CN115066402A - Waste water treatment method for waste lithium ion battery - Google Patents
Waste water treatment method for waste lithium ion battery Download PDFInfo
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- CN115066402A CN115066402A CN202080095694.5A CN202080095694A CN115066402A CN 115066402 A CN115066402 A CN 115066402A CN 202080095694 A CN202080095694 A CN 202080095694A CN 115066402 A CN115066402 A CN 115066402A
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- lithium
- acid
- lithium ion
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- waste water
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 47
- 239000002699 waste material Substances 0.000 title claims abstract description 41
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 8
- 239000002351 wastewater Substances 0.000 claims abstract description 77
- 239000002253 acid Substances 0.000 claims abstract description 58
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 53
- 239000003513 alkali Substances 0.000 claims abstract description 40
- 239000000126 substance Substances 0.000 claims abstract description 38
- 238000000909 electrodialysis Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 150000002739 metals Chemical class 0.000 claims abstract description 21
- 238000002386 leaching Methods 0.000 claims abstract description 16
- 238000010979 pH adjustment Methods 0.000 claims abstract description 11
- 239000010405 anode material Substances 0.000 claims abstract description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 167
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 90
- 239000000243 solution Substances 0.000 claims description 35
- 239000007864 aqueous solution Substances 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 13
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 13
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 9
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 9
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- 229910017052 cobalt Inorganic materials 0.000 description 15
- 239000010941 cobalt Substances 0.000 description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 15
- 239000002585 base Substances 0.000 description 12
- 239000011734 sodium Substances 0.000 description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 229910052748 manganese Inorganic materials 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 229910003251 Na K Inorganic materials 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- -1 more specifically Chemical compound 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/445—Ion-selective electrodialysis with bipolar membranes; Water splitting
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
- C02F1/4695—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis electrodeionisation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
-
- 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 provides a waste water treatment method of waste lithium ion batteries. According to an embodiment of the present invention, a method for treating waste water of waste lithium ion batteries comprises: a step of preparing a leachate by acid leaching of the anode material of the waste lithium ion battery; a step of adjusting the pH of the leachate with an alkali substance; separating valuable metals and wastewater from the leachate after pH adjustment; and a step of recovering lithium and acid by performing bipolar electrodialysis on the wastewater.
Description
Technical Field
The invention relates to a waste water treatment method of waste lithium ion batteries. More particularly, the present invention relates to a method for effectively treating wastewater generated after valuable metals are recovered from a waste lithium ion battery.
Background
As the demand for environmental protection technologies such as electric vehicles and energy storage and portable batteries increases, the demand for lithium ion batteries is also rapidly increasing.
The life of a lithium ion battery varies from several days to several decades depending on its type, charge/discharge cycle, and use environment.
The used lithium ion batteries, which have reached the end of their service life, are environmentally problematic if buried directly, and contain expensive metals such as cobalt, nickel, manganese, and lithium. Therefore, by recycling, the environmental burden can be reduced and valuable metals can be recovered, but cobalt, nickel, manganese, and the like, which are large in content and expensive, are mainly recovered.
Generally, a method for recovering valuable metals from waste lithium ion batteries mainly employs a wet process, in which anode material powder is separated from a disassembled battery, and then leached into metal ions by sulfuric acid, and then sulfates or hydroxides of cobalt, nickel and manganese are obtained by precipitation using alkali, solvent extraction, and the like.
When the method is used for recovering cobalt, nickel and manganese, a large amount of waste water is inevitably generated, and the waste water mainly contains lithium ions, sodium ions and sulfate ions. The wastewater contains a large amount of salts and needs to be treated before discharge, and lithium is one of the main raw materials for manufacturing batteries and needs to be recovered.
Disclosure of Invention
The invention provides a waste water treatment method of waste lithium ion batteries. More particularly, the present invention provides a method for effectively treating wastewater generated after valuable metals are recovered from a waste lithium ion battery.
According to an embodiment of the present invention, a method for treating waste water of waste lithium ion batteries comprises: a step of preparing a leachate by acid leaching of the anode material of the waste lithium ion battery; a step of adjusting the pH of the leachate with an alkali substance; separating valuable metals and wastewater from the leachate after pH adjustment; and a step of recovering lithium and acid by performing bipolar electrodialysis on the wastewater.
In the step of adjusting the pH of the leachate with an alkali substance, the alkali substance may be lithium hydroxide (LiOH), lithium hydroxide monohydrate (LiOH. H) 2 O) or an aqueous solution thereof.
Lithium hydroxide as the base substance may be in the form of recycling of lithium recovered in the step of subjecting the waste water to bipolar electrodialysis to recover lithium and acid.
Lithium hydroxide as the alkali substance may be 10 to 90% by weight of lithium recovered in 100% by weight of lithium recovered in the step of recovering lithium and acid by subjecting the wastewater to bipolar electrodialysis, which is recycled to the step of pH-adjusting the leachate with the alkali substance.
In the step of recovering lithium and acid by subjecting the wastewater to bipolar electrodialysis, lithium is recovered as an aqueous lithium hydroxide solution, and a step of carbonating the recovered aqueous lithium hydroxide solution to prepare lithium carbonate may be further included.
In the step of recovering lithium and acid by subjecting the wastewater to bipolar electrodialysis, lithium is recovered as an aqueous lithium hydroxide solution, and a step of concentrating the recovered aqueous lithium hydroxide solution to prepare solid lithium hydroxide may be further included.
The acid recovered in the step of recovering lithium and acid by performing bipolar electrodialysis on the wastewater can be reused as the acid in the step of preparing the leachate by performing acid leaching on the positive electrode material of the waste lithium ion battery.
In the step of preparing the leachate by acid leaching of the anode material of the waste lithium ion battery, the acid may be sulfuric acid.
On the other hand, in the step of pH-adjusting the leachate with an alkali substance, the alkali substance may be sodium hydroxide (NaOH) or an aqueous solution of sodium hydroxide (NaOH).
In the step of recovering lithium and acid by subjecting the wastewater to bipolar electrodialysis, an aqueous sodium hydroxide solution can be recovered.
The recovered aqueous sodium hydroxide solution can be reused as an alkali substance in the step of adjusting the pH of the leachate with an alkali substance.
According to the method for treating waste water of waste lithium ion batteries of one embodiment of the present invention, the environmental burden can be reduced by recovering resources from waste water, which is generated when valuable metals are recovered from waste lithium ion batteries, and minimizing the amount of waste water generated.
According to the wastewater treatment method of the waste lithium ion battery provided by the embodiment of the invention, lithium can be recovered from wastewater, and acid and alkali solutions can be prepared, and the prepared acid and alkali solutions can be used as raw materials for recovering valuable metals such as cobalt, nickel, manganese and the like from the waste lithium ion battery. That is, the prepared acid and base solutions can be recycled.
Lithium carbonate may be prepared by injecting carbonate ions into the alkali solution prepared in the waste lithium ion battery wastewater treatment method according to an embodiment of the present invention, or lithium hydroxide monohydrate may be prepared by evaporating the alkali solution.
Drawings
FIG. 1 is a schematic process flow diagram of example 1 of the present invention.
FIG. 2 is a schematic process flow diagram of example 2 of the present invention.
Detailed Description
In this specification, the terms first, second, third, etc. are used to describe various parts, components, regions, layers and/or sections, but these parts, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, a first part, component, region, layer and/or section discussed below could be termed a second part, component, region, layer and/or section without departing from the scope of the present invention.
In the present specification, when a certain portion is described as "including" a certain constituent element, it means that other constituent elements may be included and not excluded unless otherwise stated.
In this specification, the terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. The term "comprises/comprising" when used in this specification can particularly specify the presence of stated features, regions, integers, steps, acts, elements, and/or components, but does not preclude the presence or addition of other features, regions, integers, steps, acts, elements, components, and/or groups thereof.
In the present specification, the phrase "a combination of these" included in the expression of markush form means a mixture or combination of one or more kinds selected from the group consisting of the constituent elements described in the expression of markush form, and means that one or more kinds selected from the group consisting of the constituent elements described above are included.
In this specification, if a part is described as being on another part, it can be directly on the other part or there may be other parts in between. When a portion is described as being directly above another portion, there are no other portions in between.
Although not otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. To the extent that terms are defined in a dictionary, they should be interpreted as having meanings consistent with those of the relevant art documents and disclosures herein, and should not be interpreted in an idealized or overly formal sense.
In addition,% represents weight% and 1ppm is 0.0001 weight% in the case where no particular mention is made.
In one embodiment of the present invention, further including the additional element means that a part of the balance of iron (Fe) is replaced with the additional element in an amount corresponding to the added amount of the additional element.
Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art to which the present invention pertains can easily practice the present invention. The invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
According to an embodiment of the present invention, a method for treating waste water of waste lithium ion batteries comprises: a step of preparing a leachate by acid leaching of the anode material of the waste lithium ion battery; a step of adjusting the pH of the leachate with an alkali substance; separating valuable metals and wastewater from the leachate after pH adjustment; and a step of recovering lithium and acid by performing bipolar electrodialysis on the wastewater.
The steps are described below.
Firstly, acid leaching is carried out on the anode material of the waste lithium ion battery to prepare a leaching solution.
The acid in this step may be a strong acid, more specifically may be sulfuric acid.
The elements leached in this step may comprise cobalt, nickel, manganese, lithium or combinations thereof.
Then, the leachate is subjected to pH adjustment with an alkali substance.
The alkali substance in this step may include lithium hydroxide (LiOH), more specifically, lithium hydroxide (LiOH), lithium hydroxide monohydrate (LiOH · H) 2 O) or an aqueous solution thereof.
In this case, lithium hydroxide (LiOH) and lithium hydroxide monohydrate (LiOH · H) are used as alkali substances 2 O) or their aqueous solution may be in the form of a recycle of lithium recovered in the step of subjecting the waste water to bipolar electrodialysis to recover lithium and acid.
Lithium hydroxide (LiOH) and lithium hydroxide monohydrate (LiOH · H) are also examples of the alkali substance 2 O) or an aqueous solution thereof may be 10 to 90% by weight of the lithium recovered in 100% by weight of the lithium recovered in the step of recovering lithium and acid by subjecting the wastewater to bipolar electrodialysis, which is recycled to the step of pH-adjusting the leachate with an alkaline substance. More specifically, it may be 30 to 80% by weight recycled to the step of pH-adjusting the leachate with an alkaline substance. When the amount of the recovered lithium to be recycled to the pH adjustment step is large, the process cost is increased, and when the amount of the recovered lithium to be recycled to the pH adjustment step is small, the process cost is decreased.
On the other hand, the alkali substance in this step may be sodium hydroxide (NaOH) or an aqueous solution of sodium hydroxide (NaOH).
Then, the leachate after pH adjustment is separated into valuable metals and wastewater.
In this step, valuable metals can be recovered by precipitation, solvent extraction, or the like, from the leachate obtained by leaching cobalt, nickel, manganese, lithium, or the like by reacting the positive electrode material of the waste lithium ion battery or the like with an acid. The wastewater generated after the valuable metals are recovered mainly contains Na + 、Li + 、SO 4 -2 Ions, and possibly other ions in trace amounts.
At this time, the Li in the lithium-containing wastewater + The concentration may be 1.5g/L or more.
The wastewater is then subjected to bipolar electrodialysis to recover lithium and acid.
More specifically, in this step, the wastewater may be subjected to bipolar electrodialysis separationNa is separated out + 、Li + And SO 4 -2 . Bipolar electrodialysis to produce OH - And H + Mixing Na + 、Li + Transfer to OH - Chamber (chamber) for SO 4 -2 Move to produce H + So that aqueous NaOH, LiOH and H solutions can be prepared 2 SO 4 And (3) solution. In this case, the efficiency of bipolar electrodialysis can be improved by pretreatment such as dilution, concentration, or ion exchange of the wastewater.
As described above, by subjecting the waste water to electrodialysis, an acid and alkali solution can be prepared, and in the treatment of the waste lithium ion battery, the acid and alkali solution can be used as an acid and alkali raw material such as a precipitant used in leaching, pH adjustment, or recovering a salt of cobalt, nickel, or manganese. At this time, the acid or alkali concentration can be increased by evaporating the solution.
Due to bipolar electrodialysis, the primary ion Na + 、Li + 、SO 4 -2 Mostly shift to produce NaOH, LiOH, H 2 SO 4 Chamber (chamber) of the solution, and therefore the wastewater is in a state of very low electrolyte concentration and can be used as water for the next bipolar electrodialysis of the leachate. In addition, a solution in which the concentration of the electrolyte is further reduced can be prepared by electrodialysis.
First, in the step of recovering lithium and acid by performing bipolar electrodialysis on wastewater, an aqueous solution of sodium hydroxide (NaOH) or an aqueous solution of lithium hydroxide (LiOH) may be recovered. In this case, the recovered sodium hydroxide (NaOH) aqueous solution or lithium hydroxide (LiOH) aqueous solution can be reused as an alkali substance in the step of adjusting the pH of the leachate with an alkali substance. In particular, when the base substance is lithium hydroxide (LiOH), lithium hydroxide monohydrate (LiOH. H) 2 O) or an aqueous solution thereof, may be in the form of a recycle of lithium recovered in the step of subjecting the wastewater to bipolar electrodialysis to recover lithium and acid.
In addition, a step of carbonating the recovered lithium hydroxide (LiOH) aqueous solution to prepare lithium carbonate may be further included. The lithium carbonate can be prepared by adding carbonate ions such as CO into aqueous solution of NaOH and LiOH 2 (g) Or Na 2 CO 3 To prepare the compound.
In addition, a step of concentrating an aqueous lithium hydroxide (LiOH) solution to prepare solid lithium hydroxide may be further included.
That is, carbonate ions such as CO are added to an aqueous solution of NaOH, LiOH prepared by electrodialysis 2 (g) Or Na 2 CO 3 Lithium carbonate may be prepared and concentrated to give lithium hydroxide (or monohydrate). For lithium carbonate, because of Na 2 CO 3 Or NaHCO 3 Has a solubility higher than that of Li 2 CO 3 Or LiHCO 3 The solubility of (3) is such that Na ions do not precipitate, and lithium carbonate having a high purity can be produced. As a method for increasing the lithium carbonate recovery rate, there is a method of increasing the reaction temperature or evaporating.
In addition, the acid recovered in the step of recovering lithium and acid by performing bipolar electrodialysis on the wastewater can be reused as the acid in the step of preparing the leachate by performing acid leaching on the positive electrode material of the waste lithium ion battery.
On the other hand, when valuable metals such as cobalt, nickel, and manganese are recovered by leaching the waste lithium ion battery with sulfuric acid and then performing precipitation, solvent extraction, and the like, an alkali substance such as NaOH may be used as a pH adjuster or a precipitant. When LiOH or LiOH H is used as the base substance 2 O or, when an aqueous solution thereof is used, a waste water produced by recovering valuable metals such as cobalt, nickel and manganese from a leachate mainly contains Li + 、SO 4 2- Ions, by bipolar electrodialysis, can produce highly concentrated aqueous LiOH solutions and H 2 SO 4 The lithium carbonate can be obtained by carbonating these solutions.
On the other hand, before the step of recovering lithium and acid by subjecting the wastewater to bipolar electrodialysis, the wastewater used may be pretreated by dilution or concentration, ion exchange, or the like.
Hereinafter, the present invention will be described in more detail by examples. However, the following examples are only for illustrating the present invention, and the present invention is not limited to the following examples.
Examples
[ example 1]
1. Separation of waste water
The method is characterized in that the powder of the anode material and the like separated from the waste lithium ion battery is used as a raw material to recover valuable metals such as cobalt, nickel, manganese and the like, and the waste water is generally produced through the following processes.
First, a powder of a positive electrode material or the like is leached by reacting the powder with an inorganic acid such as sulfuric acid. At this time, various impurities including valuable metals such as cobalt, nickel, manganese, and lithium are ionized and present in the solution.
Then, the leachate is separated, and the pH value of the leachate is adjusted by using acid/alkali substances or valuable metals such as cobalt, nickel, manganese and the like are separated from the leachate in the form of sulfate or hydroxide by adopting a solvent extraction method and a precipitation method.
In example 1 of the present invention, NaOH was used as the base for pH adjustment.
After the above process, waste water remained after recovering valuable metals such as cobalt, nickel, manganese and the like from the leachate is generated, and the chemical composition of the waste water is shown in table 1. That is, the following table 1 shows the components of wastewater generated when the waste lithium ion battery is recycled, and the concentration unit of each element is g/L.
[ Table 1]
| Test specimen | Li | SO 4 | Ca | Na | K |
| Waste water | 2.35 | 69.08 | 0.02 | 21.18 | 0.04 |
2. Recovery of lithium from waste water
The solution was placed in a bipolar electrodialyser.
As a result, the ion concentration of each solution after bipolar electrodialysis of the wastewater is shown in table 2 below. In this case, the concentration unit of each element is g/L.
From the results of Table 2, Li as desalted water of wastewater + The concentration is reduced to 0.21g/L, SO 4 -2 Reduced to 3.51g/L, Na + The total analyzed ions of the waste water are reduced to 0.31g/L from the initial 90.32g/L to 4.03g/L, and more than 95.5 percent can be removed.
The main ion concentration of the Base chamber (Base chamber) is Li + Is 5.35g/L, Na + 69.17g/L of SO in an Acid chamber (Acid chamber) from which an aqueous solution of LiOH or NaOH was prepared was confirmed 4 -2 At a concentration of 119.32g/L, approximately 12% sulfuric acid was prepared.
These results show that an alkaline solution and an acidic solution can be efficiently produced by subjecting the wastewater to bipolar electrodialysis.
[ Table 2]
| Test specimen | Li | SO 4 | Ca | Na | K |
| Desalted water | 0.21 | 3.51 | - | 0.31 | - |
| Alkali chamber | 5.35 | 2.00 | 0.04 | 69.17 | 0.11 |
| Acid chamber | 0.10 | 119.32 | 0.02 | 1.06 | - |
A schematic of the process flow of example 1 using NaOH as the base feed is shown in fig. 1. The sulfuric acid and NaOH separated by bipolar electrodialysis can be recycled, lithium carbonate can be obtained by carbonation of the separated lithium hydroxide, and solid lithium hydroxide can be obtained by crystallization.
[ example 2]
1. Separation of waste water
Anode separated from waste lithium ion batteryWhen valuable metals such as cobalt, nickel and manganese are recovered from powders of materials or the like, LiOH. H is used 2 And replacing NaOH with O as an alkali raw material, and using the O as a pH adjusting agent, a precipitating agent and the like.
The experimental procedure was otherwise the same as in example 1.
The chemical composition of the wastewater produced at this time is shown in Table 3. The concentration of each raw material at this time was in g/L.
Li of produced wastewater + Higher concentration of Na + The concentration was 0.10g/L, showing a very low value.
[ Table 3]
| Test specimen | Li | SO 4 | Ca | Na | K |
| Waste water | 8.74 | 69.08 | 0.02 | 0.10 | 0.04 |
2. Recovery of lithium from waste water
The solution was placed in a bipolar electrodialyser.
As a result, the ion concentration of each solution after bipolar electrodialysis of the wastewater is shown in table 4 below. In this case, the concentration unit of each element is g/L.
Li as desalted water of wastewater + The concentration is reduced to 0.78g/L, SO 4 -2 At 3.53g/L, no other ions were detected. The analyzed total ions of the wastewater are reduced from the initial 78.00g/L to 4.31g/L, and can be removed by more than 94.5 percent.
Base chamber Li + The concentration is 19.90g/L, Na + 0.32g/L, it was confirmed that mainly an aqueous LiOH solution was prepared and SO in an Acid chamber (Acid chamber) was formed 4 -2 At a concentration of 119.5g/L, about 12% sulfuric acid was prepared.
In particular, since an aqueous LiOH solution having a low Na content is prepared in a Base chamber (Base chamber), high-purity lithium carbonate can be prepared when carbonate ions are supplied, and high-purity lithium hydroxide (or monohydrate) can be prepared when concentration is performed.
[ Table 4]
| Test specimen | Li | SO 4 | Ca | Na | K |
| Desalted water | 0.78 | 3.53 | - | - | - |
| Alkali chamber | 19.9 | 2.00 | 0.04 | 0.32 | 0.10 |
| Acid chamber | 0.37 | 119.50 | 0.02 | 0.01 | - |
A schematic process flow diagram of example 2 using LiOH as the base starting material is shown in fig. 2. The sulfuric acid and LiOH separated by bipolar electrodialysis can be recycled, lithium carbonate can be obtained by carbonation of the separated lithium hydroxide, and solid lithium hydroxide can be obtained by crystallization.
At this time, the recovered lithium is recycled to the step of adjusting the pH of the leachate with an alkali substance. The amount recycled is from 10 to 90% by weight.
Table 5 shows the effect of lithium recovery according to the amount of recycled to the pH adjustment step in the recovered lithium (lithium hydroxide). According to the results of table 5, when the amount of recycling is 30 to 80 wt%, the effect of the lithium recovery rate of 50 wt% or more can be exhibited.
[ Table 5]
| Amount of lithium recycled | Lithium recovery rate |
| 10% by weight | 45% by weight |
| 30% by weight | 55% by weight |
| 70% by weight | 95% by weight |
| 80% by weight | 69% by weight |
| 90% by weight | 33% by weight |
The present invention can be implemented in various different ways, and is not limited to the embodiments, and a person of ordinary skill in the art to which the present invention pertains can understand that the present invention can be implemented in other specific ways without changing the technical idea or essential features of the present invention. It should therefore be understood that the above-described embodiments are illustrative in all respects and not restrictive.
Claims (11)
1. A waste water treatment method of waste lithium ion batteries comprises the following steps:
acid leaching is carried out on the anode material of the waste lithium ion battery to prepare a leaching solution;
a step of adjusting the pH of the leachate with an alkali substance;
separating the leachate after pH adjustment into valuable metals and wastewater; and
a step of subjecting the wastewater to bipolar electrodialysis to recover lithium and acid.
2. The method for treating waste water of waste lithium ion batteries according to claim 1,
in the step of adjusting the pH of the leachate with an alkaline substance,
the alkali substance is lithium hydroxide (LiOH), lithium hydroxide monohydrate (LiOH. H) 2 O) or an aqueous solution thereof.
3. The method for treating waste water of waste lithium ion batteries according to claim 2,
lithium hydroxide (LiOH) or lithium hydroxide monohydrate (LiOH. H) as the alkali substance 2 O) or their aqueous solution is a form of recycling of the lithium recovered in the step of recovering lithium and acid by subjecting said wastewater to bipolar electrodialysis.
4. The method for treating waste water of waste lithium ion batteries according to claim 3,
lithium hydroxide (LiOH) or lithium hydroxide monohydrate (LiOH. H) as an alkali substance 2 O) or an aqueous solution thereof is 10 to 90% by weight of the 100% by weight of lithium recovered in the step of recovering lithium and acid by subjecting the wastewater to bipolar electrodialysis, and is recycled to the step of pH-adjusting the leachate with an alkaline substance.
5. The method for treating waste water of waste lithium ion batteries according to claim 1,
in the step of recovering lithium and acid by subjecting the wastewater to bipolar electrodialysis,
the lithium is recovered as an aqueous solution of lithium hydroxide,
the method further comprises the step of carbonating the recovered aqueous lithium hydroxide solution to produce lithium carbonate.
6. The method for treating waste water of waste lithium ion batteries according to claim 1,
in the step of recovering lithium and acid by subjecting the wastewater to bipolar electrodialysis,
the lithium is recovered as an aqueous solution of lithium hydroxide,
the method further comprises the step of concentrating the recovered aqueous lithium hydroxide solution to produce solid lithium hydroxide.
7. The method for treating waste water of waste lithium ion batteries according to claim 1,
and (3) performing bipolar electrodialysis on the wastewater to recover lithium and acid, wherein the acid recovered in the step is reused as the acid in the step of performing acid leaching on the positive electrode material of the waste lithium ion battery to prepare a leaching solution.
8. The method for treating waste water of waste lithium ion batteries according to claim 1,
in the step of preparing the leachate by acid leaching of the anode material of the waste lithium ion battery,
the acid is sulfuric acid.
9. The method for treating waste water of waste lithium ion batteries according to claim 1,
in the step of adjusting the pH of the leachate with an alkaline substance,
the alkali substance is sodium hydroxide (NaOH) or an aqueous solution of sodium hydroxide (NaOH).
10. The method for treating waste water of spent lithium ion batteries according to claim 1, wherein,
in the step of recovering lithium and acid by subjecting the wastewater to bipolar electrodialysis,
recovering the aqueous sodium hydroxide solution.
11. The method for treating waste water of spent lithium ion batteries according to claim 10,
the recovered aqueous sodium hydroxide solution is reused as an alkali substance in the step of adjusting the pH of the leachate with an alkali substance.
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