CN112195343A - Lithium battery recycling method and system - Google Patents
Lithium battery recycling method and system Download PDFInfo
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- CN112195343A CN112195343A CN202010953319.1A CN202010953319A CN112195343A CN 112195343 A CN112195343 A CN 112195343A CN 202010953319 A CN202010953319 A CN 202010953319A CN 112195343 A CN112195343 A CN 112195343A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000004064 recycling Methods 0.000 title claims description 29
- 238000003723 Smelting Methods 0.000 claims abstract description 35
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003546 flue gas Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000002893 slag Substances 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 25
- 238000011084 recovery Methods 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 14
- 239000000956 alloy Substances 0.000 claims abstract description 14
- 150000002739 metals Chemical class 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000007599 discharging Methods 0.000 claims abstract description 4
- 238000007781 pre-processing Methods 0.000 claims abstract description 4
- 238000002485 combustion reaction Methods 0.000 claims description 16
- 239000007921 spray Substances 0.000 claims description 14
- 239000000428 dust Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 239000002918 waste heat Substances 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000004744 fabric Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- -1 copper metals Chemical class 0.000 abstract description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 27
- 239000000292 calcium oxide Substances 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 14
- 235000012255 calcium oxide Nutrition 0.000 description 13
- 230000006872 improvement Effects 0.000 description 8
- 239000000571 coke Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 235000019738 Limestone Nutrition 0.000 description 5
- 239000000378 calcium silicate Substances 0.000 description 5
- 229910052918 calcium silicate Inorganic materials 0.000 description 5
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 5
- 239000006028 limestone Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000003912 environmental pollution Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006063 cullet Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 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 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000010926 waste battery 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/02—Particle separators, e.g. dust precipitators, having hollow filters made of flexible material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/38—Removing components of undefined structure
- B01D53/40—Acidic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- 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
- C22B1/005—Preliminary treatment of scrap
-
- 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
- C22B15/0028—Smelting or converting
- C22B15/003—Bath smelting or converting
-
- 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
-
- 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
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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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Abstract
The invention relates to a lithium battery recovery method and a lithium battery recovery system, wherein the method comprises the following steps: s1, preprocessing: discharging and crushing the lithium battery to form a recovered raw material; s2, mixing: uniformly mixing the recovered raw materials, the slagging agent and the reducing agent according to a certain proportion to obtain a mixture; s3, plasma smelting: placing the mixture into a plasma smelting furnace for smelting, wherein the plasma smelting furnace keeps a negative pressure state in the smelting process, organic matters in the mixture are gasified and cracked to form combustible synthetic gas, and valuable metals in the mixture form alloy and are discharged through a metal discharge port to obtain the alloy; inorganic matters and other metals in the mixture are molten and then discharged through a slag overflow port to finally become vitreous slag. The method adopts a plasma smelting method to treat the waste lithium battery, recovers valuable cobalt, nickel and copper metals in the waste lithium battery, effectively utilizes and treats the flue gas, reduces energy consumption, finally reaches the standard and discharges, and has the advantages of simple process, high recovery rate and large batch treatment capacity.
Description
Technical Field
The invention relates to the field of resource recovery, in particular to a lithium battery recovery method and system.
Background
In recent years, China has become the largest new energy automobile market in the world, the sales volume of electric automobiles is 7 thousands in 2014, 30 thousands in 2015 and 50 thousands in 2016, and with the development of large-scale energy storage commodities such as new energy automobiles and electronic products, lithium ion batteries are used as efficient energy storage equipment, the application scale and the yield of the lithium ion batteries are rapidly increased, and a large amount of waste lithium ion batteries are generated. The demand of the vehicle power battery in China is expected to reach 125Gwh in 2020, the scrappage reaches 32Gwh, and the scrappage battery is converted into the quality of about 50 ten thousand tons; by 2030, the scrapped amount of the power battery for the vehicle reaches 101Gwh, and the scrapped amount of the power battery is about 116 ten thousand tons.
The waste and unqualified lithium ion batteries contain a large amount of metal materials such as cobalt, nickel, manganese, copper, aluminum and the like, and if the metal materials can be effectively recycled, the waste of heavy metal resources such as cobalt, nickel, manganese and the like can be avoided, and the pressure of the waste batteries on the environment can be reduced. The method realizes the harmless and recycling treatment of the waste lithium ion battery and has important economic and social values.
In the existing waste lithium battery recovery treatment process, a dry recovery technology and a wet recovery technology are mainly adopted, wherein the wet recovery technology is relatively complex in process, and has the defects of long recovery route, large investment, more equipment, large environmental pollution and the like, and the wet technology cannot treat PVDF (polyvinylidene fluoride) in the lithium batteries; the dry recovery technology mainly comprises a high-temperature (800 ℃) dry technology and a low-temperature (400 ℃) dry technology, the dry recovery technology has short route and less equipment, can effectively treat PVDF in the PVDF, but has high energy consumption and needs to consume a large amount of heat.
The plasma is the fourth state of matter existence, which is a high-temperature, ionized, conductive gas formed after gas ionization, and has the characteristics of electric neutrality and high conductivity in a macroscopic scale. Plasma torches have the advantage of producing a high intensity heat source and are relatively simple to operate, the ionized gas within the torch transferring the arc energy to the process gas before it enters the process or gasifier.
The plasma technology has proved to be a safe, reliable and environment-friendly garbage disposal technology abroad, the economical efficiency of the technology is greatly improved in recent years, and the technology is promoted to be transited from basic research to commercial application. The waste is treated by adopting a plasma technology, a plasma torch adopts electric heating, highly ionized gas (heated ionized air) is sprayed by the plasma torch, and the temperature of the sprayed gas can reach more than 3000 ℃.
The invention aims to recover lithium batteries by adopting a plasma technology, overcomes the technical defects in the prior art, and provides a lithium battery recovery method and a lithium battery recovery system.
Disclosure of Invention
The invention aims to provide a lithium battery recovery method and system which are simple in process, high in recovery rate, large in batch processing capacity and low in environmental pollution.
In order to achieve the purpose, the invention adopts the following technical scheme: a lithium battery recycling method comprises the following steps:
s1, preprocessing: discharging and crushing the lithium battery to form a recovered raw material;
s2, mixing: uniformly mixing the recovered raw materials, the slagging agent and the reducing agent according to a certain proportion to obtain a mixture;
s3, plasma smelting: placing the mixture into a plasma smelting furnace for smelting, wherein the plasma smelting furnace keeps a negative pressure state in the smelting process, organic matters in the mixture are gasified and cracked to form combustible synthetic gas, and valuable metals in the mixture form alloy and are discharged through a metal discharge port to obtain the alloy; inorganic matters and other metals in the mixture are molten and then discharged through a slag overflow port to finally become vitreous slag.
As a further improvement of the present invention, the lithium battery recycling method further comprises the steps of: s4, combustion in a second combustion chamber: and introducing the combustible synthetic gas into a secondary combustion chamber for further combustion and decomposition, so that the combustible synthetic gas is completely converted into flue gas.
As a further improvement of the present invention, the lithium battery recycling method further comprises the steps of: s5, cooling the waste heat boiler: the flue gas passes through the waste heat boiler to exchange heat with a cold water pipe in the waste heat boiler, and the temperature of the flue gas is reduced to be below 500 ℃.
As a further improvement of the present invention, the lithium battery recycling method further comprises the steps of: s6, spray absorption: the flue gas passes through a spray absorption tower to remove part of acidic substances in the flue gas, and the temperature of the flue gas is reduced to below 200 ℃.
As a further improvement of the present invention, the lithium battery recycling method further comprises the steps of: s7, bag dust removal: the flue gas is subjected to cloth bag dust removal treatment, and dust particles are separated and recovered.
As a further improvement of the present invention, the lithium battery recycling method further comprises the steps of: s8, spraying alkali washing: the flue gas is deacidified by two stages of spraying alkaline washing towers connected in series to form deacidified tail gas, and the tail gas is sent to a chimney to be uniformly discharged.
As a further improvement of the invention, the slagging agent comprises CaO, a material which generates CaO by heating, and SiO2At least one of (1).
As a further improvement of the invention, the flue gas comprises CO2、H2O、SO2、HCl、NOXAt least one of gases.
As a further improvement of the invention, the valuable metal in the mixture comprises at least one of nickel, cobalt and copper.
The invention also provides a lithium battery recovery system which comprises a plasma smelting furnace, a secondary combustion chamber, a waste heat boiler, a spray absorption tower, a dust removal cloth bag, a spray alkaline washing tower and a chimney, wherein the plasma smelting furnace, the secondary combustion chamber, the waste heat boiler, the spray absorption tower, the dust removal cloth bag, the spray alkaline washing tower and the chimney are sequentially communicated through an air pipe, at least one plasma torch is arranged at the bottom end of the plasma smelting furnace, and meanwhile, the smelting furnace is also provided with a metal discharge.
According to the lithium battery recovery method and system, the waste lithium battery is treated by adopting the plasma smelting method, valuable cobalt, nickel and copper metals in the waste lithium battery are recovered, and meanwhile, the flue gas is effectively utilized and treated, so that the energy consumption is reduced, the standard emission is finally achieved, and the method and system have the advantages of simple flow, high recovery rate, large batch treatment capacity and less environmental pollution.
Drawings
Fig. 1 is a schematic structural diagram of a lithium battery recovery system according to the present invention.
Detailed Description
The technical solutions will be described clearly and completely in the following with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "left", "right", "top", "bottom", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the device or element referred to must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
It should be understood that the terms "first", "second", etc. are used herein to describe various information, but the information should not be limited to these terms, which are only used to distinguish one type of information from another. For example, "first" information may also be referred to as "second" information, and similarly, "second" information may also be referred to as "first" information, without departing from the scope of the present invention.
In the description of the present invention, it is to be noted that, unless otherwise explicitly specified or limited, the terms "connected" and "connected" are to be interpreted broadly, e.g., as being fixed or detachable or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
The invention provides a lithium battery recovery method, which comprises the following steps:
s1, preprocessing: discharging and crushing the lithium battery to form a recovered raw material;
s2, mixing: uniformly mixing the recovered raw materials, the slagging agent and the reducing agent according to a certain proportion to obtain a mixture;
s3, plasma smelting: placing the mixture into a plasma smelting furnace for smelting, wherein the plasma smelting furnace keeps a negative pressure state in the smelting process, organic matters in the mixture are gasified and cracked to form combustible synthetic gas, and valuable metals in the mixture form alloy and are discharged through a metal discharge port to obtain the alloy; inorganic matters and other metals in the mixture are molten and then discharged through a slag overflow port to finally become vitreous slag.
In some embodiments of the present invention, the lithium battery recycling method further comprises the steps of: s4, combustion in a second combustion chamber: and introducing the combustible synthetic gas into a secondary combustion chamber for further combustion and decomposition, so that the combustible synthetic gas is completely converted into flue gas.
In some embodiments of the present invention, the lithium battery recycling method further comprises the steps of: s5, cooling the waste heat boiler: the flue gas passes through the waste heat boiler to exchange heat with a cold water pipe in the waste heat boiler, and the temperature of the flue gas is reduced to be below 500 ℃.
In some embodiments of the present invention, the lithium battery recycling method further comprises the steps of: s6, spray absorption: the flue gas passes through a spray absorption tower to remove part of acidic substances in the flue gas, and the temperature of the flue gas is reduced to below 200 ℃.
In some embodiments of the present invention, the lithium battery recycling method further comprises the steps of: s7, bag dust removal: the flue gas is subjected to cloth bag dust removal treatment, and dust particles are separated and recovered.
In some embodiments of the present invention, the lithium battery recycling method further comprises the steps of: s8, spraying alkali washing: the flue gas is deacidified by two stages of spraying alkaline washing towers connected in series to form deacidified tail gas, and the tail gas is sent to a chimney to be uniformly discharged.
In certain embodiments of the invention, the slag former comprises CaO, a material that generates CaO upon heating, SiO2At least one of (1).
In certain embodiments of the invention, the slagging agent is quicklime or limestone.
Quicklime (the main component is CaO) is obtained by calcining limestone at high temperature, is more expensive than limestone, but is easy to react with water and is not easy to store. The use of quicklime is beneficial to reducing power consumption, but is easy to pulverize, influences the permeability of furnace charge and brings certain difficulty to operation. During the slagging reaction, when quicklime is added, free CaO is easy to form calcium silicate with acid gangue.
Limestone (main component is CaCO)3) The slag is not convenient to be pulverized, but the slag amount is increased, the power consumption is increased, and the cost is increased. CaCO3Decomposing CaO is an endothermic reaction, and heat energy is consumed when decomposing in the furnace; and CaCO3Decomposed CO2The coke and the coke are subjected to carbon corrosion reaction in a part of high-temperature regions, and part of heat and carbon are consumed, so that the power consumption and the coke consumption are increased; CaCO3Decomposed CO2The reducing atmosphere in the furnace is diluted, and the reducing effect of the alloy is influenced. In addition, when the same amount of CaO is used, the amount of limestone added is 1/3 greater than the amount of quicklime added, so that relatively more impurities are introduced and the amount of generated slag is increased.
In other embodiments of the present invention, when the silicon content of the material is low, some slag forming agent is added to obtain better quality vitrified slag, and in this case, the slag forming agent is selected from one or more of sand, silica slag, silica or cullet. These include SiO2CaO with SiO at high temperature2The reaction generates calcium silicate with melting point lower than that of the alloy, the density of the liquid calcium silicate is lower than that of the alloy melt and is immiscible, the liquid calcium silicate floats on the alloy solution, when a slag overflow port of the furnace body is opened, the liquid calcium silicate flows out first to form slag。
In certain embodiments of the invention, the reducing agent comprises a solid or gaseous substance containing C. The reducing agent may reduce the metals in the feedstock for subsequent separation. In some embodiments of the invention, the reducing agent is coke (the main component is C), the coke can form a hearth with a gap in the reaction furnace, the molten inorganic substances fall into a molten slurry pool at the bottom of the reaction furnace through the gap, and the coke also provides a part of heat energy for melting the inorganic substances. The coke hearth has a certain protection effect on the refractory materials in the furnace. In the recovery method, the negative electrode material in the recovered raw material contains graphite, lithium cobaltate in the raw material positive electrode material is reduced and recovered by utilizing the reducibility of the graphite at high temperature, and the negative electrode material in the waste lithium ion battery is used for reducing the positive electrode material. However, since the content of graphite in the negative electrode material is limited, a certain amount of reducing agent C needs to be added as an aid.
In certain embodiments of the invention, the flue gas comprises CO2、H2O、SO2、HCl、NOXAt least one of gases.
In certain embodiments of the invention, the metal values in the mixture comprise at least one of nickel, cobalt, and copper.
Correspondingly, the present invention further provides a lithium battery recycling system 100, please refer to fig. 1, which includes a plasma smelting furnace 110, a secondary combustion chamber 120, a waste heat boiler 130, a spray absorption tower 140, a dust removal cloth bag 150, a spray alkaline tower 160, and a chimney 170, which are sequentially communicated through an air pipe 180. In some embodiments of the invention, the bottom end of the plasma smelting furnace 110 is provided with at least one plasma torch 111 (i.e., a plasma generator), while the furnace contains metal tapping holes 112 and slag overflow 113.
The invention adopts a plasma smelting furnace to treat the lithium battery, and utilizes the energy generated by a plasma torch (the flame temperature of the plasma torch is more than 3000 ℃) to recombine treated molecules and atoms to generate new substances, thereby changing harmful substances into harmless substances and reusable resources. After the mixture enters an plasma smelting furnace and the like, organic substances in the mixture react rapidly under the action of high temperature of 1200 ℃, and toxic and harmful organic substances such as VOCs, dioxin, PCB and the like can be decomposed thoroughly at the high temperature, so that a working condition area for generating the organic substances is avoided from the source. The inorganic matter is melted at 1450-1600 deg.C to form molten slurry. At higher temperatures, the valuable metals nickel, cobalt, copper in the mixture also melt to form an alloy. Valuable metal alloy and molten slurry are clarified and separated in a hearth, the copper content of the molten slurry is below 0.5 percent, the molten slurry is directly discharged from a slag overflow port and is made into glass body slag after water quenching, the glass body slag is an inert substance, the permeability of the glass body slag is extremely low, and the glass body slag can be used as roadbed aggregate or building materials. The valuable metal alloy is discharged from the metal discharge hole to form an alloy cast ingot which can be recycled.
According to the lithium battery recovery method and system, the waste lithium battery is treated by adopting the plasma smelting method, valuable cobalt, nickel and copper metals in the waste lithium battery are recovered, and meanwhile, the flue gas is effectively utilized and treated, so that the energy consumption is reduced, the standard emission is finally achieved, and the method and system have the advantages of simple flow, high recovery rate, large batch treatment capacity and less environmental pollution.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Claims (10)
1. A lithium battery recycling method is characterized in that: the method comprises the following steps:
s1, preprocessing: discharging and crushing the lithium battery to form a recovered raw material;
s2, mixing: uniformly mixing the recovered raw materials, the slagging agent and the reducing agent according to a certain proportion to obtain a mixture;
s3, plasma smelting: placing the mixture into a plasma smelting furnace for smelting, wherein the plasma smelting furnace keeps a negative pressure state in the smelting process, organic matters in the mixture are gasified and cracked to form combustible synthetic gas, and valuable metals in the mixture form alloy and are discharged through a metal discharge port to obtain the alloy; inorganic matters and other metals in the mixture are molten and then discharged through a slag overflow port to finally become vitreous slag.
2. The method for recycling a lithium battery according to claim 1, wherein: the lithium battery recycling method further comprises the following steps: s4, combustion in a second combustion chamber: and introducing the combustible synthetic gas into a secondary combustion chamber for further combustion and decomposition, so that the combustible synthetic gas is completely converted into flue gas.
3. The method for recycling a lithium battery according to claim 1, wherein: the lithium battery recycling method further comprises the following steps: s5, cooling the waste heat boiler: the flue gas passes through the waste heat boiler to exchange heat with a cold water pipe in the waste heat boiler, and the temperature of the flue gas is reduced to be below 500 ℃.
4. The method for recycling a lithium battery according to claim 1, wherein: the lithium battery recycling method further comprises the following steps: s6, spray absorption: the flue gas passes through a spray absorption tower to remove part of acidic substances in the flue gas, and the temperature of the flue gas is reduced to below 200 ℃.
5. The method for recycling a lithium battery according to claim 1, wherein: the lithium battery recycling method further comprises the following steps: s7, bag dust removal: the flue gas is subjected to cloth bag dust removal treatment, and dust particles are separated and recovered.
6. The method for recycling a lithium battery according to claim 1, wherein: the lithium battery recycling method further comprises the following steps: s8, spraying alkali washing: the flue gas is deacidified by two stages of spraying alkaline washing towers connected in series to form deacidified tail gas, and the tail gas is sent to a chimney to be uniformly discharged.
7. The method for recycling a lithium battery according to claim 1, wherein: the slag former comprises CaO, a material which generates CaO by heating, and SiO2At least one of (1).
8. The method for recycling a lithium battery according to claim 1, wherein: the flue gas comprises CO2、H2O、SO2、HCl、NOXAt least one of gases.
9. The method for recycling a lithium battery according to claim 1, wherein: the valuable metal in the mixture comprises at least one of nickel, cobalt and copper.
10. A lithium battery recovery system is characterized in that: the plasma smelting furnace comprises a plasma smelting furnace, a secondary combustion chamber, a waste heat boiler, a spray absorption tower, a dust removal cloth bag, a spray alkaline washing tower and a chimney which are sequentially communicated through an air pipe, wherein the bottom end of the plasma smelting furnace is provided with at least one plasma torch, and the smelting furnace is also provided with a metal discharge hole and a slag overflow port.
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| CN113908679A (en) * | 2021-09-26 | 2022-01-11 | 江苏久发环境科技有限公司 | Synthetic gas purification method |
| CN114784271A (en) * | 2022-04-26 | 2022-07-22 | 威尔能环保科技(苏州)有限公司 | Regenerated lithium iron phosphate positive electrode material, preparation method and application |
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