CN114480850A - Method and system for recovering valuable metals in anode materials of waste lithium ion batteries through pressure reduction - Google Patents
Method and system for recovering valuable metals in anode materials of waste lithium ion batteries through pressure reduction Download PDFInfo
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- CN114480850A CN114480850A CN202210059561.3A CN202210059561A CN114480850A CN 114480850 A CN114480850 A CN 114480850A CN 202210059561 A CN202210059561 A CN 202210059561A CN 114480850 A CN114480850 A CN 114480850A
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 43
- 239000002184 metal Substances 0.000 title claims abstract description 43
- 239000002699 waste material Substances 0.000 title claims abstract description 40
- 150000002739 metals Chemical class 0.000 title claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- 239000010405 anode material Substances 0.000 title claims description 10
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 79
- 238000002386 leaching Methods 0.000 claims abstract description 51
- 239000007789 gas Substances 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 32
- 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 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000007774 positive electrode material Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims 1
- 239000002002 slurry Substances 0.000 abstract description 42
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 230000008569 process Effects 0.000 abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 abstract description 10
- 239000012736 aqueous medium Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000012495 reaction gas Substances 0.000 abstract description 3
- 238000011946 reduction process Methods 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 229910052759 nickel Inorganic materials 0.000 description 17
- 229910052748 manganese Inorganic materials 0.000 description 16
- 239000011572 manganese Substances 0.000 description 16
- 239000002253 acid Substances 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 238000012216 screening Methods 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 238000007599 discharging Methods 0.000 description 8
- 238000005086 pumping Methods 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 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
- 238000000197 pyrolysis Methods 0.000 description 4
- 239000003513 alkali Substances 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- 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
- 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
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 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
- 238000010828 elution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000009776 industrial production Methods 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 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
- 239000011780 sodium chloride Substances 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000003313 weakening effect Effects 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
- C22B7/006—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
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- 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
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- 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
- 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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- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
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- General Chemical & Material Sciences (AREA)
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- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method and a system for recovering valuable metals in a positive electrode material of a waste lithium ion battery by pressure reduction, which comprises the following steps: uniformly mixing anode powder of a waste lithium ion battery with deionized water, introducing the mixture into an autoclave for stirring, and introducing sulfur dioxide and inert gas or mixed gas of the sulfur dioxide and the inert gas respectively to maintain the pressure in the autoclave at 0.2-2 MPa, wherein the volume ratio of the inert gas is0 to 80%. The method adopts one-stage high-pressure reduction leaching, and has simple working procedures; the process can directly adopt an aqueous medium to leach the reaction gas SO2Has the functions of a reducing agent and a leaching agent, heats slurry through steam, increases the reaction pressure more greatly through the steam pressure and the pressurization of mixed gas, and accelerates the SO2The rate of dissolving the solution enhances the reaction rate of the reduction process and leaching of the high valence metals.
Description
Technical Field
The invention relates to the field of recovery of lithium ion battery anode materials, in particular to a method and a system for recovering valuable metals from waste lithium ion battery anode materials by pressure 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. The cumulative production and sale of new energy vehicles in our country will exceed 500 million in 2020, the scrappage of power batteries is about 32.77 million tons, and the market of power batteries is expected to exceed 600 million yuan by 2025.
The valuable metals in the waste lithium ion batteries are generally recovered by a wet process, namely, the valuable metals are transferred into leachate by leaching with acid/alkali solution. Sulfuric acid is often used as a leaching agent for recovering valuable metals in waste lithium ion batteries in industry, and since the valuable metals such as Ni, Co, Mn and the like in the positive electrode of the lithium ion battery are often in a high valence state difficult to leach, H is added in the leaching process2O2、Na2SO3、NaHSO3And reducing agents such as glucose enhance the leaching rate of valuable metals such as Ni, Co, Mn and the like. The method of the inorganic acid and the reducing agent can effectively recover valuable metal ions in the waste lithium ion battery, and the reducing agent can also reduce high-valence Ni, Co and Mn metal ions to low-valence states, thereby improving the leaching rate. However, the process has the disadvantages of high acid consumption in the recovery process, low utilization rate of the reducing agent, high cost and poor operation environment because alkali needs to be added for acid-alkali 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 with low acid solution under normal pressure to obtain low acid residue; and then carrying out high-acid liquid high-pressure leaching on the low-acid residue to realize the recovery of valuable metals. The patent is a method for treating waste lithium batteries, leachate obtained by low-acid leaching is high-acid high-pressure output liquid, and enrichment of lithium and valuable metals is realized after low-temperature normal-pressure reaction, and the method has the defects that 1) two-stage leaching is adopted, the normal-pressure leaching process is increased, and energy consumption is increased. 2) The high-pressure high-acid leaching stage is controlled by the pressure generated by the saturated vapor pressure of water vapor through temperature rise. The only thing that actually serves to promote the reaction is the temperature. 3) This patent is inside to add quantitative reducing substance, and the reaction process does not adopt the exhaust, and reducing atmosphere is higher in the initial reation kettle promptly, and along with the going on of reaction, reducing atmosphere's weakening can weaken going on of reaction, and then reduces reaction efficiency. The leaching takes longer, more reducing agent is consumed, and more acid needs to be formulated.
Therefore, the development of a technology for recovering valuable metals from waste lithium ion batteries with low acid consumption, high leaching rate and environmental friendliness is of great significance.
Disclosure of Invention
The invention aims to solve the technical problem that the prior art is not enough, and provides a method and a system for recovering valuable metals in a positive electrode material of a waste lithium ion battery by pressure reduction, so that the clean and efficient recovery of valuable metal ions such as Ni, Co, Mn, Li and the like in the waste lithium ion battery is realized.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for recovering valuable metals in anode materials of waste lithium ion batteries by pressure reduction 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 introducing sulfur dioxide and inert gas or mixed gas of the sulfur dioxide and the inert gas respectively 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 1.2 MPa. When the pressure in the autoclave is low, the leaching rates of Ni, Co, Mn, and Li start to decrease.
The invention adopts sulfur dioxide to perform pressure reduction leaching, and valuable metal ions in the anode powder can be cleanly and efficiently recovered without adding a reducing agent.
Further, opening a normal exhaust port of the high-pressure kettle for 3-8 min every 20-60 min, and then respectively supplementing and introducing sulfur dioxide and inert gas or introducing mixed gas of the sulfur dioxide and the inert gas.
In an autoclave, reacting gasThe fixed flow rate is introduced, and the total pressure in the kettle is mainly ensured by steam. Thus, with SO2Reacting with positive active material in the presence of SO2The concentration is reduced, and the water vapor ratio is increased to ensure the total pressure. SO (SO)2The reduction of concentration is not favorable for the reduction of valuable metals and the continuous SO3Dissolving in water to form sulfate radical essential for leaching extraction.
After the intermittent exhaust operation is adopted, the partial gas can be replaced, and SO can be replaced in a longer time range2At a higher concentration level, on the one hand, the SO is enhanced2The reaction with high-valence metal in the active powder, on the other hand, the stable supply of sulfate radicals is ensured, and the leaching efficiency of the valuable metal in unit time can be obviously improved.
In the same way, the leaching of the same amount of metals is realized, and SO needs to be introduced2It is also greatly reduced.
SO2The pressure value of the gas per se is low, and the mixed gas needs to be mixed with the inert gas to realize pressurization so as to meet the requirement of introducing into the high-pressure kettle.
In addition, more reasonable SO can be controlled2Concentration of SO further increased in the autoclave, a closed pressure vessel2The rate of dissolution and the enhanced reaction of the molecule with the valuable component, increasing the SO2The utilization efficiency of (2).
Further, the volume ratio of the sulfur dioxide to the inert gas is (2-4): (6-8). Within the range, the leaching efficiency of valuable metals and the utilization rate of sulfur dioxide can be considered. When the volume ratio of sulfur dioxide is lower, the leaching efficiency of valuable metals is reduced; when the volume of sulfur dioxide is relatively high, the utilization rate of sulfur dioxide is reduced.
Further, the inert gas is N2Or Ar, the two atmospheres play a role in pressurizing on one hand, and reasonably controlling SO in the atmosphere on the other hand2And (4) concentration.
Further, the leaching temperature in the autoclave is 25 ℃ to 150 ℃. Further preferably, the leaching temperature in the autoclave is between 80 ℃ and 120 ℃. Selecting proper reaction temperature and increasing SO2The rate of dissolution and the enhanced reaction of the molecule with the valuable component, increasing the SO2The utilization efficiency of (2).
Further, in order to accelerate leaching of valuable metals, the stirring speed is 300-800 rpm.
Furthermore, 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 anode powder to the deionized water is 3: 1-8: 1, the slurry can be well stirred in the high-pressure kettle fully in the liquid-solid ratio within the range, the water medium is sufficient, and after valuable metals are enriched in the solution, the concentration of the valuable metals is relatively high, so that the process requirements of subsequent working procedures are met.
Further, the preparation method of the anode powder of the waste lithium ion battery comprises the steps of crushing, pyrolyzing and screening the waste lithium ion battery to obtain the anode powder of the waste lithium ion battery.
The invention also discloses a system for recovering valuable metals in the anode materials of the waste lithium ion batteries by pressure reduction, which comprises a size mixing tank, a charging pump, an autoclave and a flash tank which are sequentially connected, and is characterized in that the lower area 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, a stirring paddle is arranged in each compartment, 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.
A plurality of compartments are arranged to meet continuous discharging as far as possible, multi-stage control of reaction is achieved by controlling temperature, atmosphere composition and stirring intensity of each compartment, and reaction time of slurry is controlled by controlling feeding flow. Thereby more effectively realizing valuable metal elution. The lower part is used for air inlet, reaction gas is introduced to the lower end of the paddle of the stirring paddle at the bottom, the gas is scattered into dispersed gas bubbles by the high-speed stirring paddle, the contact probability of the gas with an aqueous medium and a solid reactant is strengthened, the reaction process is strengthened, and the gas inlet is increasedRecovery of the metal values. The upper part is exhausted, the replacement of inert gas can be realized through a reasonable exhaust mechanism, and SO in the high-pressure kettle is maintained2The relative concentration of the sodium chloride can further accelerate the reaction efficiency, improve the leaching rate and simultaneously improve the SO2The utilization ratio of (2).
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 diaphragms are sorted by a wind power sorting device.
2) And (3) performing a pyrolysis process on the crushed battery core, roasting for 1-3 h at the roasting pyrolysis temperature of 400-650 ℃, and performing baking pyrolysis to remove moisture and pyrolyze organic matters to realize separation of pole powder and pole pieces.
3) The pyrolysis material is sent to a screening process, and the undersize is the superfine powder. After the oversize is magnetically separated from iron, the remaining pole pieces are separated into copper sheets and aluminum sheets through density difference.
4) Mixing the undersize product with deionized water in a size mixing tank, and pumping into the high-pressure kettle by a charging 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 inert gas is used for pressurizing in practical operation to enable the inside of the reaction kettle to reach the preset pressure, and in a horizontal high-pressure kettle, the slurry flow of a discharge pipe is controlled by adjusting a discharge valve to stabilize the pressure and the retention time of the high-pressure kettle.
6) When the autoclave is operated, the normal exhaust port of the autoclave is intermittently opened for 3-8 min every 20-60 min, and SO is caused in the autoclave2The concentration of steam and inert gas is increased, and the utilization rate of sulfur dioxide is generally improved by intermittent exhaust, and the purpose of sulfur dioxide consumption of ton materials is reduced.
And in the screening process, the pyrolyzed materials pass through a screen with 50-100 meshes to obtain undersize materials which are polar powder. And removing iron from the oversize product by electromagnetism, and separating by vortex separation or table gravity separation to obtain copper sheets and aluminum sheets.
Compared with the prior art, the invention has the beneficial effects that: (1) hair brushThe sulfur dioxide is adopted for pressure reduction leaching, so that the valuable components in the waste lithium ion battery can be efficiently recovered. SO (SO)2Reducing high valence state Ni, Co and Mn in the anode material to low valence state, and simultaneously reducing SO2Is oxidized into SO3And the obtained product is dissolved in water to provide sulfate ions of metal ions for salification, and the pressure leaching accelerates the reaction process, so that the technical effect of enhanced leaching of valuable metals in the electrode powder is realized.
(2) The efficient reduction leaching of sulfur dioxide is realized by controlling the proportion of inert gas and intermittent exhaust operation, the utilization rate of the sulfur dioxide is more than 93 percent, and the leaching rate of Ni, Co, Mn and Li is more than 98.5 percent.
(3) The leached slag after the pressure reduction leaching can be sold as a raw material of a carburant.
(4) According to the technical scheme, materials such as lithium cobaltate, lithium nickelate, lithium manganate and nickel cobalt manganese lithium ternary positive electrode materials can be simultaneously treated, classification operation is not needed, efficient and clean recovery of manganese, cobalt and nickel is realized, and industrial production is facilitated.
(5) The method adopts one-stage high-pressure reduction leaching, and the process is simple; the process can directly adopt an aqueous medium to leach the reaction gas SO2Has the functions of a reducing agent and a leaching agent, heats slurry through steam, increases the reaction pressure more greatly through the steam pressure and the pressurization of mixed gas, and accelerates the SO2The rate of dissolving the solution enhances the reaction rate of the reduction process and leaching of the high valence metals.
(6) The pressure is increased only by the temperature rise, the pressure-increasing capacity is limited, and if the temperature is increased, the reaction temperature can be increased, but a large amount 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 the connection of the device according to an embodiment of the present invention.
Detailed Description
The compositions of the electrode powders in examples 1 to 3 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1 Positive active powder chemistry
Example 1
And crushing the waste lithium batteries into small pieces of 3cm, and winnowing to obtain the diaphragm. And (3) pyrolyzing the crushed small blocks at 550 ℃ for 2h, and then screening by a 100-mesh sieve to obtain the superfine powder.
Mixing the electrode powder with deionized water, and controlling the liquid-solid ratio to be 5: 1, mixing slurry in a slurry mixing tank, pumping the slurry after mixing slurry into a five-compartment horizontal autoclave through a charging pump, reacting at the temperature of 100 ℃, and introducing gas (volume ratio SO)2：N23: 7) the flow rate of the introduced gas is 1.04kg/h, the total pressure is 0.5MPa (the gas partial pressure is 0.4MPa), the stirring speed is 400 r/m, the retention time is controlled at 90min, and the exhaust port of the high-pressure kettle is opened intermittently at intervals of 30min for 5 min. And discharging the pressure reduction leached slurry from the fifth compartment, and performing liquid-solid separation after temperature reduction and pressure reduction through a flash tank.
Under the process conditions, the leaching rates of Ni, Co, Mn and Li are respectively 98.7%, 98.6%, 98.5% and 99.2%. The utilization of sulfur dioxide was 93.5%.
Example 2:
and crushing the waste lithium batteries into small pieces of 3cm, and winnowing to obtain the diaphragm. And (3) pyrolyzing the crushed small blocks at 550 ℃ for 2h, and then screening by a 100-mesh sieve to obtain the superfine powder.
Mixing the electrode powder with deionized water, and controlling the liquid-solid ratio to be 5: 1, mixing slurry in a slurry mixing tank, pumping the slurry after mixing slurry into a five-compartment horizontal autoclave through a charging pump, reacting at the temperature of 100 ℃, and introducing gas (volume ratio SO)2：N23: 7) the flow rate of the introduced gas is 1.04kg/h, the total pressure is 0.2MPa (the gas partial pressure is 0.1MPa), the stirring speed is 400 r/m, and the residence time is controlledAnd (5) controlling the temperature for 90min, and intermittently opening the exhaust port of the high-pressure kettle every 30min to exhaust for 5 min. And discharging the pressure reduction leached slurry from the fifth compartment, and performing liquid-solid separation after temperature reduction and pressure reduction through a flash tank.
Under the process conditions, the leaching rates of Ni, Co, Mn and Li are respectively 92.4%, 88.6%, 90.4% and 93.2%. The utilization rate of sulfur dioxide is 92.3%.
Comparative example 1:
and crushing the waste lithium batteries into small pieces of 3cm, and winnowing to obtain the diaphragm. And (3) pyrolyzing the crushed small blocks at 550 ℃ for 2h, and then screening by a 100-mesh sieve to obtain the superfine powder.
Mixing the electrode powder with deionized water, and controlling the liquid-solid ratio to be 5: 1, mixing slurry in a slurry mixing tank, pumping the slurry after mixing slurry into a five-compartment horizontal autoclave through a charging pump, reacting at the temperature of 100 ℃, and introducing gas (volume ratio SO)2：N25: 5) the flow rate of the introduced gas is 1.04kg/h, the total pressure is 0.5MPa (the gas partial pressure is 0.4MPa), the stirring speed is 400 r/m, the retention time is controlled at 90min, and the exhaust port of the high-pressure kettle is opened intermittently at intervals of 30min for 5 min. And discharging the pressure reduction leached slurry from the fifth compartment, and performing liquid-solid separation after temperature reduction and pressure reduction through a flash tank.
Under the process conditions, the leaching rates of Ni, Co, Mn and Li are respectively 98.8%, 98.7%, 98.6% and 99.2%. The utilization of sulfur dioxide was 82.4%.
Comparative example 2:
and crushing the waste lithium batteries into small pieces of 3cm, and winnowing to obtain the diaphragm. And (3) pyrolyzing the crushed small blocks at 550 ℃ for 2h, and then screening by a 100-mesh sieve to obtain the superfine powder.
Mixing the electrode powder with deionized water, and controlling the liquid-solid ratio to be 5: 1, mixing slurry in a slurry mixing tank, pumping the slurry after mixing slurry into a five-compartment horizontal autoclave through a charging pump, reacting at the temperature of 100 ℃, and introducing gas (volume ratio SO)2：N23: 7) the flow rate of the introduced gas is 1.04kg/h, the total pressure is 0.2MPa (the gas partial pressure is 0.1MPa), the stirring speed is 400 r/m, the retention time is controlled at 90min, and no gas is discharged in the reaction process. And discharging the pressure reduction leached slurry from the fifth compartment, and performing liquid-solid separation after temperature reduction and pressure reduction through a flash tank.
Under the process conditions, the leaching rates of Ni, Co, Mn and Li are 82.4%, 72.6%, 78.4% and 85.2%, respectively. The utilization rate of sulfur dioxide was 65.3%.
Comparative example 2 on the basis of example 2, the reaction process does not exhaust gas, and the leaching rates of Ni, Co, Mn and Li and the utilization rate of sulfur dioxide are greatly reduced.
Example 3
And crushing the waste lithium batteries into small pieces of 3cm, and winnowing to obtain the diaphragm. And (3) pyrolyzing the crushed small blocks at 550 ℃ for 2h, and then screening by a 100-mesh sieve to obtain the superfine powder.
Mixing the polar powder with deionized water, and controlling the liquid-solid ratio to be 4: 1, mixing slurry in a slurry mixing tank, pumping the slurry after mixing slurry into a five-compartment horizontal autoclave through a charging pump, reacting at the temperature of 80 ℃, and introducing gas (volume ratio SO)2：N22: 8) the flow rate of the introduced gas is 1.56kg/h, the total pressure is 1MPa (the gas partial pressure is 0.9MPa), the stirring speed is 400 r/m, the retention time is controlled at 60min, and the exhaust port of the high-pressure kettle is opened intermittently at intervals of 20min to exhaust for 3 min. And discharging the pressure reduction leached slurry from the fifth compartment, and performing liquid-solid separation after temperature reduction and pressure reduction through a flash tank.
Under the process conditions, the leaching rates of Ni, Co, Mn and Li are respectively 99.4%, 99.5%, 99.2% and 99.9%. The utilization rate of sulfur dioxide is 94.3%.
Example 4
And crushing the waste lithium batteries into small pieces of 3cm, and winnowing to obtain the diaphragm. And (3) pyrolyzing the crushed small blocks at 550 ℃ for 2h, and then screening by a 100-mesh sieve to obtain the superfine powder.
Mixing the electrode powder with deionized water, and controlling the liquid-solid ratio to be 6: 1, mixing slurry in a slurry mixing tank, pumping the slurry after mixing slurry into a five-compartment horizontal autoclave through a charging pump, reacting at the temperature of 110 ℃, and introducing gas (volume ratio SO)2: ar is 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 1.1MPa), the stirring speed is 400 r/m, the retention time is controlled at 50min, and the exhaust port of the high-pressure kettle is opened intermittently at intervals of 20min for 3 min. And discharging the pressure reduction leached slurry from the fifth compartment, and performing liquid-solid separation after temperature reduction and pressure reduction through a flash tank.
Under the process conditions, the leaching rates of Ni, Co, Mn and Li are respectively 99.5%, 99.6%, 99.4% and 99.9%. The utilization rate of sulfur dioxide is 95.6%.
Example 5
And crushing the waste lithium batteries into small pieces of 3cm, and winnowing to obtain the diaphragm. And (3) pyrolyzing the crushed small blocks at 550 ℃ for 2h, and then screening by a 100-mesh sieve to obtain the superfine powder.
Mixing the electrode powder with deionized water, and controlling the liquid-solid ratio to be 6: 1, mixing slurry in a slurry mixing tank, pumping the slurry after mixing slurry into a five-compartment horizontal autoclave through a charging pump, reacting at the temperature of 110 ℃, and introducing gas (volume ratio SO)2: ar is 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 1.1MPa), the stirring speed is 400 r/m, the retention time is controlled at 50min, and the exhaust port of the high-pressure kettle is opened intermittently at intervals of 20min for 3 min. And discharging the pressure reduction leached slurry from the fifth compartment, and performing liquid-solid separation after temperature reduction and pressure reduction through a flash tank.
Under the process conditions, the leaching rates of Ni, Co, Mn and Li are respectively 99.5%, 99.6%, 99.5% and 99.9%. The utilization of sulfur dioxide was 75.4%.
Example 5 on the basis of example 4, SO2The proportion is increased to 90 percent, the inert gas accounts for 10 percent, the leaching rates of Ni, Co, Mn and Li are basically not influenced, but the utilization rate of sulfur dioxide is greatly reduced.
Claims (10)
1. A method for recovering valuable metals in anode materials of waste lithium ion batteries by pressure reduction is characterized by comprising 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 introducing sulfur dioxide and inert gas or mixed gas of the sulfur dioxide and the inert gas respectively to maintain the pressure in the autoclave at 0.2-2 MPa, wherein the volume ratio of the inert gas is 0-80%.
2. The method for recovering valuable metals from the positive electrode materials of the waste lithium ion batteries through pressure reduction according to claim 1, wherein normal exhaust ports of the high-pressure kettle are opened for 3-8 min every 20-60 min, and then sulfur dioxide and inert gas or mixed gas of the sulfur dioxide and the inert gas are respectively added.
3. The method for recovering valuable metals from the positive electrode materials of the waste lithium ion batteries through pressure reduction according to claim 1, wherein the volume ratio of the sulfur dioxide to the inert gas is (2-4): (6-8).
4. The method for recovering valuable metals in the anode materials of waste lithium ion batteries through pressure reduction according to claim 1, wherein the inert gas is N2Or Ar.
5. The method for recovering valuable metals in the positive electrode materials of the waste lithium ion batteries through pressure reduction according to any one of claims 1 to 4, wherein the leaching temperature in the autoclave is 25 ℃ to 150 ℃.
6. The method for recovering valuable metals from the positive electrode materials of the waste lithium ion batteries through pressure reduction according to any one of claims 1 to 4, wherein the stirring speed is 300 to 800 revolutions per minute.
7. The method for recovering valuable metals from the positive electrode materials of the waste lithium ion batteries through pressure reduction according to any one of claims 1 to 4, wherein the leaching time in the autoclave is 20min to 120 min.
8. The method for recovering valuable metals from the anode materials of the waste lithium ion batteries through pressure reduction according to any one of claims 1 to 4, wherein the liquid-solid ratio of the anode powder to the deionized water is 3: 1-8: 1.
9. The method for recovering valuable metals from the positive electrode materials of the waste lithium ion batteries through pressure reduction according to any one of claims 1 to 4, wherein the preparation method of the positive electrode powder of the waste lithium ion batteries is to crush, pyrolyze and screen the waste lithium ion batteries to obtain the positive electrode powder of the waste lithium ion batteries.
10. The utility model provides a system for valuable metal among old and useless lithium ion battery cathode material is retrieved in pressurization reduction, its characterized in that, including size mixing tank (1), charge pump (2), autoclave (3), flash tank (4) that connect gradually, its characterized in that, the lower part is regional to utilize a plurality of baffles to cut apart into and has a plurality of compartments (5) in autoclave (3), every compartment (5) bottom is provided with air inlet (6), every be provided with stirring rake (7) in compartment (5), one side at autoclave (3) top is provided with inlet (8), the opposite side at autoclave (3) top is provided with gas vent (9) and liquid outlet (10), liquid outlet (10) with flash tank (4) intercommunication.
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