CN114480850B - Method and system for recycling valuable metals in waste lithium ion battery anode materials through pressurized reduction - Google Patents
Method and system for recycling valuable metals in waste lithium ion battery anode materials through pressurized reduction Download PDFInfo
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- CN114480850B CN114480850B CN202210059561.3A CN202210059561A CN114480850B CN 114480850 B CN114480850 B CN 114480850B CN 202210059561 A CN202210059561 A CN 202210059561A CN 114480850 B CN114480850 B CN 114480850B
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 40
- 239000002184 metal Substances 0.000 title claims abstract description 40
- 239000002699 waste material Substances 0.000 title claims abstract description 38
- 150000002739 metals Chemical class 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 33
- 230000009467 reduction Effects 0.000 title claims abstract description 30
- 239000010405 anode material Substances 0.000 title claims abstract description 10
- 238000004064 recycling Methods 0.000 title claims abstract description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000002386 leaching Methods 0.000 claims abstract description 62
- 239000007789 gas Substances 0.000 claims abstract description 44
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000011261 inert gas Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims description 18
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims 2
- 230000001502 supplementing effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 230000008569 process Effects 0.000 abstract description 17
- 239000002002 slurry Substances 0.000 abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 abstract description 9
- 238000004090 dissolution Methods 0.000 abstract description 5
- 239000012495 reaction gas Substances 0.000 abstract description 4
- 239000012736 aqueous medium Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000011946 reduction process Methods 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 11
- 238000000197 pyrolysis Methods 0.000 description 10
- 238000011084 recovery Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- 238000005086 pumping Methods 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 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
- 239000002585 base Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910017703 Ni Co Mn Al Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
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
- 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
- H01M10/05—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
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (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 and a system for recycling valuable metals in waste lithium ion battery anode materials through pressurized reduction, wherein the method comprises the following steps: uniformly mixing anode powder of the waste lithium ion battery with deionized water, introducing the mixture into an autoclave for stirring, and respectively introducing sulfur dioxide and inert gas or mixed gas of the sulfur dioxide and the inert gas to maintain the pressure in the autoclave at 0.2-2 MPa, wherein the volume ratio of the inert gas is 0-80%. The invention adopts a section of high-pressure reduction leaching, and the working procedure is simple; the process can directly adopt aqueous medium for leaching, and the reaction gas SO 2 The slurry is heated by steam with the functions of reducing agent and leaching agent, and the reaction pressure can be greatly increased by pressurizing the steam pressure and the mixed gas to accelerate SO 2 The rate of dissolution of the solution increases the reaction rate of the reduction process and leaching of the higher metals.
Description
Technical Field
The invention relates to the field of lithium ion battery anode material recovery, in particular to a method and a system for recovering valuable metals in waste lithium ion battery anode materials through pressurized reduction.
Background
The lithium ion battery is widely applied to the fields of 3C products, vehicles, communication base stations and energy storage due to the advantages of high specific energy, low self-discharge rate, environmental friendliness and the like.
Wet process is generally adopted for recovering valuable metals in waste lithium ion batteriesAnd (3) recycling, namely leaching by adopting acid/alkali solution, and transferring valuable metals into the leaching solution. Sulfuric acid is commonly used in industry as a leaching agent for recovering valuable metals in waste lithium ion batteries, and because valuable metals such as Ni, co, mn and the like in the anode of the lithium ion battery are in a high valence state which is difficult to leach, H is added in the leaching process 2 O 2 、Na 2 SO 3 、NaHSO 3 Reducing agents such as glucose strengthen leaching rates of valuable metals such as Ni, co, mn and the like. The method of inorganic acid and reducing agent can effectively recycle valuable metal ions in waste lithium ion batteries, and the reducing agent can reduce high-valence Ni, co and Mn metal ions to low valence, so that the leaching rate is improved. However, the process has the advantages of high acid consumption in the recovery process, low utilization rate of the reducing agent, high cost and poor operating environment, and alkali is needed to be added for acid-base neutralization in the subsequent treatment process.
Patent publication No. CN108987841A discloses a method for recovering valuable metals from waste lithium ion batteries. The method comprises the steps of leaching the positive electrode powder of the waste battery under low acid liquor and normal pressure to obtain low acid sludge; and then high-acid liquor high-pressure leaching is carried out on the low-acid sludge, so that valuable metals are recovered. The patent is a method for treating waste lithium batteries, the leaching solution of low-acid leaching is produced liquid with high acid and high pressure, and after low-temperature normal-pressure reaction, the enrichment of lithium and valuable metals is realized, and the method has the defects that 1) two-stage leaching is adopted, normal-pressure leaching working procedures are increased, and energy consumption is increased. 2) The pressure of the high-pressure high-acid leaching stage is controlled by the pressure generated by the saturated vapor pressure of the water vapor through temperature rise. It is only the temperature that actually acts to promote the reaction. 3) The patent discloses that quantitative reducing substances are added into the reaction kettle, and the reaction process does not adopt exhaust, namely the reducing atmosphere in the initial reaction kettle is higher, and the reaction is weakened along with the progress of the reaction, so that the progress of the reaction is weakened, and the reaction efficiency is further reduced. The leaching requires longer time, consumes more reducing agent and requires more acid to be added.
Therefore, the development of the technology which has the advantages of low acid consumption, high leaching rate and environmental friendliness and is used for recovering valuable metals from the waste lithium ion batteries is significant.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method and a system for recovering valuable metals in the positive electrode material of the waste lithium ion battery by pressurized reduction, which realize clean and efficient recovery of valuable metal ions such as Ni, co, mn, li in the waste lithium ion battery.
In order to solve the technical problems, the invention adopts the following technical scheme: a method for recovering valuable metals in waste lithium ion battery anode materials through pressurized reduction comprises the following steps:
uniformly mixing anode powder of the waste lithium ion battery with deionized water, introducing the mixture into an autoclave, maintaining stirring, and respectively introducing sulfur dioxide and inert gas or introducing mixed gas of sulfur dioxide and inert gas to maintain the pressure in the autoclave at 0.2-2 MPa, wherein the volume ratio of the inert gas is 0-80%.
Further preferably, the pressure in the autoclave is 0.5 to 1.2MPa. At lower pressure in the autoclave, the leaching rate of Ni, co, mn, li began to decrease.
The invention adopts sulfur dioxide to carry out pressure reduction leaching, and can clean and efficiently recycle valuable metal ions in the positive electrode powder without adding a reducing agent.
Further, the normal exhaust port of the autoclave is opened for 3-8 min every 20-60 min, and sulfur dioxide and inert gas or mixed gas of the sulfur dioxide and the inert gas are respectively and additionally introduced.
In the autoclave, the reaction gas is introduced at a fixed flow rate, and the total pressure in the autoclave is mainly ensured by steam. Thus, with SO 2 Reacts with the positive electrode active material in the atmosphere of SO 2 The concentration is reduced, and the water vapor ratio is increased to ensure the total pressure. SO (SO) 2 The reduction of the concentration is disadvantageous for valuable metal reduction and continuous SO 3 Dissolving in water to form sulfate radical essential for leaching and extracting process.
The intermittent exhaust operation can replace the partial gas, SO in a longer time range 2 Is at a higher concentration level, oneSurface enhanced SO 2 The reaction with the high-valence metal in the active powder ensures the stable supply of sulfate radical on the other hand, and can obviously improve the leaching efficiency of the valuable metal in unit time.
Similarly, the leaching of the same metal quantity is realized, and SO is required to be introduced 2 And also significantly reduced.
SO 2 The pressure value of the self gas is lower, and the mixed gas needs to be pressurized by mixing with inert gas so as to meet the requirement of being introduced into the autoclave.
In addition, more reasonable SO can be controlled 2 Concentration in the autoclave, which is a closed pressure vessel, further increases SO 2 The rate of dissolution and the enhanced reaction of the molecule with valuable components, enhancing SO 2 Is used for the utilization efficiency of the system.
Further, the volume ratio of sulfur dioxide to inert gas is (2-4): (6-8). The leaching efficiency of valuable metals and the utilization rate of sulfur dioxide can be considered in the interval range. Leaching valuable metals when the volume of sulfur dioxide is relatively low
The efficiency is reduced; when the volume of sulfur dioxide is relatively high, the utilization rate of sulfur dioxide is reduced.
Further, the inert gas is N 2 Or Ar, which on one hand has the function of pressurizing and on the other hand reasonably controls SO in the atmosphere 2 Concentration.
Further, the leaching temperature in the autoclave is 25 ℃ to 150 ℃. Further preferably, the leaching temperature in the autoclave is 80 ℃ to 120 ℃. Selecting proper reaction temperature to raise SO 2 The rate of dissolution and the enhanced reaction of the molecule with valuable components, enhancing SO 2 Is used for the utilization efficiency of the system.
Further, in order to accelerate leaching of valuable metals, the stirring speed is 300-800 rpm.
Further, the leaching time in the autoclave is 20-120 min, the leaching time is too short, and the recovery rate of valuable metals is relatively low. The leaching time is too long, the influence on the recovery rate of valuable metals is not great, and the energy consumption index can be increased.
Further, the liquid-solid ratio of the positive electrode powder to the deionized water is 3:1-8:1, and the liquid-solid ratio in the range can well enable the slurry to be fully stirred in the autoclave, the water medium is sufficient, and the concentration of valuable metals is relatively high after the valuable metals are enriched in the solution, so that the method meets the technological requirements of subsequent procedures.
Further, the preparation method of the positive electrode powder of the waste lithium ion battery comprises the steps of crushing, pyrolyzing and screening the waste lithium ion battery to obtain the positive electrode powder of the waste lithium ion battery.
The invention also discloses a system for recovering valuable metals in the positive electrode materials of the waste lithium ion batteries by pressurized reduction, which comprises a slurry mixing tank, a feed pump, an autoclave and a flash tank which are sequentially connected, and is characterized in that the lower region in the autoclave is divided into a plurality of compartments by a plurality of partition plates, the bottom of each compartment is provided with an air inlet, each compartment is internally provided with a stirring paddle, one side of the top of the autoclave is provided with a liquid inlet, the other side of the top of the autoclave is provided with an air outlet and a liquid outlet, and the liquid outlet is communicated with the flash tank.
The multiple compartments are arranged, continuous discharging is realized as much as possible, multistage control of reaction is realized by controlling temperature, atmosphere composition and stirring intensity of each compartment, and meanwhile, the reaction time of slurry is controlled by controlling the feeding flow. Thereby better realizing the dissolution of valuable metals. The lower part is used for introducing the reaction gas to the lower end of the stirring paddle blade at the bottom, and the gas is dispersed into dispersed gas bubbles through the high-speed stirring paddle, so that the contact probability of the gas, an aqueous medium and a solid reactant is enhanced, the reaction process is enhanced, and the recovery rate of valuable metals is increased. The upper part is discharged, the replacement of inert gas can be realized through a reasonable exhaust mechanism, and SO in the autoclave is maintained 2 The reaction efficiency is further accelerated, the leaching rate is improved, and the SO can be improved 2 Is used for the utilization of the system.
The invention specifically comprises the following steps:
1) The waste batteries are crushed into small pieces of 1-5 cm by a crusher, and the separation membranes are separated by a wind power separation device.
2) And (3) carrying out pyrolysis on the crushed battery core for 1-3 hours at the roasting pyrolysis temperature of 400-650 ℃, removing water through roasting pyrolysis, and pyrolyzing organic matters to realize the separation of the electrode powder and the electrode plate.
3) And (3) conveying the pyrolyzed material to a sieving process, wherein the sieved material is polar powder. After the iron on the screen is separated by magnetic separation, the rest pole pieces separate copper sheets and aluminum sheets by density difference.
4) The undersize material and deionized water are mixed and stirred in a slurry mixing tank, and pumped into an autoclave through a feed pump.
5) Under the condition of keeping stirring, heating the slurry to a set temperature at normal temperature or heating the slurry to a set temperature, introducing mixed gas of sulfur dioxide and inert gas to a set pressure, wherein the sulfur dioxide is difficult to pressurize, the actual operation is to pressurize through the inert gas, so that the inside of the reaction kettle reaches the preset pressure, and in the horizontal autoclave, the pressure and the residence time of the autoclave are stabilized by controlling the flow rate of the slurry of the discharging pipe through adjusting the discharging valve.
6) When the autoclave is operated, the normal exhaust port of the autoclave is intermittently opened for 3-8 min at intervals of 20-60 min, and the autoclave is internally provided with a high-pressure oxygen (SO) source 2 The concentration of vapor and inert gas is increased, and the utilization rate of sulfur dioxide is generally improved through intermittent exhaust, and meanwhile, the purpose of reducing the sulfur dioxide consumption of ton materials is achieved.
The screening process is that the pyrolyzed material passes through a screen mesh with 50-100 meshes to obtain undersize material which is polar powder. The oversize material is subjected to electromagnetic iron removal and then is subjected to vortex separation or shaking table reselection separation to obtain copper sheets and aluminum sheets.
Compared with the prior art, the invention has the following beneficial effects: (1) According to the invention, sulfur dioxide is adopted for pressurized reduction leaching, so that the efficient recovery of valuable components in the waste lithium ion batteries is realized. SO (SO) 2 Reducing high valence Ni, co and Mn in the positive electrode material to low valence and SO simultaneously 2 Is oxidized to SO 3 And then the sulfate ions are provided after the metal ions are dissolved in water, and the reaction process is accelerated by pressure leaching, so that the technical effect of intensified leaching of valuable metals in the polar powder is realized.
(2) The high-efficiency reduction leaching of sulfur dioxide is realized by controlling the proportion of inert gas and intermittent exhaust operation, the utilization rate of sulfur dioxide is more than 93 percent, and the leaching rate of Ni, co, mn, li is more than 98.5 percent.
(3) The leached slag after pressure reduction leaching can be used as a carburant raw material for sale.
(4) According to the technical scheme, the simultaneous treatment of materials such as lithium cobaltate, lithium nickelate, lithium manganate, nickel cobalt manganese lithium ternary anode materials and the like can be realized, classification operation is not needed, the simultaneous efficient clean recovery of manganese cobalt nickel is realized, and the industrial production is facilitated.
(5) The application adopts a section of high-pressure reduction leaching, so that the working procedure is simple; the process can directly adopt aqueous medium for leaching, and the reaction gas SO 2 The slurry is heated by steam with the functions of reducing agent and leaching agent, and the reaction pressure can be greatly increased by pressurizing the steam pressure and the mixed gas to accelerate SO 2 The rate of dissolution of the solution increases the reaction rate of the reduction process and leaching of the higher metals.
(6) The pressure is raised only by the temperature rise, and the pressure raising capability is limited, and if the temperature is increased once, the reaction temperature can be increased, but a great deal of energy consumption is wasted.
Therefore, the method has the advantages of high leaching rate, short reaction time, small acid consumption, no consumption of other reducing agents, good closed operation environment of the reaction container, great reduction of the recovery cost of valuable metals, environmental friendliness, good safety and great industrial application prospect.
Drawings
FIG. 1 is a process flow diagram of an embodiment of the present invention.
FIG. 2 is a schematic diagram of a device connection according to an embodiment of the present invention.
Detailed Description
The pole powder compositions in examples 1 to 3 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1 Positive electrode active powder chemical composition
| Element(s) | Li | Ni | Co | Mn | Al | Cu | Fe | C | P |
| Percentage of | 6.03 | 3.85 | 41.7 | 11.6 | 0.13 | 0.078 | 0.021 | 0.5 | 0.15 |
Example 1
Crushing the waste lithium batteries into small pieces of 3cm, and winnowing to obtain the diaphragm. And (3) delivering the crushed small blocks to a condition of 550 ℃ for pyrolysis for 2 hours, and sieving by a 100-mesh sieve to obtain the polar powder.
Polar powderMixing with deionized water, and controlling the liquid-solid ratio to be 5:1, mixing pulp in a pulp mixing tank, pumping the pulp into a five-compartment horizontal autoclave through a feed pump after mixing pulp, reacting at 100 ℃, and introducing gas (volume ratio SO) 2 ：N 2 =3: 7) The gas flow rate is 1.04kg/h, the total pressure is 0.5MPa (the gas partial pressure is 0.4 MPa), the stirring speed is 400 rpm, the residence time is controlled to be 90min, the gas outlet of the autoclave is intermittently opened every 30min, and the gas is exhausted for 5min. And the pressurized reduction leaching slurry is discharged from the fifth compartment, and is subjected to liquid-solid separation after being cooled and depressurized through a flash tank.
Under the process conditions, the leaching rate of Ni, co, mn, li is 98.7%,98.6%,98.5% and 99.2% respectively. The utilization rate of sulfur dioxide is 93.5%.
Example 2:
crushing the waste lithium batteries into small pieces of 3cm, and winnowing to obtain the diaphragm. And (3) delivering the crushed small blocks to a condition of 550 ℃ for pyrolysis for 2 hours, and sieving by a 100-mesh sieve to obtain the polar powder.
Mixing the polar powder with deionized water, and controlling the liquid-solid ratio to be 5:1, mixing pulp in a pulp mixing tank, pumping the pulp into a five-compartment horizontal autoclave through a feed pump after mixing pulp, reacting at 100 ℃, and introducing gas (volume ratio SO) 2 ：N 2 =3: 7) The gas flow rate is 1.04kg/h, the total pressure is 0.2MPa (the gas partial pressure is 0.1 MPa), the stirring speed is 400 rpm, the residence time is controlled to be 90min, the gas outlet of the autoclave is intermittently opened every 30min, and the gas is exhausted for 5min. And the pressurized reduction leaching slurry is discharged from the fifth compartment, and is subjected to liquid-solid separation after being cooled and depressurized through a flash tank.
Under the process conditions, the leaching rate of Ni, co, mn, li is 92.4%,88.6%,90.4% and 93.2% respectively. The utilization rate of sulfur dioxide is 92.3%.
Comparative example 1:
crushing the waste lithium batteries into small pieces of 3cm, and winnowing to obtain the diaphragm. And (3) delivering the crushed small blocks to a condition of 550 ℃ for pyrolysis for 2 hours, and sieving by a 100-mesh sieve to obtain the polar powder.
Mixing the polar powder with deionized water, and controlling the liquid-solid ratio to be 5:1, mixing pulp in a pulp mixing tank, pumping the pulp into a five-compartment horizontal autoclave through a feed pump after mixing pulp, reacting at 100 ℃, and introducing gas (body)Product ratio SO 2 ：N 2 =5: 5) The gas flow rate is 1.04kg/h, the total pressure is 0.5MPa (the gas partial pressure is 0.4 MPa), the stirring speed is 400 rpm, the residence time is controlled to be 90min, the gas outlet of the autoclave is intermittently opened every 30min, and the gas is exhausted for 5min. And the pressurized reduction leaching slurry is discharged from the fifth compartment, and is subjected to liquid-solid separation after being cooled and depressurized through a flash tank.
Under the process conditions, the leaching rate of Ni, co, mn, li is 98.8%,98.7%,98.6% and 99.2% respectively. The utilization rate of sulfur dioxide is 82.4%.
Comparative example 2:
crushing the waste lithium batteries into small pieces of 3cm, and winnowing to obtain the diaphragm. And (3) delivering the crushed small blocks to a condition of 550 ℃ for pyrolysis for 2 hours, and sieving by a 100-mesh sieve to obtain the polar powder.
Mixing the polar powder with deionized water, and controlling the liquid-solid ratio to be 5:1, mixing pulp in a pulp mixing tank, pumping the pulp into a five-compartment horizontal autoclave through a feed pump after mixing pulp, reacting at 100 ℃, and introducing gas (volume ratio SO) 2 ：N 2 =3: 7) The flow rate of the introduced gas is 1.04kg/h, the total pressure is 0.2MPa (the partial pressure of the gas is 0.1 MPa), the stirring speed is 400 rpm, the residence time is controlled at 90min, and no exhaust gas is generated in the reaction process. And the pressurized reduction leaching slurry is discharged from the fifth compartment, and is subjected to liquid-solid separation after being cooled and depressurized through a flash tank.
Under the process conditions, the leaching rate of Ni, co, mn, li is 82.4%,72.6%,78.4% and 85.2% respectively. The utilization rate of sulfur dioxide is 65.3 percent.
Comparative example 2 on the basis of example 2, the reaction process was not exhausted, and the leaching rate of Ni, co, mn, li and the utilization rate of sulfur dioxide were both greatly reduced.
Example 3
Crushing the waste lithium batteries into small pieces of 3cm, and winnowing to obtain the diaphragm. And (3) delivering the crushed small blocks to a condition of 550 ℃ for pyrolysis for 2 hours, and sieving by a 100-mesh sieve to obtain the polar powder.
Mixing the polar powder with deionized water, and controlling the liquid-solid ratio to be 4:1, mixing pulp in a pulp mixing tank, pumping the pulp into a five-compartment horizontal autoclave through a feed pump after mixing pulp, reacting at 80 ℃, and introducing gas (volume ratio SO 2 ：N 2 =2: 8) The gas flow rate is 1.56kg/h, the total pressure is 1MPa (gas partial pressure is 0.9 MPa), the stirring speed is 400 rpm, the residence time is controlled to be 60min, the gas outlet of the autoclave is intermittently opened every 20min, and the gas is exhausted for 3min. And the pressurized reduction leaching slurry is discharged from the fifth compartment, and is subjected to liquid-solid separation after being cooled and depressurized through a flash tank.
Under the process conditions, the leaching rate of Ni, co, mn, li is 99.4%,99.5%,99.2% and 99.9% respectively. The utilization rate of sulfur dioxide is 94.3%.
Example 4
Crushing the waste lithium batteries into small pieces of 3cm, and winnowing to obtain the diaphragm. And (3) delivering the crushed small blocks to a condition of 550 ℃ for pyrolysis for 2 hours, and sieving by a 100-mesh sieve to obtain the polar powder.
Mixing the polar powder with deionized water, and controlling the liquid-solid ratio to be 6:1, mixing pulp in a pulp mixing tank, pumping the pulp into a five-compartment horizontal autoclave through a feed pump after mixing pulp, reacting at 110 ℃, and introducing gas (volume ratio SO 2 : ar=4: 6) The flow rate of the introduced gas is 1.04kg/h, the total pressure is 1.2MPa (the partial pressure of the mixed gas is 1.1 MPa), the stirring speed is 400 rpm, the residence time is controlled at 50min, the exhaust port of the autoclave is intermittently opened every 20min, and the exhaust is carried out for 3min. And the pressurized reduction leaching slurry is discharged from the fifth compartment, and is subjected to liquid-solid separation after being cooled and depressurized through a flash tank.
Under the process conditions, the leaching rate of Ni, co, mn, li is 99.5%,99.6%,99.4% and 99.9% respectively. The utilization rate of sulfur dioxide is 95.6%.
Example 5
Crushing the waste lithium batteries into small pieces of 3cm, and winnowing to obtain the diaphragm. And (3) delivering the crushed small blocks to a condition of 550 ℃ for pyrolysis for 2 hours, and sieving by a 100-mesh sieve to obtain the polar powder.
Mixing the polar powder with deionized water, and controlling the liquid-solid ratio to be 6:1, mixing pulp in a pulp mixing tank, pumping the pulp into a five-compartment horizontal autoclave through a feed pump after mixing pulp, reacting at 110 ℃, and introducing gas (volume ratio SO 2 : ar=9: 1) The flow rate of the introduced gas is 1.04kg/h, the total pressure is 1.2MPa (the partial pressure of the mixed gas is 1.1 MPa), the stirring speed is 400 rpm, the residence time is controlled to be 50min, the exhaust port of the high-pressure kettle is intermittently opened every 20min, and the exhaust is carried out for 3min. And the pressurized reduction leaching slurry is discharged from the fifth compartment, and is subjected to liquid-solid separation after being cooled and depressurized through a flash tank.
Under the process conditions, the leaching rate of Ni, co, mn, li is 99.5%,99.6%,99.5% and 99.9% respectively. The utilization rate of sulfur dioxide is 75.4%.
Example 5 SO on the basis of example 4 2 The ratio is increased to 90%, at this time, the inert gas accounts for 10%, the leaching rate of Ni, co, mn, li is basically not affected, but the utilization rate of sulfur dioxide is greatly reduced.
Claims (7)
1. The method for recovering valuable metals in the anode material of the waste lithium ion battery by pressurized reduction is characterized by comprising the following steps of:
uniformly mixing anode powder of the waste lithium ion battery with deionized water, introducing the mixture into an autoclave for stirring, and respectively introducing sulfur dioxide and inert gas or mixed gas of the sulfur dioxide and the inert gas to maintain the pressure in the autoclave at 0.2-2 MPa, wherein the volume ratio of the inert gas is 0-80%;
the volume ratio of sulfur dioxide to inert gas is (2-4): (6-8);
and (3) opening a normal exhaust port of the autoclave for 3-8 min every 20-60 min, and respectively supplementing and introducing sulfur dioxide and inert gas or introducing mixed gas of the sulfur dioxide and the inert gas.
2. The method for recovering valuable metals in waste lithium ion battery cathode materials by pressurized reduction according to claim 1, wherein the inert gas is N 2 Or Ar.
3. The method for recovering valuable metals in waste lithium ion battery cathode materials by pressurized reduction according to any one of claims 1-2, wherein the leaching temperature in the autoclave is 25 ℃ to 150 ℃.
4. The method for recovering valuable metals in the positive electrode material of the waste lithium ion battery by pressurized reduction according to any one of claims 1-2, wherein the stirring speed is 300-800 rpm.
5. The method for recovering valuable metals in the anode material of the waste lithium ion battery by pressure reduction according to any one of claims 1-2, which is characterized in that the leaching time in the autoclave is 20-120 min.
6. The method for recycling valuable metals in the waste lithium ion battery anode material through pressurized reduction according to any one of claims 1-2, wherein the liquid-solid ratio of the anode powder to the deionized water is 3:1-8:1.
7. The method for recycling valuable metals in the positive electrode material of the waste lithium ion battery through pressurized reduction according to any one of claims 1-2, wherein the preparation method of the positive electrode powder of the waste lithium ion battery is to crush, pyrolyze and screen the waste lithium ion battery to obtain the positive electrode powder of the waste lithium ion battery.
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