CN113061725A - Method for recovering lithium from waste lithium ion battery by pyrogenic process - Google Patents
Method for recovering lithium from waste lithium ion battery by pyrogenic process Download PDFInfo
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- CN113061725A CN113061725A CN202110262168.XA CN202110262168A CN113061725A CN 113061725 A CN113061725 A CN 113061725A CN 202110262168 A CN202110262168 A CN 202110262168A CN 113061725 A CN113061725 A CN 113061725A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 43
- 239000002699 waste material Substances 0.000 title claims abstract description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 34
- 230000001698 pyrogenic effect Effects 0.000 title claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 45
- 239000002893 slag Substances 0.000 claims abstract description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052802 copper Inorganic materials 0.000 claims abstract description 39
- 238000003723 Smelting Methods 0.000 claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000011084 recovery Methods 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 16
- 230000000996 additive effect Effects 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005507 spraying Methods 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001313 Cobalt-iron alloy Inorganic materials 0.000 claims abstract description 4
- 239000003546 flue gas Substances 0.000 claims abstract description 4
- OBLMUVZPDITTKB-UHFFFAOYSA-N [Fe].[Co].[Cu] Chemical compound [Fe].[Co].[Cu] OBLMUVZPDITTKB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000007599 discharging Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000009853 pyrometallurgy Methods 0.000 claims description 2
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000010926 waste battery Substances 0.000 description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- 229910002519 Co-Fe Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B7/001—Dry 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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0054—Slag, slime, speiss, or dross treating
-
- 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
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/023—Obtaining nickel or cobalt by dry processes with formation of ferro-nickel or ferro-cobalt
-
- 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
- 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
- C22B7/04—Working-up slag
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for recovering lithium from waste lithium ion batteries by a pyrogenic process, which is characterized by comprising the following steps: uniformly mixing the pretreated waste lithium ion battery and an additive, and spraying the mixture into copper slag through a feeding device for reduction smelting; in the reduction smelting process, lithium element interacts with an additive to be converted into a volatile lithium-containing compound, the volatile lithium-containing compound is volatilized into a gas phase, and the lithium-containing flue gas is collected after being condensed; copper slag, copper, cobalt and part of iron elements in the waste lithium ion battery are reduced and smelted and then separated from the slag phase in a metal phase form to obtain copper-cobalt-iron alloy; according to the invention, the additive is added to volatilize the lithium element in the slag into gas phase in the reduction smelting process, the lithium element is recovered by rapid condensation, the high-efficiency enrichment and recovery of lithium are realized while copper, cobalt and iron are recovered, the process is simple, the operability is strong, and the large-scale production and application are easy.
Description
Technical Field
The invention belongs to the field of comprehensive utilization of resources, and particularly relates to a method for recovering lithium from waste lithium ion batteries by a pyrogenic process.
Background
Since the commercialization of lithium ion batteries in the early 90's of the last century, their use has become more widespread. Lithium ion batteries are almost ubiquitous from notebook computers, mobile phones to electric vehicles and energy storage devices. With the consequent increase in the number of used lithium ion batteries at a surprising rate. The lithium ion battery often contains a large amount of valuable metals such as cobalt, copper, lithium and the like, and the waste lithium ion battery is efficiently recycled, so that the problem of environmental pollution caused by battery discarding can be solved, the contradiction between supply and demand of lithium, cobalt and copper resources can be relieved, and sustainable development can be realized.
The pyrometallurgical reduction smelting can realize the high-efficient recovery of valuable metals in the waste lithium ion batteries, and the high-temperature reduction characteristics of the cathode carbon and the metal aluminum in the waste lithium ion batteries can replace the traditional reducing agents, so that the metallization reduction of cobalt, copper and iron oxides in the high-temperature smelting process is realized, the additional input of reducing agent resources is avoided, the recovery cost of valuable metals in the waste lithium ion batteries is undoubtedly reduced, and the large-scale treatment is easy to realize. However, in the recovery process, lithium element is usually solidified in the slag, and the lithium element in the slag needs to be recovered by adopting acid leaching and other modes, so that the risk of secondary environmental pollution exists.
The application number is 201610479966.7, coal powder is used as a reducing agent to roast waste lithium battery materials, and then roasted products are treated by CO2Preparing lithium bicarbonate aqueous solution by means of carbonization water immersion, and finally further processing the lithium bicarbonate aqueous solution to prepare the lithium bicarbonateThe process flow of the lithium carbonate is complex, and the large-scale production is not facilitated. The patent with application number 201910716016.5 discloses a method for efficiently and selectively extracting lithium from waste lithium batteries by flash reduction, which comprises the steps of adding a lithium battery anode material and a reducing gas into a flash furnace in a spraying manner, wherein the lithium battery anode material falls from the flash furnace in a suspension state and is completely reduced within 2-10 seconds; and then, selectively separating lithium by a water leaching mode, but the process can realize the recovery of nickel, cobalt and manganese by further treating leached residues.
Disclosure of Invention
In order to solve the problems of difficult lithium recovery and complex operation process in the current pyrogenic process treatment process of the waste lithium ion battery, the invention provides a method for pyrogenically recovering lithium from the waste lithium ion battery, which comprises the following specific steps:
the method comprises the following steps: pretreating the waste lithium ion battery;
step two: transferring high-temperature copper slag produced in the copper pyrometallurgical process into a dilution furnace;
step three: uniformly mixing the pretreated waste lithium ion battery and the additive, and spraying the mixture into molten slag through a feeding device for reduction smelting;
step four: in the reduction smelting process, lithium element and an additive interact and volatilize to enter a gas phase, and the lithium-containing flue gas is collected after being condensed;
step five: and after the copper, cobalt and iron elements in the slag are reduced to a metal state, standing and settling, separating a metal phase from the slag phase, wherein the upper layer is molten slag, and discharging the lower layer of metal melt from the bottom of the dilution furnace to obtain the copper-cobalt-iron alloy.
Preferably, the pretreatment process of the waste lithium ion battery material in the first step sequentially comprises the following steps: physical discharging, soaking treatment, electrolyte recovery treatment, drying, disassembly, crushing, presintering and grinding.
Preferably, in the second step, the Cu content in the copper slag is 0.5-5%, and the Fe content is 20.0-45.0%.
Preferably, the temperature in the lean furnace in the second step is controlled at 1300-1500 ℃.
Preferably, the consumption of the waste lithium ion battery in the third step is 5-30% of the total mass of the copper slag.
Preferably, the dosage of the additive in the third step is 2-20% of the total mass of the copper slag.
Preferably, in the fourth step, lithium element is volatilized into a gas phase in the form of lithium chloride.
Preferably, the reduction smelting time in the fifth step is 10-60 min.
Preferably, the Cu content in the Cu-Co-Fe alloy phase obtained in the fifth step is 10-20%, the Fe content is 60-75%, and the Co content is 10-20%.
The invention has the beneficial effects that:
(1) the method reduces Cu, Co and Fe elements in the copper slag and the waste battery into metal states in a high-temperature reduction smelting mode, and recovers the copper slag and the waste battery in a slag-gold separation mode;
(2) according to the invention, the additive is added to volatilize the lithium element in the slag into a gas phase in the reduction smelting process, and the lithium element is recovered by rapid condensation, so that the process is simple and the operation is convenient;
(3) the invention fully utilizes the heat of the thermal-state copper slag, reduces the energy consumption of pyrogenic recovery treatment of the waste battery, utilizes the depletion furnace for production, is convenient for industrial implementation, and reduces the operation cost;
(4) compared with the original copper slag, the smelting slag generated by the invention has no obvious physical property change, belongs to common industrial solid wastes, can be used as a cement additive or for preparing microcrystalline glass and the like, and realizes harmless and resource utilization of the waste slag.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited to the examples.
The equipment used in the invention is a depletion furnace, copper-containing high-temperature slag generated in the copper smelting process and a waste lithium ion battery are used as raw materials, and N is used as a raw material2As carrier gas, spraying the treated waste lithium ion battery into the molten slag by adopting a material spraying devicePowders and additives.
The components of the copper slag used in the examples of the present invention are shown in table 1.
Table 1 composition of copper slag components (mass%,%)
The waste lithium ion battery used in the embodiment of the invention comprises the rest components after shelling and recycling of electrolyte components, including a positive electrode material, a negative electrode, an aluminum foil, a copper foil and the like (table 2).
Table 2 composition of waste lithium ion battery components (mass%)
Example 1
(1) Pretreating the waste lithium ion battery: physical discharging, soaking treatment after valve breaking, electrolyte recovery treatment, drying, disassembling, crushing, presintering at 300 ℃, and grinding to 40-60 meshes.
(2) Introducing high-temperature copper slag into a depletion furnace, and introducing N2Controlling the temperature rise rate, and maintaining the temperature of the copper slag at 1450 ℃.
(3) Uniformly mixing the pretreated waste lithium ion battery powder and an additive, and adding N2The carrier gas is blown into the molten slag through a material spraying device for reduction smelting, wherein the dosage of the waste lithium ion battery is 50 percent of the total mass of the copper molten slag, and the dosage of the additive is 20 percent of the total mass of the copper molten slag.
(4) In the reduction smelting process, lithium element volatilizes into a gas phase, and the volatilized flue gas is quickly condensed to recover a lithium-containing volatile matter.
(5) And settling for 50min after the blowing is finished, and discharging the molten metal from the furnace bottom to obtain the cobalt-nickel-iron alloy.
In the embodiment, the separation effect of the molten slag and the alloy melt is good, and the obtained alloy contains 63.8% of Fe, 14.8% of Co and 15.1% of Cu; the recovery rate of iron is 98.8 percent, the recovery rate of cobalt is 99.2 percent, and the recovery rate of copper is 97.2 percent. The lithium volatilization rate was 87.8%.
Example 2
(1) Pretreating the waste lithium ion battery: physical discharging, soaking treatment after valve breaking, electrolyte recovery treatment, drying, disassembling, crushing, presintering at 300 ℃, and grinding to 40-60 meshes.
(2) Introducing high-temperature copper molten slag into a dilution furnace, and introducing N2Controlling the temperature rise rate, and maintaining the temperature of the copper slag at 1450 ℃.
(3) Uniformly mixing the pretreated waste lithium ion battery powder and an additive, and adding N2The carrier gas is blown into the molten slag through a material spraying device for reduction smelting, wherein the dosage of the waste lithium ion battery is 35 percent of the total mass of the copper smelting slag, and the dosage of the additive is 15 percent of the total mass of the copper smelting slag.
(4) In the reduction smelting process, lithium element volatilizes into gas phase, and volatilized smoke dust and smoke gas are quickly condensed to recover lithium-containing volatile matters.
(5) And settling for 50min after the blowing is finished, and discharging the molten metal from the furnace bottom to obtain the cobalt-nickel-iron alloy.
In the embodiment, the separation effect of the slag and the alloy melt is good, and the obtained alloy contains 68.88% of Fe, 13.1% of Co and 13.6% of Cu; the recovery rate of iron is 65.3 percent, the recovery rate of cobalt is 97.9 percent, and the recovery rate of copper is 92.8 percent; the lithium volatilization rate was 76.3%.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (9)
1. A method for recovering lithium from waste lithium ion batteries by a pyrogenic process is characterized by comprising the following steps:
the method comprises the following steps: pretreating the waste lithium ion battery;
step two: transferring high-temperature copper slag produced in the copper pyrometallurgical process into a dilution furnace;
step three: uniformly mixing the pretreated waste lithium ion battery and the additive, and spraying the mixture into molten slag through a feeding device for reduction smelting;
step four: in the reduction smelting process, lithium element and an additive interact and volatilize to enter a gas phase, and the lithium-containing flue gas is collected after being condensed;
step five: and after the copper, cobalt and iron elements in the slag are reduced to a metal state, standing and settling, separating a metal phase from the slag phase, wherein the upper layer is molten slag, and discharging the lower layer of metal melt from the bottom of the dilution furnace to obtain the copper-cobalt-iron alloy.
2. The method for recovering lithium from waste lithium ion batteries by a pyrogenic process according to claim 1, wherein the pretreatment of the waste lithium ion battery material in the first step sequentially comprises: physical discharging, soaking treatment, electrolyte recovery treatment, drying, disassembly, crushing, presintering and grinding.
3. The method for recovering lithium from waste lithium ion batteries by a pyrogenic process according to claim 1, wherein in the second step, the copper slag contains 0.5% -5% of Cu and 20.0-45.0% of Fe.
4. The method for pyrogenically recovering lithium from spent lithium ion batteries according to claim 1, wherein the temperature in the abatement furnace in the second step is controlled at 1300-1500 ℃.
5. The method for recovering lithium from waste lithium ion batteries through a pyrogenic process according to claim 1, wherein the amount of the waste lithium ion batteries used in the third step is 5 to 30% of the total mass of the copper slag.
6. The method for recovering lithium from waste lithium ion batteries by a pyrogenic process according to claim 1, wherein the amount of the additive used in the third step is 2 to 20% of the total mass of the copper slag.
7. The method for pyrogenically recovering lithium from waste lithium ion batteries according to claim 1, wherein in the step four, lithium element is volatilized into a gas phase in the form of lithium chloride.
8. The method for recovering lithium from waste lithium ion batteries by a pyrogenic process according to claim 1, wherein the reduction smelting time in the fifth step is 10-60 min.
9. The method for recovering lithium from waste lithium ion batteries by a pyrogenic process according to claim 1, wherein the copper-containing cobalt-iron alloy phase obtained in the fifth step contains 10 to 20% of Cu, 60 to 75% of Fe, and 10 to 20% of Co.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114015873A (en) * | 2021-09-18 | 2022-02-08 | 昆明理工大学 | Method for preparing manganese-silicon alloy from lithium ore and enriching lithium |
| CN114350957A (en) * | 2022-01-07 | 2022-04-15 | 江西理工大学 | Method for comprehensively recovering valuable elements from waste lithium batteries |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107964593A (en) * | 2017-11-28 | 2018-04-27 | 北京科技大学 | A kind of method that lithium in lithium cell slag is scrapped by chloridising roasting evaporation recycling |
| CN112176190A (en) * | 2020-09-17 | 2021-01-05 | 昆明理工大学 | Method for recovering cobalt, copper and iron from waste cobalt-containing lithium ion battery |
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2021
- 2021-03-10 CN CN202110262168.XA patent/CN113061725A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107964593A (en) * | 2017-11-28 | 2018-04-27 | 北京科技大学 | A kind of method that lithium in lithium cell slag is scrapped by chloridising roasting evaporation recycling |
| CN112176190A (en) * | 2020-09-17 | 2021-01-05 | 昆明理工大学 | Method for recovering cobalt, copper and iron from waste cobalt-containing lithium ion battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114015873A (en) * | 2021-09-18 | 2022-02-08 | 昆明理工大学 | Method for preparing manganese-silicon alloy from lithium ore and enriching lithium |
| CN114350957A (en) * | 2022-01-07 | 2022-04-15 | 江西理工大学 | Method for comprehensively recovering valuable elements from waste lithium batteries |
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