CN113512646A - Recovery processing method of waste power battery - Google Patents
Recovery processing method of waste power battery Download PDFInfo
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- CN113512646A CN113512646A CN202110571589.0A CN202110571589A CN113512646A CN 113512646 A CN113512646 A CN 113512646A CN 202110571589 A CN202110571589 A CN 202110571589A CN 113512646 A CN113512646 A CN 113512646A
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- roasting
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- battery powder
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- 239000002699 waste material Substances 0.000 title claims abstract description 31
- 238000011084 recovery Methods 0.000 title abstract description 18
- 238000003672 processing method Methods 0.000 title abstract description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 62
- 239000000843 powder Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 51
- 230000009467 reduction Effects 0.000 claims abstract description 33
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 31
- 238000002485 combustion reaction Methods 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 6
- 125000005587 carbonate group Chemical group 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 37
- 239000003638 chemical reducing agent Substances 0.000 claims description 25
- 238000004064 recycling Methods 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 229910017052 cobalt Inorganic materials 0.000 claims description 18
- 239000010941 cobalt Substances 0.000 claims description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 13
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 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 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 230000002829 reductive effect Effects 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 239000002028 Biomass Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052744 lithium Inorganic materials 0.000 abstract description 28
- 238000002386 leaching Methods 0.000 abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 25
- 239000011572 manganese Substances 0.000 description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- 229910052748 manganese Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 229940044175 cobalt sulfate Drugs 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 229940073644 nickel Drugs 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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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- Geology (AREA)
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- Geochemistry & Mineralogy (AREA)
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Abstract
The invention discloses a recovery processing method of waste power batteries, and belongs to the technical field of lithium ion batteries. The recovery processing method of the waste power battery comprises the following steps: reducing and roasting the battery powder and the combustion improver, and then recovering metal by taking the battery powder after the reducing and roasting as a raw material; wherein the combustion improver is carbonate. The inventor creatively adds sodium carbonate and/or potassium carbonate as combustion improver in the reduction roasting process, and can remarkably improve the leaching rate of lithium by improving the reduction roasting stage and matching with the conventional metal separation process.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a recovery processing method of waste power batteries.
Background
With the popularization and application of new energy automobiles, scrapped power batteries are more and more, the disassembled power battery powder contains a large amount of valuable metals such as nickel, cobalt, manganese, lithium, copper and the like, and particularly the recovery value of lithium is very high.
At present, the recovery methods of power batteries mainly comprise two methods:
the first method is to recover nickel, cobalt and manganese and then lithium. Specifically, the battery powder is reduced and dissolved, a nickel-cobalt-manganese-lithium removing solution is dissolved, iron in the solution is removed through a chemical method, nickel, cobalt and manganese are recovered through an extraction method, and lithium is recovered from raffinate. The process has the advantages of slow reduction and dissolution of battery powder, low lithium yield and high cost.
The second method is to reduce and bake the battery powder statically, and recover nickel, cobalt and manganese after recovering lithium. Specifically, battery powder is reduced and roasted in a static reduction furnace, the roasted anode powder is subjected to the working procedures of crushing, sieving and the like, lithium is directly leached by water and recovered, leaching slag of the lithium is dissolved and leached by acid, and nickel, cobalt and manganese are recovered from the leaching solution through an extraction method. This method also has problems of low lithium yield and high cost.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a recovery processing method of a waste power battery, aiming at remarkably improving the yield of lithium.
The invention is realized by the following steps:
the invention provides a recovery processing method of waste power batteries, which comprises the following steps: reducing and roasting the battery powder and the combustion improver, and then recovering metal by taking the battery powder after the reducing and roasting as a raw material; wherein the combustion improver is carbonate.
The invention has the following beneficial effects: the inventor creatively adds carbonate as a combustion improver in the reduction roasting process, and can remarkably improve the leaching rate of lithium by improving the reduction roasting stage and matching with the conventional metal separation process.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a process flow chart of a method for recycling waste power batteries according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Referring to fig. 1, the embodiment of the invention provides a recovery processing method of a waste power battery, which comprises reduction roasting and metal recovery.
S1, reduction roasting
And reducing and roasting the battery powder and a combustion improver, wherein the combustion improver is carbonate. In some embodiments, the combustion improver is selected from at least one of sodium carbonate, potassium carbonate, and sodium bicarbonate. The inventor creatively adds a combustion improver in the reduction roasting stage, and finds that the leaching rate of lithium can be obviously improved by matching with the conventional metal recovery process after roasting.
The inventor has made a certain study on the mechanism that the lithium leaching rate can be significantly improved, and the chemical reaction equation is as follows:
12LiNixCoyMnzO2(s) +7C(s) + Combustion improver → 6Li2CO3(s)+12(x-zm/n)Ni(s)+12(z/n)(NiO)m·(MnO)n(s)+12yCo(s)+3z(1+m/n)CO2(g)(1)。
The inventors surmise that the combustion improver mainly plays a role in accelerating the reduction reaction during the roasting process.
Specifically, the battery powder is obtained by discharging and crushing waste power batteries, and the particle size of the battery powder is larger than 100 meshes.
In some embodiments, the combustion improver is sodium carbonate, and the mass ratio of the combustion improver to the battery powder is 2.5-7: 10; preferably 4-6:10, and may be 2.5:10, 3:10, 4:10, 5:10, 6:10, 7:10, etc., or may be intermediate values between any of the above adjacent ratio values.
The consumption of the combustion improver is too small, so that the leaching rate of lithium is not favorably and greatly improved; the consumption of the combustion improver is too large, so that raw materials are wasted, and the recovery rate of lithium cannot be further improved.
Further, the reducing agent used in the reducing roasting process is selected from any one of hydrogen, carbonaceous reducing agent and biomass; the reducing agent may be hydrogen gas or a general carbonaceous reducing agent.
In a preferred embodiment, the reducing agent is a carbonaceous reducing agent, such as graphite electrode powder. The operating temperature with hydrogen is lower, but the safety is poor. The mass ratio of the graphite electrode powder to the battery powder is 2-4:10, can be 2:10, 3:10, 4:10 and the like, and can also be a middle value in any adjacent ratio value.
Furthermore, in the reduction roasting process, the roasting temperature is controlled at 600-. Specifically, the baking temperature may be 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃, 660 ℃, 670 ℃, 680 ℃, 690 ℃, 700 ℃, or the like, or may be an intermediate value between any of the above adjacent temperature values; the baking time may be 1 hour, 2 hours, 3 hours, etc., or may be intermediate values between any of the above adjacent time values.
The inventor finds that the roasting temperature and the roasting time also have obvious influence on the leaching rate of lithium, and the leaching rate of lithium is reduced when the roasting temperature is too low; the energy consumption is obviously increased when the roasting temperature is too high, but the leaching rate of lithium is not obviously increased.
In a preferred embodiment, the reduction roasting is dynamic reduction roasting, and compared with static reduction roasting, the raw materials are turned over in the dynamic reduction roasting process, so that the leaching rate of lithium is further improved.
S2, recovering metals
The method for recovering metal by taking battery powder after reduction roasting as a raw material comprises the following steps: and dissolving and filtering the battery powder after reduction roasting to obtain filtrate and filter residues, and evaporating and separating the filtrate to obtain lithium carbonate. Lithium carbonate can be dissolved in water and exists in the filtrate, and the lithium carbonate is separated by depositing through evaporation; whereas the metal compounds of nickel, cobalt and manganese are insoluble in water and are present in the filter residue after filtration.
In some embodiments, the battery powder after reduction roasting is mixed and dissolved with water, and the liquid-solid ratio is controlled to be 1:0.5-1.5, can be 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.5 and the like, and can also be an intermediate value between any adjacent ratio values. By accurately controlling the liquid-solid ratio, the lithium carbonate can be fully dissolved, the excessive water consumption is prevented, and the energy consumption is increased in the evaporation process.
In some embodiments, the filtrate is evaporated and centrifuged, and the resulting solid is dried to obtain lithium carbonate; the operation temperature is controlled to be 80-100 ℃ in the evaporation process, and the operation time is 3-5 h. And controlling no crystal to precipitate again in the evaporation process so as to fully recover the lithium element.
In a preferred embodiment, the liquid obtained after the centrifugal separation is mixed with sodium carbonate, battery powder and a reducing agent, dried, and used as a raw material for the reduction roasting process. The excessive sodium carbonate is used, so that the liquid after centrifugal separation contains more sodium carbonate, the part of the raw materials can be recycled, and the sodium carbonate, the battery powder and the reducing agent with proper amount are supplemented for drying, so that the sodium carbonate can be used as the raw materials for reduction roasting.
It is necessary to supplement that the amount of sodium carbonate is added according to the limited amount when the sodium carbonate is recovered for the first time, and the amount of sodium carbonate is adjusted to the specified range when the sodium carbonate is supplemented partially according to the amount of the recovered sodium carbonate in the subsequent test.
In some embodiments, the filter residue is mixed with acid liquor and a reducing agent to be leached to obtain a solution containing nickel, cobalt and manganese, and then extraction separation is carried out; the acid solution is a sulfuric acid solution with the concentration of 0.5-2mol/L, and the volume of the sulfuric acid solution corresponding to each gram of filter residue is 2-20 ml; the reducing agent is oxalic acid, and the mass of the reducing agent per gram of filter residue is 0.01-0.1 g. After dissolving the filter residue in acid liquor, extracting and separating to obtain nickel sulfate, cobalt sulfate and manganese sulfate, treating raffinate with wastewater, and discharging the raffinate.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a recovery processing method of waste power batteries, which is used for obtaining battery powder after discharging and crushing waste power battery powder, and the specific components are shown in table 1.
TABLE 1 Battery powder Metal content test results
| Element(s) | Co | Ni | Cu | Fe | Mn | Li | Al |
| Content of raw Material (%) | 4.31 | 9.66 | 3.17 | 1.61 | 24.21 | 3.11 | 0.79 |
Recovering lithium, nickel, cobalt and manganese in the battery powder by the following method:
(1) mixing graphite electrode powder, sodium carbonate and battery powder (larger than 100 meshes) according to the mass ratio of 3:2.5:10, and carrying out dynamic reduction roasting treatment at the roasting temperature of 600 ℃ for 3h to obtain the reduction-roasted battery powder.
(2) Dissolving the treated battery powder in water according to a liquid-solid ratio of 1:1, filtering to obtain filtrate and filter residue, evaporating the filtrate (controlling the temperature to be 100 ℃ and the time to be 3 hours) and carrying out centrifugal separation, drying the solid obtained after the centrifugal separation to obtain lithium carbonate, supplementing sodium carbonate to the liquid obtained after the centrifugal separation, and mixing and drying the liquid, the battery powder and graphite electrode powder to be used as a roasting raw material of the next recovery process;
adding sulfuric acid (the concentration is 1mol/L, the volume of a sulfuric acid solution corresponding to each gram of filter residue is 10ml) and a small amount of oxalic acid reducing agent (the mass of the reducing agent corresponding to each gram of filter residue is 0.1g) into the filter residue, leaching to obtain a solution containing nickel, cobalt and manganese, extracting and separating to obtain nickel, cobalt and manganese sulfate, treating raffinate by waste water, and discharging.
Example 2
This example provides a method for recycling waste power batteries, which recovers lithium, nickel, cobalt, and manganese in the battery powder shown in table 1 by the following methods:
(1) mixing graphite electrode powder, sodium carbonate and battery powder (larger than 100 meshes) according to a mass ratio of 3:5:10, carrying out dynamic reduction roasting treatment at the roasting temperature of 600 ℃, and preserving heat for 3 hours to obtain the reduction roasted battery powder.
(2) Dissolving the treated battery powder in water according to a liquid-solid ratio of 1:1, filtering to obtain filtrate and filter residue, evaporating the filtrate (controlling the temperature to be 95 ℃ and the time to be 4 hours) and carrying out centrifugal separation, drying the solid obtained after the centrifugal separation to obtain lithium carbonate, supplementing sodium carbonate to the liquid obtained after the centrifugal separation, and mixing and drying the liquid, the battery powder and graphite electrode powder to be used as a roasting raw material of the next recovery process;
adding sulfuric acid (the concentration is 1mol/L, the volume of a sulfuric acid solution corresponding to each gram of filter residue is 10ml) and a small amount of oxalic acid reducing agent (the mass of the reducing agent corresponding to each gram of filter residue is 0.1g) into the filter residue, leaching to obtain a solution containing nickel, cobalt and manganese, extracting and separating to obtain nickel, cobalt and manganese sulfate, treating raffinate by waste water, and discharging.
Example 3
This example provides a method for recycling waste power batteries, which recovers lithium, nickel, cobalt, and manganese in the battery powder shown in table 1 by the following methods:
(1) mixing graphite electrode powder, sodium carbonate and battery powder (larger than 100 meshes) according to a mass ratio of 3:5:10, carrying out dynamic reduction roasting treatment at the roasting temperature of 700 ℃, and preserving heat for 3 hours to obtain the reduction-roasted battery powder.
(2) Dissolving the treated battery powder in water according to a liquid-solid ratio of 1:1, filtering to obtain filtrate and filter residue, evaporating the filtrate (controlling the temperature to be 90 ℃ and the time to be 5 hours) and carrying out centrifugal separation, drying the solid obtained after the centrifugal separation to obtain lithium carbonate, supplementing sodium carbonate to the liquid obtained after the centrifugal separation, and mixing and drying the liquid, the battery powder and graphite electrode powder to be used as a roasting raw material of the next recovery process;
adding sulfuric acid (the concentration is 1mol/L, the volume of a sulfuric acid solution corresponding to each gram of filter residue is 10ml) and a small amount of oxalic acid reducing agent (the mass of the reducing agent corresponding to each gram of filter residue is 0.1g) into the filter residue, leaching to obtain a solution containing nickel, cobalt and manganese, extracting and separating to obtain nickel, cobalt and manganese sulfate, treating raffinate by waste water, and discharging.
Example 4
The present embodiment provides a method for recycling waste power batteries, which is substantially the same as embodiment 1, except that: the roasting temperature is 550 ℃, and the temperature is kept for 3 hours.
Example 5
The present embodiment provides a method for recycling waste power batteries, which is substantially the same as embodiment 1, except that: the roasting temperature is 750 ℃, and the temperature is kept for 3 h.
Example 6
The present embodiment provides a method for recycling waste power batteries, which is substantially the same as embodiment 1, except that: the mass ratio of the sodium carbonate to the battery powder is 2: 10.
Example 7
The present embodiment provides a method for recycling waste power batteries, which is substantially the same as embodiment 1, except that: the mass ratio of the sodium carbonate to the battery powder is 8: 10.
Example 8
The present embodiment provides a method for recycling waste power batteries, which is substantially the same as embodiment 1, except that: sodium carbonate was replaced with potassium carbonate.
Comparative example 1
This comparative example provides a method of recycling spent power cells, substantially the same as example 1, except that: no sodium carbonate was added during the reduction roasting.
Comparative example 2
This comparative example provides a method of recycling spent power cells, substantially the same as example 1, except that: sodium carbonate was replaced with sodium bicarbonate.
Test examples
The amount of lithium carbonate obtained in the test examples and the comparative examples was measured, and the leaching rate of lithium was calculated, the test method being described in GB/T11064.1-2013, and the results of the leaching rate test are shown in Table 2.
TABLE 2 leaching rates of lithium by the recovery methods in examples and comparative examples
| Group of | Lithium extraction Rate (%) | Manganese leaching rate (%) | Cobalt leaching rate (%) | Nickel leaching rate (%) |
| Example 1 | 77.9 | <0.01 | <0.01 | <0.01 |
| Example 2 | 84.6 | <0.01 | <0.01 | <0.01 |
| Example 3 | 78.9 | <0.01 | <0.01 | <0.01 |
| Example 4 | 50.5 | <0.01 | <0.01 | <0.01 |
| Example 5 | 78.5 | <0.01 | <0.01 | <0.01 |
| Example 6 | 76.8 | <0.01 | <0.01 | <0.01 |
| Example 7 | 66.5 | <0.01 | <0.01 | <0.01 |
| Example 8 | 77.5 | <0.01 | <0.01 | <0.01 |
| Comparative example 1 | 8.3 | <0.01 | <0.01 | <0.01 |
| Comparative example 2 | 75.5 | <0.01 | <0.01 | <0.01 |
As can be seen from table 2, the addition of sodium carbonate, the amount of sodium carbonate, and the calcination conditions all have an effect on the leaching rate of the final lithium, and it is preferable to control the above parameters within the ranges defined in the present application.
In summary, an embodiment of the present invention provides a method for recycling a waste power battery, including: reducing and roasting the battery powder and the combustion improver, and then recovering metal by taking the battery powder after the reducing and roasting as a raw material; wherein the combustion improver is at least one of sodium carbonate and potassium carbonate; the inventor creatively adds sodium carbonate and/or potassium carbonate as combustion improver in the reduction roasting process, and can remarkably improve the leaching rate of lithium by improving the reduction roasting stage and matching with the conventional metal separation process.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for recycling waste power batteries is characterized by comprising the following steps: reducing and roasting the battery powder and the combustion improver, and then recovering metal by taking the battery powder after the reducing and roasting as a raw material;
wherein the combustion improver is carbonate.
2. The method for recycling the waste power battery as claimed in claim 1, wherein the combustion improver is sodium carbonate, and the mass ratio of the combustion improver to the battery powder is 2.5-7: 10; preferably 4-6: 10;
preferably, the combustion improver is at least one selected from sodium carbonate, potassium carbonate and sodium bicarbonate;
preferably, the battery powder is obtained by discharging and crushing waste power batteries.
3. The method for recycling waste power cells as claimed in claim 1, wherein the reducing agent used in the reductive roasting process is selected from any one of hydrogen, carbonaceous reducing agent and biomass; preferably a carbonaceous reducing agent.
4. The method for recycling waste power batteries according to claim 3, wherein the carbonaceous reducing agent is graphite electrode powder;
preferably, the mass ratio of the graphite electrode powder to the battery powder is 2-4: 10.
5. The method for recycling and treating the waste power battery as claimed in claim 1, wherein in the process of reduction roasting, the roasting temperature is controlled to be 600-700 ℃, and the roasting time is 1-3 h;
preferably, the reduction firing is performed as a dynamic reduction firing.
6. The method for recycling and treating the waste power batteries according to any one of claims 1 to 5, wherein the process for recycling metal by using the battery powder after reduction roasting as a raw material comprises the following steps: and dissolving and filtering the battery powder after reduction roasting to obtain filtrate and filter residue, and evaporating and separating the filtrate to obtain lithium carbonate.
7. The method for recycling waste power batteries according to claim 6, wherein the battery powder after reduction roasting is mixed and dissolved with water, and the liquid-solid ratio is controlled to be 1: 0.5-1.5.
8. The method for recycling and processing the waste power batteries according to claim 6, wherein the filtrate is evaporated and centrifugally separated, and the obtained solid is dried to obtain the lithium carbonate;
preferably, the operation temperature is controlled to be 80-100 ℃ in the evaporation process, and the operation time is 3-5 h.
9. The method for recycling waste power batteries according to claim 8, wherein the liquid obtained after the centrifugal separation is mixed with sodium carbonate, battery powder and a reducing agent, dried and used as a raw material in the reduction roasting process.
10. The method for recycling the waste power batteries according to claim 6, wherein the filter residue is mixed with acid liquor and a reducing agent to be leached to obtain a solution containing nickel, cobalt and manganese, and then the solution is extracted and separated;
preferably, the acid solution is a sulfuric acid solution with the concentration of 0.5-2mol/L, and the volume of each gram of filter residue corresponding to the sulfuric acid solution is 2-20 ml;
preferably, the reducing agent is oxalic acid, and the mass of the reducing agent per gram of filter residue is 0.01-0.1 g.
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