts from discarded lithium ion battery, battery substandard products and anodal substandard products, after separating out cobalt hydroxide, generate the caked cobalt hydroxide of cobalt hydroxide through dehydration and form the piece generating apparatus; And, for this cobalt hydroxide being formed piece, carry out electrowinning and handle as the cobalt electrolyte that electrolyte uses, reclaim the electrowinning device of the metallic cobalt of separating out; And, with the electrolysis residue of free in this electrolyte or precipitation by Separation of Solid and Liquid handle reclaim after, be mixed into the equipment for separating liquid from solid of the acid flux material of above-mentioned the 2nd extraction element.When the cobalt that contains in the cobalt cleaning fluid can be formed the piece recovery with cobalt hydroxide, can also reclaim metallic cobalt efficiently as dielectric electrolyte from this cobalt hydroxide is formed piece, and can reclaim the cobalt that contains in this electrolysis residue again.
And, in the cobalt recovery circuit in the lithium ion battery of the present invention, it is characterized in that, electrolyte after the processing that separates from above-mentioned electrolysis residue according to above-mentioned equipment for separating liquid from solid, form piece with the cobalt hydroxide of forming the generation of piece generating apparatus according to above-mentioned cobalt hydroxide and mix, generate the molten slurry of cobalt hydroxide; The molten slurry of this cobalt hydroxide is mixed into the dilute electrolyte at above-mentioned electrowinning device.
According to cobalt recovery circuit of the present invention, remove after the processing of electrolysis residue electrolyte according to above-mentioned equipment for separating liquid from solid and form piece with above-mentioned cobalt hydroxide and mix, generate the molten slurry of cobalt hydroxide after, be mixed into the dilute electrolyte of above-mentioned electrowinning device; When suppressing the reduction of electrolyte pH of above-mentioned electrowinning device, replenish cobalt (Co to this electrolyte
2+); And suppress the reduction of the current efficiency that above-mentioned electrowinning handles.
Description of drawings
Fig. 1 is the flow chart of the processing procedure of the cobalt recovery method in the lithium ion battery in the expression embodiment of the invention;
Fig. 2 is for representing the flow chart of the processing procedure that the cobalt extraction according to the sulfuric acid solvent in the cobalt recovery method in the lithium ion battery is handled in the embodiment of the invention;
Fig. 3 is the flow chart of the processing procedure of the clean of the cobalt extract in the cobalt recovery method in the lithium ion battery in the expression embodiment of the invention;
Fig. 4 is the flow chart of the processing procedure of the caked generation processing of the cobalt hydroxide in the cobalt recovery method in the lithium ion battery in the expression embodiment of the invention;
Fig. 5 is the flow chart of the processing procedure of the electrowinning processing of the metallic cobalt in the cobalt recovery method in the lithium ion battery in the expression embodiment of the invention;
Fig. 6 is the block diagram of the summary formation of the cobalt recovery circuit in the lithium ion battery in the expression embodiment of the invention.
Embodiment
Below, with reference to the accompanying drawings the cobalt recovery method in the lithium ion battery that the present invention relates to and the embodiment of cobalt recovery circuit are elaborated.And, can not limit the present invention with present embodiment.
At first, to being elaborated about the cobalt recovery method in the lithium ion battery in the embodiments of the invention.
Fig. 1 reclaims the flow chart of the processing procedure of metallic cobalt for representing according to about the cobalt recovery method in the lithium ion battery of the embodiment of the invention from recycle objects such as discarded lithium ion battery and anodal substandard products.And in Fig. 1, thick-line arrow is that expression is handled after cobalt recycle object proposition separation of cobalt according to each, reclaims the processing procedure of metallic cobalt; To be expression extract the processing procedure of cobalt from the residue of each processing etc. to thin-line arrow again.
In Fig. 1, after discarded lithium ion battery, substandard products battery and anodal substandard products reclaimed as cobalt recycle object obsolete material, these positive pole substandard products were handled with the solvent extraction that the sulfuric acid solvent carries out cobalt, obtained the 1st cobalt extract and the 1st and extracted residue.Then, the 1st extraction residue and the Powdered magnetic metal that obtains from discarded lithium ion battery and substandard products battery are handled with the solvent extraction that same sulfuric acid solvent carries out cobalt again, obtain the 2nd cobalt extract (stage S100).
Secondly, after separating out or precipitating and remove the metal impurities that contain in the 1st cobalt extract and the 2nd cobalt extract, obtain cobalt cleaning fluid that the cobalt composition has been concentrated and the clean liquid residue that forms by metal impurities.And, wash this cobalt by pulp clean again attached to clean liquid residue surface after, obtain containing the filtrate of this cobalt.Handle again according to solvent extraction processing or solvent extraction among the stage S100, extract the cobalt (stage S200) that contains in this filtrate again.
In addition, the cobalt cleaning fluid according to stage S200 obtains after separating out cobalt hydroxide with mixing of cobalt hydroxide solution, carries out the dehydrate that processed obtains cobalt hydroxide.And, wash the impurity of above-mentioned dehydrate surface attachment with pulp clean again, form piece (stage S300) thereby generate cobalt hydroxide.
Above-mentioned cobalt hydroxide is formed piece and is dissolved into the sulfuric acid solvent, become the electrolyte (below, note do cobalt electrolyte) of cobalt after, carry out electrowinning and handle, separate out cobalt on negative electrode one lateral electrode surface.To reclaim as metallic cobalt at the cobalt that above-mentioned negative electrode one lateral electrode is separated out.And, propose to handle electrolyte after the processing of fully separating out behind the cobalt (below, note is done the electrolysis tail washings) according to electrolysis, mix suitable coagulating agent after, handle by carrying out Separation of Solid and Liquid, be separated into the electrolysis tail washings and the hydrogen oxide cobalt oxide electrolysis residues such as (ォ キ シ water acidifying コ バ Le ト) of cleaning.The electrolysis tail washings of this cleaning mixes above-mentioned cobalt hydroxide and forms piece, obtain the molten slurry of cobalt hydroxide after, the pH that handles as this electrowinning adjusts agent, or uses as the cobalt replenishers.In addition, the molten slurry of this electrolysis is handled according to the solvent extraction among the stage S100 again, extracts its cobalt that contains (stage S400) once more.
More than, according to the cobalt recovery method in the lithium ion battery of the embodiment of the invention, the processing procedure that reclaims metallic cobalt from cobalt recycle object obsolete material has been carried out general description, below the variety of processes of above-mentioned stage S100～S400 is described in detail.
Fig. 2 is illustrated in the cobalt recovery method in the lithium ion battery of the embodiment of the invention, from corresponding variety of processes classification cobalt recycle object obsolete material, from discarded lithium ion battery and substandard products battery, select the pulverous magnetic metal of difference on the one hand, from anodal substandard products, carry out the solvent extraction cobalt on the other hand, after obtaining the 1st cobalt extract and the 1st extraction residue, this magnetic metal and the 1st extraction residue one are reinstated same sulfuric acid solvent and are carried out solvent extraction once more, the processing procedure till obtaining the 2nd cobalt extract; And at length represented the processing procedure of above-mentioned stage S100.
In Fig. 2, discarded lithium ion electric field and anodal substandard products as the recovery of cobalt recycle object obsolete material, at first, be categorized into the anodal substandard products (stage S101) of discarded lithium ion battery, substandard products battery and positive plate monomer with formation that its positive/negative plate is configured to insert external packing shell inside.
(stage S102 not), after the processing of inside battery high-pressure trend, calcines under the calcining heat of 500～1000 ℃ of scopes when its external packing shell prevents to calcine, and obtains burned material (stage S103) for discarded lithium ion battery that is classified and substandard products battery.Constitute porous matter polypropylene that is used to spacer of each waste battery etc., as 6 fluorinated phosphate lithiums of bath composition etc., as the poly-organic materials such as inferior ethene of fluoridizing of electrode active material bond, be decomposed, burn or volatilize and remove by this calcination processing.
And, as the external packing shell of discarded lithium ion battery or substandard products battery, perhaps on its part, if what use is plastics, as preferably crush its parts of plastics and peeling off of the pre-treatment of above-mentioned calcination processing.
Secondly, this comburant of crushing powder (stage S104) that obtains crushing.In this case, the granularity that is crushed to the cobalt that contains in the comburant is for smaller or equal to 2000 μ m.And, in this crushing is handled, can be fit to use the known crushing machine that utilizes impact, friction, shearing, compression alone or in combination.
And this crushing powder uses the standard screen of screen size 2000 μ m among the JIS Z8801 to sieve (stage S105), and available sieve back powder is the crushing powder of the granularity of the cobalt that contains smaller or equal to 2000 μ m.In this case, the crushing powder that just is removed of the residue on the sieve is the aluminium foil that constitutes positive plate, copper mesh, Copper Foil or the external packing shell etc. that constitute negative plate.And the screen size of this standard screen is preferably smaller or equal to 2000 μ m's.When being set at tiny screen size, the cobalt rate of recovery of sieve back powder may reduce.Therefore, the lower limit of screen size is preferably set to about 400 μ m.
Then, granularity is selected difference (stage S107) smaller or equal to the crushing powder (stage S106 is) of 2000 μ m by magnetic, is separated into magnetic metal and nonmagnetic metal such as carbon, copper or aluminium such as cobalt, iron.But, select difference according to this magnetic, it is very difficult to be separated into magnetic metal and nonmagnetic metal fully, and the magnetic metal that is recovered contains the copper and the aluminium of trace.
In addition, to anodal substandard products (the stage S102 that is classified from cobalt recycle object obsolete material, be), each that do not implement in the above-mentioned stage 103～107 handled, and by being immersed in the sulfuric acid solvent, solvent extraction constitutes the cobalt as the cobalt acid lithium of positive active material, and, by filtering this solvent extraction treatment fluid, be separated into the 1st cobalt extract and the 1st and extract residue (stage S109).In this case, being used in the sulfuric acid solvent that this solvent extraction handles is that sulfuric acid concentration is the aqueous sulfuric acid of 100～250g/l.And, for improving the efficient that this solvent extraction is handled, preferably solvent temperature is set at about 40～70 ℃.
Here, the cobalt that constitutes cobalt acid lithium is 3 valencys, is insoluble to acid flux material.Therefore, extract processing, need the cobalt of this 3 valency is reduced into the reducing agent of divalent for promoting the cobalt in the above-mentioned sulfuric acid solution.Here, in stage S109, by anodal substandard products are immersed the sulfuric acid solvent under untreated state, the aluminium that constitutes positive plate uses as the reducing agent that the cobalt with 3 valencys is reduced into divalent, to reach the solvent extraction of cobalt.
But, in the solvent extraction of above-mentioned cobalt is handled, can extract 80% of the cobalt that contains in the anodal substandard products, promptly the 1st cobalt extract contains the cobalt of the rate of recovery 80%, and the 1st extracts residue contains 20% cobalt.
Then, the 1st extract residue (stage S110 is) and magnetic metal (stage S108 is) immerses in the same sulfuric acid solvent by what will obtain, obtain can solvent extraction the 1st extraction residue and magnetic metal in the solvent extraction treatment fluid again of the cobalt that contains.And, by filtering this solvent extraction treatment fluid again, isolate the 2nd cobalt extract and the 2nd and extract residue (stage S111).In this case, the sulfuric acid solvent that is used in the solvent extraction of cobalt is that sulfuric acid concentration is the aqueous sulfuric acid of 100～250g/l, and the 1st extraction residue that is immersed is that solute concentration is the molten slurry of 50～150g/l.And for improving the efficient that above-mentioned solvent extraction is handled again, preferably the temperature with the sulfuric acid solvent is set at about 40～70 ℃.
And, to handle again in (stage S111) in this solvent extraction, trace iron that contains in the magnetic metal (stage S108 is) and aluminium use as the reducing agent that 3 valency cobalts is reduced into the divalent cobalt.
But, handle (stage S111) again according to this solvent extraction, when from discarded lithium ion battery and substandard products battery, extracting cobalt with 90% the rate of recovery, remain in the 1st and extract residue (stage S110, be) in 20% the cobalt, can in the 2nd cobalt extract, (stage S112 denys) extract 19% cobalt.Promptly, consideration is 80% o'clock according to stage S109 from the processing rate of recovery that anodal substandard products extract cobalt, handling (stage S109～S111) by carrying out solvent extraction processing and solvent extraction continuously, can from reclaiming cobalt extract with the rate of recovery 90% when, discarded lithium ion battery and substandard products battery can also extract, reclaim cobalt with the rate of recovery 99% from anodal substandard products.
And (stage S106) is not recovered as resource to handle the crushing powder that remains on the sieve according to above-mentioned screening; In addition, select nonmagnetic metal (the stage S108 of differentiated treatment separation according to above-mentioned magnetic, not), handle the 2nd of separation again according to above-mentioned solvent extraction and extract residue (stage S112 is) and make its slagization with the stove fusion of molten ore deposit, thereby environmental sound (stage S113).
Then, in the cobalt recovery method in the lithium ion battery of embodiments of the invention, the processing sequence of the clean (stage S200) of above-mentioned cobalt extract is elaborated.To be expression remove beginning from the metal impurities that will contain to Fig. 3 in the cobalt that utilizes the sulfuric acid solvent extract to be handled the 1st and the 2nd cobalt extract (stage S100), the flow chart of the processing procedure till obtaining the cobalt cleaning fluid that the cobalt composition has been concentrated; And at length represented the processing procedure in above-mentioned stage 200.
In Fig. 3, to the 1st and the 2nd cobalt extract of handling recovery according to above-mentioned solvent extraction processing and solvent extraction again (stage S110, not; Stage S112) does not immerse Powdered or tabular metallic cobalt, thus precipitating metal impurity copper (stage S201).In this case, metallic cobalt is the metal higher than the ionization tendency of copper, uses as the reducing agent of going back native copper.Therefore, the copper (Cu that contains in the 1st and the 2nd cobalt extract
2+) replaced precipitating metal copper by metallic cobalt according to redox reaction.This redox reaction is represented with chemical formula (1).
Cu
2++Co→Co
2++Cu?↓ …(1)
And, at the addition of removing in the processing (stage S201) metallic cobalt that uses of above-mentioned copper, for this copper (Cu
2+) fully separate out with metallic copper, being necessary to set is the amount suitable with copper at least, preferably sets 2～3 times amount.And, because metallic cobalt is replaced as the cobalt (Co of divalent by the redox reaction with copper
2+), be dissolved in acid flux material easily, can handle according to following electrowinning and reclaim again as metallic cobalt.
Then,, mix the molten slurry of calcium hydroxide of 200～300g/l, behind the sulfate precipitate calcium (stage S202), mix sodium hydroxide solution precipitation iron hydroxide and aluminium hydroxide (stage S203) again for the 1st and the 2nd cobalt extract that is removed copper.
In this case, the molten slurry of calcium hydroxide by with the 1st and the 2nd cobalt extract in the sulfuric acid reaction that contains generate calcium sulfate, suppress separating out of sulfate crystal (saltcake) that the NaOH that adds among the stage S203 in stage afterwards and sulfuric acid reaction generate.Because sodium sulphate makes in the cobalt extract and separates out saltcake, and filtration treatment thereafter needs the plenty of time, cause the reduction of cobalt recycling efficient under hypersaturated state.And the addition of the molten slurry of calcium hydroxide is for adjusting to 2～3 degree with the pH value of the 1st and the 2nd cobalt extract.
And the addition of the NaOH in the stage 203 is for can adjust to the pH value of the 1st and the 2nd cobalt extract 4～5.5, preferred 4～4.5 degree.This be because, metal impurities-iron that contains in the 1st and the 2nd cobalt extract and aluminium are 4～4.5 the easy coprecipitated hydroxide of scope in the pH value, but the pH value is greater than 5.5 o'clock, cobalt forms hydroxide easily and precipitates.And chemical formula (2), (3) expression are used in the precipitation reaction of this iron hydroxide and aluminium hydroxide respectively.
Fe
3++3NaOH→3Na
2++Fe(OH)
3↓ …(2)
Al
3++3NaOH→3Na
2++Al(OH)
3↓ …(3)
But, iron in acid flux material with divalent iron (Fe
2+) and 3 valency iron (Fe
3+) coexistence, generate the Fe (OH) shown in the chemical formula (2) by adding NaOH
3Here, because Fe (OH)
2Be dissolved in acid flux material easily and do not precipitate, be difficult to make divalent iron precipitation and remove by above-mentioned stage S203.Therefore, when making divalent iron be oxidized to 3 valencys, make ferric hydroxide precipitate (stage S204) by adding hydrogen peroxide.And, the addition of this hydrogen peroxide be set at least with the 1st and the 2nd cobalt extract in the amount worked as of the divalent iron phase that contains for well.And behind the above-mentioned divalent iron of oxidation, the reaction of precipitation iron hydroxide is represented with chemical formula (4).
2Fe
2++H
2O
2+2H
++6NaOH
→6N
a++2H
2O+2Fe(OH)
3↓ …(4)
Each the 1st and the 2nd cobalt extract of handling of implementing above-mentioned stage S201～S204 becomes each sediment of metallic copper, iron hydroxide, aluminium hydroxide and calcium sulfate and has been concentrated the mixed solution of the cobalt cleaning fluid of cobalt composition, by filtering, be separated into above-mentioned sediment and cobalt cleaning fluid (stage S205).In this case, when can obtain the cobalt cleaning fluid as filtrate, separate above-mentioned sediment as clean liquid residue.
Here, the cobalt cleaning fluid that obtains contains the cobalt in 80% the 1st and the 2nd cobalt extract, and separated clean liquid residue contains as the cobalt in 10% the 1st and the 2nd cobalt extract of solid.And, on the surface of this clean liquid residue, adhere to the cobalt in 10% the 1st and the 2nd cobalt extract.That is,, when reclaiming cobalt with the rate of recovery 72%, reclaim cobalt with the rate of recovery 79.2% from anodal substandard products from discarding lithium ion battery and substandard products battery according to this cobalt cleaning fluid.
And above-mentioned clean liquid residue (stage S206 is) is made the mixed aqueous solution of clean liquid residue, after carrying out pulp again and cleaning, by filtering, the cobalt attached to above-mentioned clean liquid residue surface is recovered in (stage S207) in the filtrate.This filtrate (stage S208,) do not handle (stage S111) again by solvent extraction processing (stage S109) or the solvent extraction carried out among the above-mentioned stage S100, can reclaim the cobalt in 10% the 1st and the 2nd cobalt extract, promptly reclaim 9% of the cobalt that contains in discarded lithium ion battery and the substandard products battery, reclaim 9.9% of the cobalt that contains in the anodal substandard products simultaneously.
Therefore, above-mentioned cobalt cleaning fluid (stage S206 denys) and the wash filtrate (stage S208 denys) that obtains according to pulp clean again, reclaim 81% of the cobalt that contains in discarded lithium ion battery and the substandard products battery, reclaim 89.1% of the cobalt that contains in the anodal substandard products simultaneously.
In addition, the cleaning residue (stage S208 is) that separates according to pulp clean again contains each sediment of metallic copper, iron hydroxide, aluminium hydroxide and calcium sulfate, contains simultaneously as the cobalt in 10% 1st and the 2nd cobalt extract of solid.But, because this cobalt solid constituent reclaims relatively difficulty with above-mentioned processing, thus with its with above-mentioned sediment in the stove of molten ore deposit fusion by slagization, thereby environmental sound (stage S209).
Then, in the cobalt recovery method in the lithium ion battery of embodiments of the invention, the processing procedure that (stage S300) handled in the caked generation of above-mentioned cobalt hydroxide is elaborated.Fig. 4 is that expression begins from separating out cobalt hydroxide by the clean liquid processing (stage S200) of the 1st and the 2nd cobalt extract the cobalt cleaning fluid, the flow chart of the processing procedure till obtaining cobalt hydroxide to form piece, and at length represented the processing procedure of above-mentioned stage S300.
In Fig. 4, handle the cobalt cleaning fluid (stage S206 denys) that (stage S200) obtains by the clean liquid of the 1st and the 2nd cobalt extract, its pH value is adjusted to 4～4.5, by adding the NaOH neutralization, separates out cobalt hydroxide (stage S301) simultaneously.In this case, represent with chemical formula (5) by the neutralization reaction at the cobalt cleaning fluid of adding NaOH.
Co
2++2H
++2SO
4 2-+4NaOH
→2Na
2SO
4+Co(OH)
2↓+2H
2O …(5)
And the addition of NaOH is set to 8～9 degree set by the pH value adjustment with above-mentioned cobalt cleaning fluid.In this case, because the sodium sulphate that generates in the represented neutralization reaction of chemical formula (5) does not reach hypersaturated state, so do not separate out saltcake.
Then, make the cobalt hydroxide sediment that obtains, obtain cobalt hydroxide dehydrate and dehydration waste liquid by solid-liquid separating methods such as known pressurization separation, vacuum suction or centrifugation dehydration (stage S302).But the surface attachment of this cobalt hydroxide dehydrate has impurity.
And, make the cobalt hydroxide dehydrate (stage S303 is) that obtains be dissolved in water, obtain the mixed aqueous solution of cobalt hydroxide dehydrate after, pulp is cleaned again.Then, this mixed aqueous solution obtains cobalt hydroxide and forms piece and clean waste liquid (stage S304) by the dehydration of solid-liquid separating methods such as known pressurization separation, vacuum suction or centrifugation.In this case, remove as cleaning waste liquid, form piece and generate cobalt hydroxide attached to the lip-deep impurity of above-mentioned cobalt hydroxide dehydrate.
In addition, and above-mentioned dehydration waste liquid (stage S303 denys) and cleaning waste liquid (stage S305, not) by after the processing of known drainage processing method environmental sound, draining (stage S306).
Then, in the cobalt recovery method in the lithium ion battery of embodiments of the invention, the handling procedure that the electrowinning of above-mentioned metallic cobalt is handled (stage S400) is elaborated.Fig. 5 is that expression is formed the flow chart that reclaims the processing sequence of metallic cobalt the piece from the cobalt hydroxide that obtains by the caked generation processing of cobalt hydroxide (stage S300), and has represented the processing procedure of above-mentioned stage S400 in detail.
In Fig. 5, the cobalt hydroxide that obtains is formed piece (stage S305 is) and is dissolved in aqueous sulfuric acid, obtains cobalt electrolyte (stage S401).In this case, for the pH value that makes cobalt electrolyte is 2～3, and the concentration that contains cobalt is about 50～100g/l, forms the amount of piece, sulfuric acid and water and adjust cobalt hydroxide, and mixes.And the temperature of this cobalt electrolyte is preferably adjusted to 40～60 ℃.
Then, the cobalt electrolyte supply that obtains arrives the insoluble electrodes such as titanium (DSE) of usefulness platinum coating as anode, with after the known electrowinning device of metals such as aluminium as negative electrode, at 200～400A/m
2Current density under by electrolysis.By this electrolysis, after cathode surface precipitating metal cobalt, metallic cobalt is reclaimed (stage S402) by physical method such as peeling off.In this case, use the redox reaction shown in chemical formula (6), (7) on above-mentioned anode and the negative electrode respectively, the precipitating metal cobalt.
2H
2O→4H
++4e
-+O
2↑ …(6)
2Co
2++ 4e
-→ 2Co (separating out) at negative electrode ... (7)
And, when continuing the above-mentioned cobalt electrolyte of electrolysis, in this cobalt electrolyte, hydrogen ion (H
+) concentration increase, the pH value is reduced to less than 2 the time, the cobalt (Co after the ionization
2+) concentration reduce, the electrowinning efficient (current efficiency) of metallic cobalt reduces.Usually, the current efficiency of metallic cobalt is the theory amount of separating out of 1.099g for the metallic cobalt of being separated out with respect to the 1A electric current, for the ratio of the inhibition metallic cobalt amount of separating out with this theory amount of separating out significantly reduces, promptly suppress the reduction of current efficiency, be necessary to replenish hydroxide ion (OH to cobalt electrolyte
-) and cobalt (Co
2+), then supply with the molten slurry of following cobalt hydroxide.
And, above-mentioned electrowinning is handled the electrolysis tail washings after (stage S402), owing to contain insoluble electrolysis residue in sulfuric acid solvents such as hydrogen oxide cobalt oxide, reclaim this electrolysis tail washings (stage S403, and be separated into the electrolysis tail washings (stage S404) of electrolysis residue and cleaning by solid-liquid separating methods such as known pressurization separation, vacuum suction or centrifugations the electrolysis tail washings).Then, this electrolysis residue (stage S405 is) extracts the cobalt that processing (stage S111) solvent extraction contains again by the solvent in above-mentioned stage S100.
In addition, (stage S405) does not mix by forming piece with the cobalt hydroxide that is generated by stage S300 the electrolysis tail washings of this cleaning, becomes the molten slurry of cobalt hydroxide (stage S406) of 100～150g/l.Here the molten slurry of the cobalt hydroxide that obtains is as replenishing hydroxide ion and cobalt (Co to above-mentioned cobalt electrolyte
2+) replenishers use.
Here, the electrolysis residue of Separation of Solid and Liquid processing (stage S404) is handled (stage S111) again by solvent extraction after, when its cobalt that contains was reclaimed once again, the rate of recovery of handling the metallic cobalt (stage S403, metallic cobalt) that (stage S402) be recovered by electrowinning further improved.
By above-mentioned explanation, the cobalt recovery method in the lithium ion battery can reclaim the cobalt that contains in the cobalt recycle object obsolete material effectively, and can reclaim with high-recovery with the metallic cobalt form according to an embodiment of the invention.Particularly, when reclaiming, can also reclaim metallic cobalt with 80% the rate of recovery from discarded lithium ion battery and substandard products battery from anodal substandard products more than or equal to 70% the rate of recovery.
And, handle again in (stage S111) in solvent extraction processing (stage S109) and solvent extraction, because as the reducing agent that 3 valency cobalts is reduced into divalent, tabular aluminium or the iron of waiting that contains in the cobalt recycle object obsolete material is used, the time do not have dangerous reagent such as hydrogen peroxide so do not reuse operation, can be safely and implement metallic cobalt at low cost and reclaim operation.
Below, the cobalt recovery circuit in the lithium ion battery of embodiments of the invention is elaborated.Fig. 6 is that the summary of the cobalt recovery circuit in the lithium ion battery in the embodiment of the invention constitutes block diagram.But the solid arrow among Fig. 6 represents by the flowing of the material of belt conveyor etc., and dotted arrow is represented flowing by the material of pipeline etc.
In Fig. 6, cobalt recovery circuit in the lithium ion battery, comprise: the cobalt that is contained in the cobalt recycle object obsolete material that solvent extraction is made of discarded lithium ion battery, substandard products battery and anodal substandard products obtains the solvent extraction device 100 of the 1st and the 2nd cobalt extract; Clean liquid handles the 1st and the 2nd cobalt extract, when removing its metal impurities, obtains the clean liquid device 200 of the cobalt cleaning fluid that the cobalt composition has been concentrated; Reclaim the caked cobalt hydroxide of cobalt hydroxide from this cobalt cleaning fluid and form piece generating apparatus 300; From form the cobalt electrolyte that piece forms by this cobalt hydroxide, reclaim the metallic cobalt electrowinning device 400 of metallic cobalt.This metallic cobalt recovery system has the structure that can reclaim metallic cobalt individually from cobalt recycle object obsolete material.
Then, the structure about this solvent extraction device 100 is elaborated with reference to Fig. 6.In Fig. 6, solvent extraction device 100, comprise: after will discarding lithium ion battery and substandard products battery and in calciner 101, calcining, with crushing machine 102 crushing, with screening machine 103 by sieve smaller or equal to designated size its crushing powder after, by magnetic separator 104, its sieve back powder is selected to be separated into magnetic metal and nonmagnetic metal; In addition, behind the cobalt that contains in the anodal substandard products of solvent extraction machine 105 solvent extractions, filter the solvent extraction treatment fluid that obtains, be separated into the 1st cobalt extract and the 1st and extract residue with filter 107; Then, handle again through the magnetic metal of magnetic separator 104 selection differences and the 1st extraction residue that obtains by filter 107 with 106 solvent extractions of solvent extraction machine, filter the solvent extraction that obtains treatment fluid again with filter 108, be separated into the 2nd cobalt extract and the 2nd and extract residue.And, this solvent extraction device 100 will reclaim as resource by the residue of screening machine 103 screenings, in addition, to select the nonmagnetic metal of difference and extract residue by slagizations such as molten ore deposit stoves through magnetic separator 104, and make it innoxious with the 2nd of filter 108 separation.
Crushing machine 102 has following function: for the calcined material that obtains in calciner 101, the cobalt crushing that contains in this calcined material is processed into smaller or equal to designated size (for example, 2000 μ m), and sends its crushing powder.And,, can use the crushing machine that utilizes known impact, friction, shearing, compression alone or in combination as this crushing machine 102.
In addition, solvent extraction machine 105 has following function: mix sulfuric acid and water, (for example be modulated into normal concentration, behind 100～250g/l) the aqueous sulfuric acid, by anodal substandard products are immersed this aqueous sulfuric acid, the solvent extraction that contains cobalt is handled, and sends by the 1st cobalt extract and the 1st and extract the solvent extraction treatment fluid that residue forms.Here, the 1st cobalt extract is to extract the cobalt-carrying solution that separates from anodal substandard products, and the 1st extract residue and be, free or be deposited in the solvent extraction that this solvent extraction forms as cobalt composition in the above-mentioned aqueous sulfuric acid of sulfuric acid solvent and resinous principle etc. in handling and handle dregs.
And, solvent extraction machine 106 has following function: mix sulfuric acid and water, (for example be modulated into normal concentration, behind 100～250g/l) the aqueous sulfuric acid, to immerse together this aqueous sulfuric acid with the magnetic metal of selecting difference to separate by magnetic separator 104 from the 1st extraction residue that filter 107 is sent, handle again with this solvent extraction that contains cobalt, send by the 2nd cobalt extract and the 2nd and extract solvent extraction that residue forms treatment fluid again.Here, the 2nd cobalt extract is the solution that contains from the cobalt of the 1st extraction residue and magnetic metal extraction separation, and the 2nd extract residue and be, free or be deposited in this solvent extraction and handle dregs again as the solvent extraction of the formation such as resinous principle in the above-mentioned aqueous sulfuric acid of sulfuric acid solvent in handling again.
Below, be elaborated with reference to Fig. 6 about the structure of clean liquid device 200.In Fig. 6, clean liquid device 200, comprise: behind the metal impurities such as copper, iron and aluminium that precipitate and separate contains, send the clean liquid machine 201 of the clean liquid treatment fluid that contains cobalt cleaning fluid that the cobalt composition has been concentrated and these metal impurities from the 1st and the 2nd cobalt extract that solvent extraction device 100 is sent; By filtering this clean liquid treatment fluid, be separated into the filter 203 of cobalt cleaning fluid and clean liquid residue; The cobalt that adheres on this clean liquid residue surface of pulp clean again, the cleaning machine of pulp again 202 of this cobalt of recovery in its clean liquid; The cobalt that contains in the clean liquid that will obtain according to this pulp clean again reclaims as wash filtrate, discharges the filter 204 that cleans residue simultaneously; And the calcium hydroxide that the molten slurry of the calcium hydroxide of adjusting to normal concentration is supplied to clean liquid machine 201 is supplied with machine 205.Above-mentioned clean liquid device 200, on the one hand reclaim the cobalt cleaning fluid that the cobalt composition has been concentrated from the 1st and the 2nd cobalt extract, in wash filtrate, reclaim cobalt on the other hand, pass out to solvent extraction machine 105 or 106 then, reclaim the cobalt that contains once more attached to this clean liquid residue.
Clean liquid machine 201 has following function: send the Powdered or tabular cobalt that the 2nd cobalt extract immerses ormal weight to the 1st cobalt extract of sending from filter 107 and from filter 108, after separating out the metal impurities copper in the 1st and the 2nd cobalt extract, supply is supplied with the molten slurry of calcium hydroxide that machine 205 is sent from calcium hydroxide, then by adding the NaOH of ormal weight, add the hydrogen peroxide of ormal weight again, thereby precipitate after the additional metals impurity iron and aluminium in the 1st and the 2nd cobalt extract, send the clean liquid treatment fluid that contains cobalt cleaning fluid and above-mentioned metal impurities etc.Here, the cobalt cleaning fluid is by from the 1st and the 2nd cobalt extract separating metal impurity, to have concentrated the solution of cobalt composition in the solution.
Calcium hydroxide is supplied with machine 205 and is had following function: calcium hydroxide is adjusted to normal concentration (for example, behind the molten slurry of 200～300g/l) calcium hydroxide, the molten slurry of this calcium hydroxide is supplied to clean liquid machine 201.And the supply of the molten slurry of this calcium hydroxide is implemented control before handling in clean liquid machine 201 NaOH being added into the 1st and the 2nd cobalt extract.
Below, the structure of cobalt hydroxide being formed piece generating apparatus 300 with reference to Fig. 6 is elaborated.In Fig. 6, cobalt hydroxide is formed piece generating apparatus 300, comprising: the cobalt hydroxide that makes the cobalt cleaning fluid of sending from clean liquid device 200 separate out, precipitate cobalt hydroxide is separated out machine 301; Contain the sedimentary treatment fluid of separating out of this cobalt hydroxide by processed, reclaim the filter 303 of cobalt hydroxide dehydrate; Clean the cleaning machine of pulp again 302 of the impurity that adheres on the surface of this cobalt hydroxide dehydrate; The cobalt hydroxide of removing impurity by this pulp clean is again carried out processed, and reclaim the caked filter 304 of cobalt hydroxide.Above-mentioned cobalt hydroxide is formed piece generating apparatus 300, reclaims after the cobalt hydroxide of cobalt cleaning fluid generation is formed piece, passes out to metallic cobalt electrorefining device 400.
Cobalt hydroxide is separated out machine 301 and is had following function: by add the NaOH of ormal weight to the cobalt cleaning fluid sent from filter 203, separate out cobalt hydroxide after, send and contain the sedimentary Treatment Solution of separating out of this cobalt hydroxide to filter 303.
Below, with reference to Fig. 6, the structure of metallic cobalt electrowinning device 400 is elaborated.In Fig. 6, metallic cobalt electrowinning device 400, comprise: will form cobalt hydroxide that piece generating apparatus 300 sends from cobalt hydroxide and form piece and be dissolved in the sulfuric acid solvent that cobalt electrolyte generates normal concentration the machine 401, and generation cobalt electrolyte, this cobalt electrolyte of electrolytic treatments in electrolysis machine 402, and precipitating metal cobalt; And Separation of Solid and Liquid is handled the electrolysis tail washings of sending from this electrolysis machine 402 in solid-liquid separating machine 403, and after being separated into the electrolysis tail washings of electrolysis residue and cleaning, sends this electrolysis residue to solvent extraction machine 106, reclaims the cobalt that contains in this electrolysis residue once more; In addition, supply with the electrolysis tail washings that mixes the cleaning of sending from solid-liquid separating machine 403 in the machine 404 and form the cobalt hydroxide that piece generating apparatus 300 sends from cobalt hydroxide and form piece at the molten slurry of cobalt hydroxide, and after generating the molten slurry of cobalt hydroxide, supply to electrolysis machine 402.And, generate machine 401 or the molten slurry of cobalt hydroxide to cobalt electrolyte and supply with the above-mentioned cobalt hydroxide that machine 404 supplies with and form piece, be the needs corresponding to separately, in dispenser 405, distribute the cobalt hydroxide of sending from the molten slurry generating apparatus 300 of cobalt hydroxide to form piece.
Cobalt electrolyte generates machine 401 and has following function: will form the aqueous sulfuric acid that piece is dissolved in normal concentration from filter 304 cobalt hydroxides that send, that be assigned with machine 405 distribution, and behind the generation cobalt electrolyte, send cobalt electrolyte to electrolysis machine 402.And control is used to concentration and the addition that this cobalt electrolyte generates the aqueous sulfuric acid of handling, and making the cobalt electrolyte ph after the generation is in 2～3 scopes.
Solid-liquid separating machine 403 has following function: handle being recovered in after the electrode residue that precipitates from the electrolysis tail washings that electrolysis machine 402 is sent by Separation of Solid and Liquid, send this electrolysis residue on the one hand to solvent extraction machine 106, the electrolysis tail washings that the electrolysis residue is removed passes out to the molten slurry of cobalt hydroxide as peace and quiet electrolysis tail washings and supplies with machine 404 on the other hand.But, carry out this Separation of Solid and Liquid when handling, promote the precipitation of the electrolysis residue in the electrolysis tail washings by the coagulating agent that adds necessary amount to the electrolysis tail washings, can easily separate and reclaim this electrolysis residue.And,, can use and utilize solid-liquid separating machine alone or in combination with known pressurization separation, vacuum suction or centrifugation etc. as this solid-liquid separating machine 403.
The molten slurry of cobalt hydroxide is supplied with machine 404 and is had following function: mix the electrolysis tail washings of the cleaning of sending from solid-liquid separating machine 403 and form piece from the cobalt hydroxide that dispenser 405 is assigned with, (for example generate normal concentration, behind the molten slurry of 100～150g/l) cobalt hydroxide, the molten slurry of this cobalt hydroxide is supplied to electric seperator 402.Controlling the supply of the molten slurry of this cobalt hydroxide and handle, is in electric seperator 402, and the pH value of the cobalt electrolyte after the electrolytic treatments is supplied with the molten slurry of cobalt hydroxide of necessary amount less than under 2 the situation to electrolysis machine 402.Therefore, the current efficiency of the metallic cobalt in the electrolysis machine 402, (the 1.099g cobalt is separated out/A) is not significantly reduced with respect to its theory amount of separating out.
By above-mentioned explanation, cobalt recovery circuit in the lithium ion battery of embodiments of the invention, comprise: carry out on the one hand processing up to the magnetic metal that obtains to contain cobalt from discarded lithium ion battery and substandard products battery, cobalt by containing in the anodal substandard products of solvent extraction machine 105 solvent extractions on the other hand, the 1st cobalt extract and the 1st that has obtained extracting this cobalt extracts after the residue, the 1st extraction residue and above-mentioned magnetic metal are handled by 106 solvent extractions of solvent extraction machine together again, obtained the solvent extraction device 100 of the 2nd cobalt extract; And, remove impurity from the 1st and the 2nd cobalt extract on the one hand, and obtain the cobalt cleaning fluid, on the other hand after the cobalt that in clean liquid, adheres in this impurity surface of recovery, send this clean liquid once more to solvent extraction device 100, and carry out the clean liquid device 200 that solvent extraction is handled; And, generate the caked cobalt hydroxide of cobalt hydroxide by the cobalt cleaning fluid and form piece generating apparatus 300; And, handle by electrowinning on the one hand and form the cobalt electrolyte that piece gets by cobalt hydroxide, separate out, reclaim metallic cobalt, electrolysis tail washings after handling from this electrowinning on the other hand separate reclaim the electrolysis residue after, reclaim the metallic cobalt electrowinning device 400 of the cobalt that contains in this electrolysis residue once more at solvent extraction device 100.Therefore, can reclaim the cobalt that contains in the cobalt recycle object obsolete material with metallic state efficiently, and can reclaim with high-recovery.
And in solvent extraction device 100, in the solvent extraction processing according to solvent extraction machine 105, the tabular aluminium that contains in the anodal substandard products is used as reducing agent; And, in handling again according to the solvent extraction of solvent extraction machine 106, the aluminium or the iron of the tabular grade that contains from the magnetic metal that magnetic separator 104 is sent are used as reducing agent, therefore have dangerous reagent such as hydrogen peroxide in the time of can not reusing operation, and can be safely and implement metallic cobalt at low cost and reclaim operation, thereby can realize this cobalt recovery circuit.
And, in an embodiment of the present invention,, the situation of using sulfuric acid being described as the solvent that extracts separation of cobalt, the present invention not only is defined to this, also can use inorganic acids such as hydrochloric acid, nitric acid as solvent.
And, in an embodiment of the present invention, illustrated that the present invention not only is defined to this in order to separate out the situation that cobalt hydroxide adds NaOH, also can use alkaline reagents such as lithium hydroxide.
And, in an embodiment of the present invention, illustrated that the present invention not only is defined to this, also can use alkaline reagents such as lithium hydroxide in order to precipitate the situation that metal impurities that the 1st and the 2nd cobalt contains in extracting also add NaOH.
And, in an embodiment of the present invention, the situation of adding the molten slurry of calcium hydroxide of separating out of handling (stage S200) middle saltcake for the clean liquid that suppresses the cobalt extract has been described, the present invention not only is defined to this, also can use the solid hydrogen calcium oxide of Powdered grade, and, if the acid flux material of handling again as solvent extraction processing and solvent extraction uses the inorganic acid beyond the sulfuric acid, be not suitable for adding the molten slurry or the solid of calcium hydroxide.
And, in an embodiment of the present invention, the carrying method as material in each device has been described, use the situation of belt conveyor or pipeline, the present invention not only is defined to this, also can use carrying methods such as downpipe or injection.
The industry utilizability
As mentioned above, the cobalt recovery method in the lithium ion battery that the present invention relates to and cobalt reclaim System can be effective with high-recovery from discarded lithium ion battery, substandard products battery and anodal substandard products Rate ground reclaims cobalt, and has improved the security of cobalt recovery operation.
Claims (9)
1. the cobalt recovery method that lithium ion battery is interior is characterized in that, comprising:
Handle the discarded lithium ion battery in the middle of the cobalt recycle object obsolete material obtain in the lithium ion battery and/or the crushing powder of substandard products battery by the crushing after the calcination processing, it according to after sieving smaller or equal to the granularity of regulation, is selected this crushing powder magnetic to distinguish into the magnetic separation operation of magnetic metal and nonmagnetic metal;
The cobalt that anodal substandard products contained in the middle of the cobalt recycle object obsolete material in the above-mentioned lithium ion battery is extracted the 1st abstraction process that separates under the 1st acid flux material;
To under the 2nd acid flux material, extract the 2nd abstraction process that separates according to the above-mentioned cobalt that contains in the extraction residue of free or precipitation in the cobalt that contains in the selected magnetic metal of distinguishing out of magnetic operation and above-mentioned the 1st acid flux material that selects.
2. the cobalt recovery method in the lithium ion battery as claimed in claim 1 is characterized in that, comprising:
Separate out contain extract the 1st cobalt extract of the cobalt that separates by above-mentioned the 1st abstraction process and contain extract the metal impurities that dissolve in the 2nd cobalt extract of the cobalt that separates by above-mentioned the 2nd abstraction process after, separation contains the clean liquid operation of the clean liquid residue of the cobalt detergent remover of above-mentioned cobalt and the formation of above-mentioned metal impurities;
Above-mentioned clean liquid residue is separated into the pulp residue and the pulp matting again of pulp filtrate more again;
The filtrate of pulp again that obtains by above-mentioned pulp matting again is mixed into above-mentioned the 1st acid flux material or above-mentioned the 2nd acid flux material.
3. the cobalt recovery method in the lithium ion battery as claimed in claim 2 is characterized in that, comprising:
To above-mentioned cobalt cleaning fluid mixed-alkali reagent and after separating out cobalt hydroxide, carry out processed and generate the caked cobalt hydroxide of cobalt hydroxide and form piece and generate operation;
Form the cobalt liquor that piece is dissolved in the 3rd acid flux material with above-mentioned cobalt hydroxide and use, handle the electrowinning operation that reclaims metallic cobalt by electrowinning from this electrolyte as electrolyte;
The solid-liquid separation process that will separate with electrolyte after the processing at the electrolysis residue of free in the electrolyte after above-mentioned electrowinning is handled or precipitation;
Above-mentioned electrolysis residue is mixed into the 2nd acid flux material.
4. the cobalt recovery method in the lithium ion battery as claimed in claim 3, it is characterized in that: electrolyte and above-mentioned cobalt hydroxide are formed piece and are mixed and generate the molten slurry of cobalt hydroxide after the above-mentioned processing, and the molten slurry of this cobalt hydroxide is mixed into the dilute electrolyte in above-mentioned electrowinning operation.
5. the cobalt recovery method in the lithium ion battery as claimed in claim 2, it is characterized in that: when the above-mentioned the 1st and the 2nd acid flux material is the sulfuric acid solvent, above-mentioned clean liquid operation is: in the above-mentioned the 1st and the 2nd cobalt extract behind the mixed calcium hydroxide, carry out the processing of separating out as the iron of above-mentioned metal impurities or aluminium.
6. the cobalt recovery circuit that lithium ion battery is interior is characterized in that, comprising:
Handle the discarded lithium ion battery in the middle of the cobalt recycle object obsolete material in the lithium ion battery obtain and/or the crushing powder of substandard products battery by crushing after the calcination processing, and, the magnetic that this crushing powder magnetic is selected to distinguish into magnetic metal and nonmagnetic metal is selected the difference device by after smaller or equal to designated size it being sieved;
The anodal cobalt that substandard products contained in the middle of the cobalt recycle object obsolete material in the above-mentioned lithium ion battery is extracted the 1st of separation extract separator under the 1st acid flux material;
Select the cobalt in the magnetic metal that the difference device selects to distinguish out and be contained in cobalt in the extraction residue of free or precipitation in the treatment fluid of above-mentioned the 1st extraction element being contained in, under the 2nd acid flux material, extract the 2nd extraction element of separation according to above-mentioned magnetic.
7. the cobalt recovery circuit in the lithium ion battery as claimed in claim 6 is characterized in that, comprising:
Separate out contain extract the 1st cobalt extract of the cobalt that separates by above-mentioned the 1st extraction element and contain extract the metal impurities that dissolve in the 2nd cobalt extract of the cobalt that separates by above-mentioned the 2nd extraction element after, be separated into the clean liquid device of the clean liquid residue of the cobalt cleaning fluid that contains above-mentioned cobalt and the formation of above-mentioned metal impurities;
Above-mentioned clean liquid residue is separated into the pulp residue and the cleaning device of pulp again of pulp filtrate more again;
The above-mentioned filtrate of pulp again is mixed into the 1st acid flux material in above-mentioned the 1st extraction element or the 2nd acid flux material in above-mentioned the 2nd extraction element.
8. the cobalt recovery circuit in the lithium ion battery as claimed in claim 7 is characterized in that, comprising:
To above-mentioned cobalt cleaning fluid mixed-alkali reagent, separate out cobalt hydroxide after, carry out processed and generate the caked cobalt hydroxide of cobalt hydroxide forming the piece generating apparatus;
Above-mentioned cobalt hydroxide is formed the cobalt liquor that piece is dissolved in the 3rd acid flux material use, handle the electrowinning device that reclaims metallic cobalt from this electrolyte with electrowinning as electrolyte;
Be separated into free or the electrolysis residue of precipitation and the equipment for separating liquid from solid of processing back electrolyte in the electrolyte after above-mentioned electrowinning is handled;
Above-mentioned electrolysis residue is mixed into the 2nd acid flux material at above-mentioned the 2nd extraction element.
9. the cobalt recovery circuit in the lithium ion battery as claimed in claim 8, it is characterized in that: electrolyte is formed piece with the cobalt hydroxide of forming the generation of piece generating apparatus according to above-mentioned cobalt hydroxide and is mixed after the processing that separates from above-mentioned electrolysis residue with above-mentioned equipment for separating liquid from solid, and generating the molten slurry of cobalt hydroxide, the molten slurry of this cobalt hydroxide is mixed into the dilute electrolyte at above-mentioned electrowinning device.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002382372A JP4099057B2 (en) | 2002-12-27 | 2002-12-27 | Cobalt recovery method and cobalt recovery system in lithium ion battery |
| JP382372/2002 | 2002-12-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1732589A CN1732589A (en) | 2006-02-08 |
| CN100401577C true CN100401577C (en) | 2008-07-09 |
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| CNB2003801076239A Expired - Fee Related CN100401577C (en) | 2002-12-27 | 2003-12-25 | Method of recovering cobalt from lithium ion battery and cobalt recovering system |
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| Country | Link |
|---|---|
| JP (1) | JP4099057B2 (en) |
| KR (1) | KR100706094B1 (en) |
| CN (1) | CN100401577C (en) |
| AU (1) | AU2003292808A1 (en) |
| WO (1) | WO2004062023A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11069887B2 (en) | 2015-07-28 | 2021-07-20 | Murata Manufacturing Co., Ltd. | Negative electrode, battery, battery pack, electronic apparatus, electrically driven vehicle, electrical storage device, and electric power system |
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| KR100665626B1 (en) * | 2005-03-21 | 2007-01-09 | 리메텍(주) | Dry-method of separating Co from battery scarp |
| KR100659510B1 (en) * | 2006-02-16 | 2006-12-20 | 삼성전기주식회사 | Method for manufacturing a substrate with cavity |
| KR100709268B1 (en) * | 2006-05-04 | 2007-04-19 | 한국지질자원연구원 | A recycling apparatus for used zinc-carbon and alkaline batteries and its method |
| CN101692510B (en) * | 2009-10-15 | 2011-07-27 | 同济大学 | Recycling separation process of electrode component materials of used lithium batteries |
| JP2012079630A (en) * | 2010-10-05 | 2012-04-19 | Dowa Eco-System Co Ltd | Recovery method of valuables from lithium ion secondary battery and recovered material having valuables |
| KR101138176B1 (en) | 2011-10-24 | 2012-04-25 | 주광옥 | Apparatus and method for abstraction electrolytic copper foil |
| JP6735192B2 (en) * | 2016-09-07 | 2020-08-05 | Ｊｘ金属株式会社 | Lithium-ion battery scrap processing method |
| CN107069078B (en) * | 2017-03-24 | 2019-12-27 | 中航锂电（洛阳）有限公司 | Method for recovering lithium ion battery electrode plate material |
| KR20200096965A (en) * | 2017-12-19 | 2020-08-14 | 바스프 에스이 | Battery recycling by treatment of leachate using metallic nickel |
| CN109256596B (en) * | 2018-09-19 | 2020-09-04 | 中国科学院青海盐湖研究所 | Method and system for reversely preparing aluminum-doped ternary precursor |
| JP6676124B1 (en) * | 2018-10-11 | 2020-04-08 | Ｄｏｗａエコシステム株式会社 | Method of recovering valuable resources from lithium ion secondary batteries |
| CN113302005B (en) * | 2019-04-03 | 2022-09-13 | 株式会社神户制钢所 | Method for recovering valuable metals |
| KR102205442B1 (en) * | 2020-05-26 | 2021-01-20 | 주식회사 에코프로이노베이션 | Method for recovering valuable metals using lithium carbonate from waste electrode materials of lithium-ion batteries |
| WO2023212815A1 (en) * | 2022-05-04 | 2023-11-09 | Seneca Experts-Conseils Inc. | Process for extraction of common and precious metals from wasted circuit boards |
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- 2002-12-27 JP JP2002382372A patent/JP4099057B2/en not_active Expired - Fee Related
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- 2003-12-25 WO PCT/JP2003/016733 patent/WO2004062023A1/en active Application Filing
- 2003-12-25 AU AU2003292808A patent/AU2003292808A1/en not_active Abandoned
- 2003-12-25 CN CNB2003801076239A patent/CN100401577C/en not_active Expired - Fee Related
- 2003-12-25 KR KR20057009897A patent/KR100706094B1/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1732589A (en) | 2006-02-08 |
| JP4099057B2 (en) | 2008-06-11 |
| WO2004062023A1 (en) | 2004-07-22 |
| AU2003292808A1 (en) | 2004-07-29 |
| KR100706094B1 (en) | 2007-04-12 |
| JP2004214025A (en) | 2004-07-29 |
| KR20050088093A (en) | 2005-09-01 |
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