CN115066402B - Waste water treatment method for waste lithium ion batteries - Google Patents
Waste water treatment method for waste lithium ion batteries Download PDFInfo
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- CN115066402B CN115066402B CN202080095694.5A CN202080095694A CN115066402B CN 115066402 B CN115066402 B CN 115066402B CN 202080095694 A CN202080095694 A CN 202080095694A CN 115066402 B CN115066402 B CN 115066402B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- 239000002699 waste material Substances 0.000 title claims abstract description 42
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 16
- 239000002351 wastewater Substances 0.000 claims abstract description 65
- 239000002253 acid Substances 0.000 claims abstract description 57
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 51
- 238000000909 electrodialysis Methods 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 30
- 238000002386 leaching Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 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 20
- 238000010979 pH adjustment Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000010405 anode material Substances 0.000 claims abstract description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 141
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 88
- 239000000243 solution Substances 0.000 claims description 40
- 239000003513 alkali Substances 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 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
- 238000011084 recovery Methods 0.000 claims description 11
- 239000007774 positive electrode material Substances 0.000 claims description 10
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 7
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 7
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- 239000010941 cobalt Substances 0.000 description 15
- 229910017052 cobalt Inorganic materials 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 10
- 150000002500 ions Chemical class 0.000 description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 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
- 239000000843 powder Substances 0.000 description 6
- 238000001556 precipitation Methods 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
- 230000007613 environmental effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- 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
- 238000004458 analytical method Methods 0.000 description 2
- 239000000470 constituent Substances 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
- 238000005516 engineering process Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- -1 CO to aqueous NaOH Chemical compound 0.000 description 1
- 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
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Urology & Nephrology (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Manufacturing & Machinery (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a waste water treatment method of waste lithium ion batteries. According to one embodiment of the invention, a method for treating waste water of waste lithium ion batteries comprises the following steps: carrying out acid leaching on the anode material of the waste lithium ion battery to prepare leaching liquid; a step of adjusting the pH of the leachate with an alkaline 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.
Description
Technical Field
The invention relates to a waste water treatment method of waste lithium ion batteries. More particularly, the invention relates to a method for effectively treating wastewater generated after valuable metals are recovered from waste lithium ion batteries.
Background
With the increasing demand for environmental protection technologies such as electric vehicles and energy storage, and portable batteries, the demand for lithium ion batteries is also rapidly increasing.
The life of a lithium ion battery varies from days to decades, depending on its type, charge/discharge cycle and use environment.
For the waste lithium ion battery which has reached the service life, if the battery is directly buried, the battery can cause environmental problems, and the battery contains expensive metals such as cobalt, nickel, manganese, lithium and the like. Therefore, the recycling can reduce environmental load and recover valuable metals, but mainly recover cobalt, nickel, manganese, and the like, which are high in content and price.
In general, a method for recovering valuable metals from waste lithium ion batteries mainly adopts a wet method, separates positive electrode material powder from disassembled batteries, leaches the positive electrode material powder into metal ions through sulfuric acid, and then obtains sulfates or hydroxides of cobalt, nickel and manganese through precipitation with alkali, solvent extraction and the like.
When cobalt, nickel and manganese are recovered by the method, a large amount of wastewater is inevitably generated, and the wastewater mainly contains lithium ions, sodium ions and sulfate ions. The waste water contains a large amount of salts, which are required to be treated before discharge, and lithium is one of the main raw materials for manufacturing batteries, and its recovery technology is required.
Disclosure of Invention
The invention provides a waste water treatment method of waste lithium ion batteries. More specifically, the invention provides a method for effectively treating wastewater generated after valuable metals are recovered from waste lithium ion batteries.
According to one embodiment of the invention, a method for treating waste water of waste lithium ion batteries comprises the following steps: carrying out acid leaching on the anode material of the waste lithium ion battery to prepare leaching liquid; a step of adjusting the pH of the leachate with an alkaline 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.
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.
The lithium hydroxide as the alkaline material may be in the form of lithium recycle recovered in the step of subjecting the wastewater to bipolar electrodialysis to recover lithium and acid.
The lithium hydroxide as the alkaline substance may be 10 to 90 wt% of 100 wt% of the lithium recovered in the step of subjecting the wastewater to bipolar electrodialysis to recover lithium and acid, which is recycled to the step of pH-adjusting the leachate with the alkaline substance.
In the step of subjecting the wastewater to bipolar electrodialysis to recover lithium and acid, lithium is recovered as an aqueous lithium hydroxide solution, and may further comprise the step of carbonating the recovered aqueous lithium hydroxide solution to produce lithium carbonate.
In the step of subjecting the wastewater to bipolar electrodialysis to recover lithium and acid, lithium is recovered as an aqueous lithium hydroxide solution, and may further comprise the step of concentrating the recovered aqueous lithium hydroxide solution to prepare solid lithium hydroxide.
The acid recovered in the step of subjecting the wastewater to bipolar electrodialysis to recover lithium and acid can be reused as the acid in the step of acid leaching the positive electrode material of the waste lithium ion battery to prepare a leachate.
In the step of preparing the leaching solution by acid leaching the positive electrode material of the waste lithium ion battery, the acid can be sulfuric acid.
On the other hand, in the step of adjusting the pH of the leachate with an alkali substance, the alkali substance may be sodium hydroxide (NaOH) or an aqueous sodium hydroxide (NaOH) solution.
In the step of subjecting the wastewater to bipolar electrodialysis to recover lithium and acid, an aqueous sodium hydroxide solution may be recovered.
The recovered aqueous sodium hydroxide solution may be reused as the alkali substance in the step of adjusting the pH of the leachate with the alkali substance.
According to the wastewater treatment method of the waste lithium ion battery of one embodiment of the present invention, environmental load can be reduced by recovering resources from wastewater generated when valuable metals are recovered from the waste lithium ion battery and minimizing the amount of wastewater generated.
According to the wastewater treatment method of the waste lithium ion battery, disclosed by the embodiment of the invention, lithium can be recovered from the 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 alkali solutions can be recycled.
Lithium carbonate may be prepared by injecting carbonate ions into an alkali solution prepared in the wastewater treatment method of waste lithium ion batteries 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 illustration of the process flow 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 and the like 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 portion, component, region, layer and/or section from another portion, component, region, layer and/or section. Accordingly, a first portion, component, region, layer and/or section discussed below could be termed a second portion, component, region, layer and/or section without departing from the scope of the present invention.
In this specification, when a certain portion is described as "including" a certain component, unless specifically stated to the contrary, it means that other components may be included, and other components are not excluded.
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 is intended to include the plural unless the context clearly dictates otherwise. As used in this specification, the term "comprises/comprising" may specify the presence of stated features, regions, integers, steps, actions, elements, and/or components, but do not preclude the presence or addition of other features, regions, integers, steps, actions, elements, components, and/or groups thereof.
In the present specification, "a combination of these" included in the markush type expression means a mixture or a combination of one or more selected from the group consisting of the constituent elements described in the markush type expression, and means that one or more selected from the group consisting of the constituent elements described above are included.
In this specification, if a certain portion is described as being above another portion, then the other portion may exist directly above or between the other portions. When a portion is described as directly above another portion, there are no other portions therebetween.
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. Terms defined in the dictionary should be interpreted as having meanings consistent with the relevant technical literature and the disclosure herein, and should not be interpreted in an idealized or overly formal sense.
In addition, unless otherwise mentioned,% represents weight% and 1ppm is 0.0001 weight%.
In one embodiment of the present invention, further comprising an additional element means that a part of the balance of iron (Fe) is replaced by the additional element in an amount corresponding to the addition amount of the additional element.
Hereinafter, embodiments of the present invention will be described in detail to enable those skilled in the art to which the present invention pertains to easily practice the present invention. The invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein.
According to one embodiment of the invention, a method for treating waste water of waste lithium ion batteries comprises the following steps: carrying out acid leaching on the anode material of the waste lithium ion battery to prepare leaching liquid; a step of adjusting the pH of the leachate with an alkaline 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.
The steps are described below.
Firstly, acid leaching is carried out on the anode material of the waste lithium ion battery to prepare leaching liquid.
The acid in this step may be a strong acid, more specifically sulfuric acid.
The elements leached in this step may comprise cobalt, nickel, manganese, lithium, or combinations thereof.
The leachate is then pH adjusted with an alkaline material.
The alkali material in this step may comprise lithium hydroxide (LiOH), more specifically lithium hydroxide (LiOH), lithium hydroxide monohydrate (LiOH H 2 O) or an aqueous solution thereof.
At this time, lithium hydroxide (LiOH) and lithium hydroxide monohydrate (lioh·h) as alkali substances 2 O) or their aqueous solutions may be in the form of lithium recycle recovered in the step of subjecting the wastewater to bipolar electrodialysis to recover lithium and acid.
In addition, lithium hydroxide (LiOH) and lithium hydroxide monohydrate (lioh.h) are used as the alkali substances 2 O) or their aqueous solutions may be 10 to 90% by weight of the 100% by weight of lithium recovered in the step of subjecting the wastewater to bipolar electrodialysis to recover lithium and acid, recycled to the step of pH adjustment of the leachate with alkaline substances. More specifically, it may be 30 to 80% by weight recycled to the step of pH adjustment of the leachate with alkaline material. The amount recycled to the pH adjustment step when the recovered lithiumIn many cases, the process cost increases, and in small cases, the amount of recycled lithium to the pH adjustment step in the recovered lithium decreases.
On the other hand, the alkaline substance in this step may be sodium hydroxide (NaOH) or an aqueous sodium hydroxide (NaOH) solution.
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 an extract obtained by leaching cobalt, nickel, manganese, lithium, or the like by reacting a positive electrode material or the like of a waste lithium ion battery with an acid. The wastewater generated after the valuable metal is 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 to separate Na + 、Li + And SO 4 -2 . Bipolar electrodialysis to produce OH - And H + Na is mixed with + 、Li + Move to generate OH - Is to SO 4 -2 Move to generate H + To prepare NaOH, liOH aqueous solution and H 2 SO 4 A solution. In this case, the efficiency of bipolar electrodialysis can be improved by pretreating the wastewater by dilution, concentration, ion exchange, or the like.
As described above, acid and alkali solutions can be prepared by electrodialysis of wastewater, and can be used as acid and alkali raw materials such as precipitants used in leaching, pH adjustment or recovery of cobalt, nickel, manganese salts in the treatment of waste lithium ion batteries. At this time, the acid or base concentration can be increased by evaporating the solution.
Due to bipolar electrodialysis, the primary ion Na + 、Li + 、SO 4 -2 Most move to produce NaOH, liOH, H 2 SO 4 Of solutionsThe chamber, thus 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, solutions with further reduced electrolyte concentrations can be prepared by electrodialysis.
First, in the step of subjecting the wastewater to bipolar electrodialysis to recover lithium and acid, an aqueous sodium hydroxide (NaOH) solution or an aqueous lithium hydroxide (LiOH) solution may be recovered. In this case, the recovered aqueous sodium hydroxide (NaOH) solution or lithium hydroxide (LiOH) solution may be reused as an alkali substance in the step of adjusting the pH of the leachate with the alkali substance. In particular, when the base is lithium hydroxide (LiOH), lithium hydroxide monohydrate (LiOH. H) 2 O) or their aqueous solutions, can be in the form of lithium recycle recovered in the step of subjecting the wastewater to bipolar electrodialysis to recover lithium and acid.
In addition, the method may further comprise a step of carbonating the recovered lithium hydroxide (LiOH) aqueous solution to prepare lithium carbonate. The lithium carbonate can be added with carbonate ions such as CO by NaOH and LiOH aqueous solution 2 (g) Or Na (or) 2 CO 3 Is prepared.
In addition, a step of concentrating an aqueous solution of lithium hydroxide (LiOH) to prepare solid lithium hydroxide may be included.
That is, by adding carbonate ions such as CO to aqueous NaOH, liOH solutions prepared by electrodialysis 2 (g) Or Na (or) 2 CO 3 Lithium carbonate can be prepared and concentrated to give lithium hydroxide (or monohydrate). For lithium carbonate, because of Na 2 CO 3 Or NaHCO 3 Is higher than Li 2 CO 3 Or LiHCO 3 The Na ions do not precipitate, so that lithium carbonate with high purity can be prepared. As a method for improving the recovery rate of lithium carbonate, there is a method of increasing the reaction temperature or evaporating.
In addition, the acid recovered in the step of performing bipolar electrodialysis on the wastewater to recover lithium and acid can be reused as the acid in the step of performing acid leaching on the positive electrode material of the waste lithium ion battery to prepare the leaching solution.
On the other hand, the waste lithium ion battery is usedWhen valuable metals such as cobalt, nickel, and manganese are recovered by precipitation, solvent extraction, or the like after sulfuric acid leaching, alkali such as NaOH can be used as the pH adjuster or the precipitant. When LiOH or LiOH.H is used as the alkali substance 2 When O or an aqueous solution thereof is used, the wastewater produced after recovering valuable metals such as cobalt, nickel, manganese and the like from the leachate mainly contains Li + 、SO 4 2- Ions, by bipolar electrodialysis, can prepare high-concentration LiOH aqueous solution and H 2 SO 4 Solutions, lithium carbonate can be obtained by carbonating these solutions.
On the other hand, before the step of subjecting the wastewater to bipolar electrodialysis to recover lithium and acid, 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 way of examples. However, the following examples are merely illustrative of the present invention, and the present invention is not limited to the following examples.
Examples
Example 1
1. Separation of waste water
Valuable metals such as cobalt, nickel, manganese and the like are recovered from powder of positive electrode materials and the like separated from waste lithium ion batteries as raw materials, and wastewater is generally generated through the following process.
First, a powder of a positive electrode material or the like is reacted with a mineral acid such as sulfuric acid to leach out the powder. 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 of the leachate is regulated 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 alkali substance for adjusting pH.
After the above-mentioned process, waste water remained after recovering valuable metals such as cobalt, nickel, manganese, etc. from the leachate was produced, and the chemical compositions thereof are 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 units of the respective elements are g/L.
TABLE 1
| Sample preparation | Li | SO 4 | Ca | Na | K |
| Waste water | 2.35 | 69.08 | 0.02 | 21.18 | 0.04 |
2. Recovery of lithium from wastewater
The solution was placed in a bipolar electrodialyzer.
As a result, the ion concentration of each solution after bipolar electrodialysis of wastewater is shown in table 2 below. At this time, the concentration unit of each element is g/L.
From the results in 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 + Reduced to 0.31g/L, the total ion of the wastewater after analysis is reduced from the initial 90.32g/L to 4.03 g-L can be removed by more than 95.5%.
The main ion concentration of the Base chamber (Base chamber) is Li + 5.35g/L, na + As a result, it was confirmed that an aqueous solution of LiOH and NaOH was prepared and that SO was produced in an Acid chamber (Acid chamber) 4 -2 At a concentration of 119.32g/L, approximately 12% sulfuric acid was prepared.
Such results indicate that alkaline and acidic solutions can be efficiently prepared by bipolar electrodialysis of wastewater.
TABLE 2
| Sample preparation | 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 material is shown in fig. 1. Sulfuric acid and NaOH separated by bipolar electrodialysis can be recycled, and 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
When valuable metals such as cobalt, nickel and manganese are recovered from powder of positive electrode materials and the like separated from waste lithium ion batteries as raw materials, liOH H is used 2 O replaces NaOH as a base raw material for pH adjustment, precipitation and the like.
Except for this, the experimental procedure was the same as in example 1.
The chemical composition of the wastewater produced at this time is shown in Table 3. The concentration unit of each raw material at this time is g/L.
Li of the produced wastewater + Concentration becomes high, na + The concentration was 0.10g/L, showing a very low value.
TABLE 3
| Sample preparation | Li | SO 4 | Ca | Na | K |
| Waste water | 8.74 | 69.08 | 0.02 | 0.10 | 0.04 |
2. Recovery of lithium from wastewater
The solution was placed in a bipolar electrodialyzer.
As a result, the ion concentration of each solution after bipolar electrodialysis of wastewater is shown in table 4 below. At this time, 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 total ion of the wastewater after analysis is reduced from the initial 78.00g/L to 4.31g/L, and more than 94.5% of the total ion can be removed.
Li of alkali Chamber (Base Chamber) + The concentration is 19.90g/L, na + At 0.32g/L, it was confirmed that an aqueous LiOH solution was mainly prepared, and SO in an Acid chamber (Acid chamber) 4 -2 About 12% sulfuric acid was prepared at a concentration of 119.5 g/L.
In particular, since an aqueous solution of LiOH having a low Na content is prepared in a Base chamber (Base chamber), lithium carbonate of high purity can be prepared when carbonate ions are supplied, and lithium hydroxide (or monohydrate) of high purity can be prepared when concentration is performed.
TABLE 4
| Sample preparation | 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 of the process flow of example 2 using LiOH as the base material is shown in fig. 2. The sulfuric acid and LiOH separated by bipolar electrodialysis can be recycled, and for the separated lithium hydroxide, lithium carbonate can be obtained by carbonation, and solid lithium hydroxide can be obtained by crystallization.
At this time, the recovered lithium is recycled to the step of pH-adjusting the leachate with alkaline substances. The amount of recirculation is from 10 to 90% by weight.
Table 5 shows the effect of lithium recovery according to the amount of recycled lithium (lithium hydroxide) to the pH adjustment step in the recovered lithium. According to the results of table 5, when the amount of recycling is 30 to 80 wt%, the effect of lithium recovery of 50 wt% or more can be exhibited.
TABLE 5
| Amount of lithium recycled | Lithium recovery rate |
| 10 wt.% | 45 wt.% |
| 30% by weight | 55 wt.% |
| 70 wt.% | 95 wt.% |
| 80 wt.% | 69 wt.% |
| 90% by weight | 33 wt% |
The present invention can be embodied in various forms and is not limited to the embodiments, and it will be understood by those skilled in the art that the present invention can be embodied in other specific forms without changing the technical spirit or essential characteristics of the present invention. Accordingly, it should be understood that the above-described embodiments are illustrative in all respects, and not restrictive.
Claims (9)
1. A method for treating waste water from waste lithium ion batteries, comprising:
carrying out acid leaching on the anode material of the waste lithium ion battery to prepare leaching liquid;
a step of pH-adjusting the leachate with an alkaline substance;
a step of separating valuable metals and wastewater from the leachate after the pH adjustment; and
a step of bipolar electrodialysis of the wastewater to recover lithium and acid,
the lithium recovered in the step of subjecting the wastewater to bipolar electrodialysis to recover lithium and acid is in recycled form,
from 30 to 80% by weight of the recovered lithium 100% by weight is recycled to the step of pH adjustment of the leachate with alkaline material.
2. The wastewater treatment method of waste lithium ion batteries according to claim 1, wherein,
in the step of pH-adjusting 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 wastewater treatment method of waste lithium ion batteries according to claim 1, wherein,
in the step of subjecting the wastewater to bipolar electrodialysis for the recovery of lithium and acid,
the lithium is recovered as an aqueous lithium hydroxide solution,
the method further comprises the step of carbonating the recovered aqueous lithium hydroxide solution to produce lithium carbonate.
4. The wastewater treatment method of waste lithium ion batteries according to claim 1, wherein,
in the step of subjecting the wastewater to bipolar electrodialysis for the recovery of lithium and acid,
the lithium is recovered as an aqueous lithium hydroxide solution,
the method further comprises the step of concentrating the recovered aqueous lithium hydroxide solution to produce solid lithium hydroxide.
5. The wastewater treatment method of waste lithium ion batteries according to claim 1, wherein,
and (3) carrying out bipolar electrodialysis on the wastewater to recover lithium and acid, wherein the acid recovered in the step of carrying out acid leaching on the positive electrode material of the waste lithium ion battery to prepare leaching liquid is reused as the acid in the step of preparing the leaching liquid.
6. The wastewater treatment method of waste lithium ion batteries according to claim 1, wherein,
in the step of preparing the leaching solution by carrying out acid leaching on the anode material of the waste lithium ion battery,
the acid is sulfuric acid.
7. The wastewater treatment method of waste lithium ion batteries according to claim 1, wherein,
in the step of pH-adjusting the leachate with an alkaline substance,
the alkaline substance is sodium hydroxide (NaOH) or an aqueous sodium hydroxide (NaOH) solution.
8. The wastewater treatment method of waste lithium ion batteries according to claim 7, wherein,
in the step of subjecting the wastewater to bipolar electrodialysis for the recovery of lithium and acid,
recovering the aqueous sodium hydroxide solution.
9. The wastewater treatment method of waste lithium ion batteries according to claim 8, wherein,
the recovered aqueous sodium hydroxide solution is reused as an alkaline substance in the step of pH-adjusting the leachate with an alkaline substance.
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| CN108517409A (en) * | 2018-04-04 | 2018-09-11 | 长沙矿冶研究院有限责任公司 | A method of recycling valuable metal from waste and old power battery anode waste material |
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