CN113502396A - Method for safely leaching waste battery and application - Google Patents
Method for safely leaching waste battery and application Download PDFInfo
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- CN113502396A CN113502396A CN202110601341.4A CN202110601341A CN113502396A CN 113502396 A CN113502396 A CN 113502396A CN 202110601341 A CN202110601341 A CN 202110601341A CN 113502396 A CN113502396 A CN 113502396A
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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
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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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
- 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
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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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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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
- C22B47/00—Obtaining manganese
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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
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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
- 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
Abstract
The invention belongs to the technical field of waste battery recovery, and discloses a method for safely leaching a waste battery and application thereof, wherein the method comprises the following steps: discharging, roasting and screening the waste lithium battery to obtain copper-aluminum foil and battery powder; adding the battery powder into water, and adding a flotation agent for flotation to obtain a floating material and a precipitate; leaching the floating material with alkali liquor, and filtering to obtain filtrate b and filter residue a; washing the filter residue a, filtering to obtain a filter residue c, and adding a leaching agent and a reducing agent for leaching to obtain a leaching solution. The method can remove the aluminum in the waste lithium battery from the source by combining safe, efficient and low-energy-consumption physical methods such as roasting, screening and flotation and chemical methods such as dilute alkali dissolution.
Description
Technical Field
The invention belongs to the technical field of waste battery recovery, and particularly relates to a method for safely leaching a waste battery and application thereof.
Background
The waste lithium ion battery is composed of a positive electrode, a negative electrode, an electrolyte, a diaphragm and the like. The negative electrode is composed of graphite, a binder, a conductive agent and a current collector, and the positive electrode is prepared by coating active substance powder, the binder and the conductive agent on the current collector. Among the metals having potential recycling value are Ni, Mn, Co, Li, Al, etc.
The present useless lithium ion battery recovery processing mainly includes that the particulate matter that obtains waste lithium battery powder after carrying out a series of operations such as coarse crushing, physical screening, fine-crushing to useless lithium ion battery, but the useless lithium battery powder of retrieving contains low volume aluminium sediment granular impurities, and the granularity size of impurity is close with useless lithium ion battery powder, mixes together with granule such as active substance powder, binder, can react with acid-base, therefore aluminium sediment impurity granule handles the degree of difficulty great. Because flammable and explosive hydrogen is generated in the recovery process of the aluminum and the subsequent valuable metals, the method is dangerous.
And at present, the anode material prepared by using hydrometallurgy recovery mostly faces the problem of overproof aluminum content, the treatment method mainly focuses on the front-stage treatment of the battery, and acid leaching, high-temperature heat treatment or alkali leaching are adopted, but the three methods have respective defects, the acid leaching cost is high, the unsafe problem of hydrogen generation is also generated, the high-temperature treatment energy consumption is high, aluminum can not be removed, and the aluminum content in the anode material prepared after the alkali leaching is used for removing the aluminum is still higher than the standard of the battery grade. Therefore, it is necessary to improve the removal rate of aluminum slag particles in the battery powder particles and improve the safety of the leaching process of metals such as Ni, Co, Li, and the like.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a safe leaching method and application of waste batteries, and the method can remove aluminum in the waste batteries from the source by combining safe, efficient and low-energy-consumption physical methods such as roasting, sorting and flotation and chemical methods such as dilute alkali dissolution.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for leaching a waste battery comprises the following steps:
(1) discharging, roasting and screening the waste lithium battery to obtain copper-aluminum foil and battery powder;
(2) adding the battery powder into water, and adding a flotation agent for flotation to obtain a floating material and a precipitate;
(3) leaching the floating material with alkali liquor, and filtering to obtain filtrate b and filter residue a;
(4) washing the filter residue a, filtering to obtain a filter residue c, adding a leaching agent and a reducing agent for leaching to obtain the Li-containing material+、Co2+、Mn2+、Ni2+An acid solution of (a).
Preferably, in the step (1), the roasting temperature is 240-580 ℃, the roasting time is 1.5-5 h, and the roasting temperature rise speed is 5-30 ℃/min.
Preferably, in the step (1), the gas generated by the roasting is collected by using lye.
Further preferably, the alkali liquor is at least one of sodium hydroxide, magnesium hydroxide, potassium hydroxide, barium hydroxide, zinc hydroxide or calcium hydroxide.
More preferably, the concentration of the alkali liquor is 0.01-0.15 mol/L.
Preferably, in the step (2), the solid-to-liquid ratio of the battery powder to the water is 1 (1.5-4) g/ml.
Preferably, in the step (2), the flotation agent is one of oxidized paraffin soap, sodium oleate or dodecylamine.
Preferably, in the step (2), the density of the flotation agent in the flotation is 1.80-2.65 g/cm3。
Preferably, in the step (3), the alkali solution is at least one of sodium hydroxide, magnesium hydroxide, potassium hydroxide or calcium hydroxide.
Further preferably, the concentration of the alkali liquor is 0.10-0.80 mol/L.
Preferably, in the step (3), the solid-to-liquid ratio of the floating materials to the alkali liquor is 5 g/L-15 g/L.
The principle of flotation aluminum precipitation:
the density of the aluminum slag is 2.70g/cm3The density of the waste lithium battery powder is as follows: the bulk density of the lithium iron phosphate is 1.523g/cm3Tap density of 1.2g/cm3The tap density of the nickel cobalt lithium manganate is between 2.0 and 2.4g/cm3. And performing flotation by utilizing the density difference, wherein the density of the aluminum slag is greater than that of the waste lithium battery powder.
Preferably, in the step (3), the leaching time is 10-120 min, and the leaching temperature is 30-90 ℃.
Preferably, in the step (3), the generated gas is vented during the leaching process, and the concentration of the hydrogen in the exhaust port is monitored by a hydrogen detection instrument; aeration maintains hydrogen concentrations below 0.5% VOL (air to volume) or 5000 ppm.
Preferably, in the step (4), the solid-to-liquid ratio during leaching is 2-30 g/L.
Preferably, in the step (4), the leaching time is 1-6 h, and the leaching temperature is 40-95 ℃.
Preferably, in the step (4), the leaching agent is an organic acid.
Preferably, in the step (4), the concentration of the organic acid is 0.5-5 mol/L.
Preferably, in step (4), the organic acid is tartaric acid.
Preferably, in step (4), the reducing agent is hydrogen peroxide.
Preferably, in the step (4), the washed water washing liquid e and the filtrate d of the step (3) are mixed to obtain a mixed liquid, and the mixed liquid can be used as the alkali liquor in the step (3) for recycling.
The invention also provides application of the waste battery leaching method in valuable metal recovery.
The leaching solution obtained by the method for leaching the waste battery contains Li+、Co2+、Mn2+、Ni2+The acid solution of (3) can further recover Li, Co, Mn and Ni.
Compared with the prior art, the invention has the following beneficial effects:
1. the method can remove the aluminum in the waste lithium battery from the source by combining safe, efficient and low-energy-consumption physical methods such as roasting, screening and flotation and chemical methods such as dilute alkali dissolution.
2. The method comprises the steps of separating aluminum foil and battery powder by roasting and screening, settling impurities such as aluminum slag, copper and the like in the battery powder by using a flotation agent, further removing aluminum, avoiding generation of a large amount of hydrogen in the subsequent leaching process, improving the safety of the leaching process, leaching by using dilute alkali, and dissolving aluminum without dissolving waste lithium battery powder by using the dilute alkali, so that residual aluminum slag can be removed completely, and the method is also used for avoiding generation of hydrogen in the leaching process of positive active substance powder and improving the leaching safety.
3. When the waste lithium battery powder is roasted, the adhesive property of the adhesive (polyvinylidene fluoride and polytetrafluoroethylene) is reduced, the waste lithium battery powder becomes brittle, and meanwhile, the waste lithium battery powder is easy to fall off from a current collector through vibration, the adhesive and the conductive agent graphite are gradually decomposed and combusted at high temperature, the roasting process changes the molecular structure of the positive electrode material, reduces the charge of transition metal ions in the positive electrode material, and creates conditions for subsequent leaching and recovery. After roasting, the waste lithium battery powder mainly takes black as main material, the aluminum foil is silver bright color, the copper foil is light yellow, and most of the aluminum foil and the copper foil can be conveniently sorted and removed by utilizing a color sorter for screening.
4. According to the method, the consumption of acid and alkali can be reduced by adopting a low solid-liquid ratio in two leaching processes, aluminum and anode active substance powder can be further efficiently leached, and meanwhile, the filtrate b and the washing liquid d are mixed to obtain a mixed liquid which can be recycled, so that the consumption of the alkali is reduced.
5. Compared with the leaching of inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and the like, the leaching of the organic acid tartaric acid is adopted, so that the leaching reaction is relatively mild while the leaching rate of valuable metal elements is ensured, and the adverse effects of generated gases such as sulfur dioxide, hydrochloric acid and the like on the environment and equipment are avoided. Meanwhile, the boiling point of tartaric acid is about 399 ℃, and compared with hydrochloric acid, the tartaric acid is not easy to volatilize at the leaching reaction temperature of 30-95 ℃. Therefore, the tartaric acid is adopted for leaching, and the whole leaching process is more environment-friendly and safer.
Drawings
Fig. 1 is a flow chart of a method for safely leaching a waste battery according to embodiment 1 of the invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The method for safely leaching the waste battery comprises the following specific steps:
(1) the recycled lithium iron phosphate battery is disassembled to discharge, after mechanical coarse crushing, the crushed waste lithium battery pieces are placed in a sintering kiln to be roasted, the roasting temperature is controlled to be 350 ℃, the roasting time is 4.8 hours, the temperature rising speed is controlled to be about 15 ℃/min, gas generated by roasting is collected by 0.01mol/L sodium hydroxide alkali liquor, the roasted waste lithium battery pieces are subjected to vibration screening, a color sorter sorts aluminum foils and copper foils, and then the sorted waste lithium battery powder is ground by a ball grinder;
(2) adding waste lithium battery powder after ball milling into pure water, wherein the waste lithium battery powder comprises the following components in parts by weight: the solid-to-liquid ratio of water is 1:1.5g/ml, the floating impurities are removed by stirring, and sodium oleate is added until the density of the flotation liquid is about 2.06g/cm3Recovering the floating material;
(3) leaching the floating material by using 0.15mol/L sodium hydroxide, controlling the leaching time to be 104min, controlling the solid-to-liquid ratio during leaching to be 8g/L, controlling the temperature of a reaction system to be about 53 ℃, rapidly filtering until no gas is generated to obtain filter residue a and filter liquor b, ventilating to discharge the generated gas, and monitoring the concentration of the hydrogen at an exhaust port by using a rapid hydrogen detector;
(4) washing the filter residue a with pure water for 4 times on the basis of the step (3), filtering and collecting a washing liquid d, separating to obtain a filter residue c, leaching the filter residue c with 0.5mol/L tartaric acid and 1.5% hydrogen peroxide by volume, wherein the solid-to-liquid ratio is 5g/L, the temperature of a leaching reaction system is controlled at 42 ℃, and filtering to obtain the Li-containing solution after leaching is finished+、Co2+、Mn2+、Ni2+Mixing the acid solution (leachate g), the residue f, the filtrate b and the water washing solution d according to the volume ratio of 1:1, and using the mixed solution for leaching in the step (3).
Fig. 1 is a flow chart of a method for safely leaching waste batteries according to embodiment 1 of the invention, and as can be seen from fig. 1, in the waste battery leaching, aluminum is mainly removed through four steps of screening, sorting, flotation and alkali liquor addition.
Example 2
The method for safely leaching the waste battery comprises the following specific steps:
(1) the recycled lithium iron phosphate battery is disassembled to discharge, after mechanical coarse crushing, the crushed waste lithium battery pieces are placed in a sintering kiln to be roasted, the roasting temperature is controlled to be 580 ℃, the roasting time is stabilized for 2.4 hours, the temperature rising speed is controlled to be 23 ℃/min, gas generated by roasting is collected by 0.04mol/L sodium hydroxide alkali liquor, the roasted waste lithium battery pieces are subjected to vibration screening, a color sorter sorts aluminum foils and copper foils, and then the sorted waste lithium battery powder is ground by a ball grinder;
(2) adding waste lithium battery powder after ball milling into pure water, wherein the waste lithium battery powder comprises the following components in parts by weight: the solid-to-liquid ratio of water is 1:2.5g/ml, the floating impurities are removed by stirring, sodium oleate is added until the density of the flotation liquid is about 2.37g/cm3Recovering the floating material;
(3) leaching the floating material by using 0.38mol/L calcium hydroxide, controlling the leaching time to be 73min, controlling the solid-to-liquid ratio during leaching to be 8g/L, controlling the temperature of a reaction system to be 65 ℃, rapidly filtering until gas is not generated to obtain filter residue a and filter liquid b, ventilating to discharge the generated gas, and monitoring the concentration of the hydrogen at an exhaust port by using a rapid hydrogen detector;
(4) washing the filter residue a with pure water for 2 times on the basis of the step (3), filtering and collecting a washing liquid d, separating to obtain a filter residue c, leaching the filter residue c with 2.5mol/L tartaric acid and 3.4% hydrogen peroxide by volume ratio, wherein the solid-to-liquid ratio is 5g/L during leaching, controlling the temperature of a leaching reaction system at 58 ℃, and filtering after leaching to obtain the Li-containing material+、Co2+、Mn2+、Ni2+Mixing the acid solution, the residue f, the filtrate b and the water washing liquid d according to the volume ratio of 1:1.4, and using the mixed liquid for leaching in the step (3).
Example 3
The method for safely leaching the waste battery comprises the following specific steps:
(1) the recycled lithium iron phosphate battery is disassembled to discharge, after mechanical coarse crushing, the crushed waste lithium battery pieces are placed in a sintering kiln to be roasted, the roasting temperature is controlled to be 420 ℃, the roasting time is stabilized for 3.5 hours, the temperature rising speed is controlled to be 18 ℃/min, gas generated by roasting is collected by 0.09mol/L sodium hydroxide alkali liquor, the roasted waste lithium battery pieces are subjected to vibration screening, a color sorter sorts aluminum foils and copper foils, and then the sorted waste lithium battery powder is ground by a ball grinder;
(2) adding waste lithium battery powder after ball milling into pure water, wherein the waste lithium battery powder comprises the following components in parts by weight: the solid-to-liquid ratio of water is 1:2.5g/ml, the floating impurities are removed by stirring, sodium oleate is added until the density of the flotation liquid is about 2.18g/cm3Recovering the floating material;
(3) leaching the floating material by using 0.67mol/L sodium hydroxide, controlling the leaching time to be 24min, controlling the solid-to-liquid ratio during leaching to be 15g/L, controlling the temperature of a reaction system to be about 70 ℃, rapidly filtering until no gas is generated to obtain filter residue a and filter liquor b, ventilating to discharge the generated gas, and monitoring the concentration of the hydrogen at an exhaust port by using a rapid hydrogen detector;
(4) washing the filter residue a with pure water for 3 times on the basis of the step (3), filtering and collecting a washing liquid d, separating to obtain a filter residue c, leaching the filter residue c with 3.8mol/L tartaric acid and 5.5% hydrogen peroxide by volume, wherein the solid-to-liquid ratio is 12g/L during leaching, controlling the temperature of a leaching reaction system at 61 ℃, and filtering after leaching to obtain the Li-containing solution+、Co2+、Mn2+、Ni2+Mixing the acid solution, the residue f, the filtrate b and the water washing liquid d according to the volume ratio of 1:1.8, and using the mixed liquid for leaching in the step (3).
Example 4
The method for safely leaching the waste battery comprises the following specific steps:
(1) the recycled nickel cobalt lithium manganate battery is disassembled to discharge, after mechanical coarse crushing, the crushed waste lithium battery pieces are placed in a sintering kiln to be roasted, the roasting temperature is controlled to be 550 ℃, the roasting time is controlled to be 1h, the temperature rising speed is controlled to be 20 ℃/min, gas generated by roasting is collected by 0.12mol/L sodium hydroxide alkali liquor, the roasted waste lithium battery pieces are subjected to vibration screening, a color sorter sorts aluminum foils and copper foils, and then the sorted waste lithium battery powder is ground by a ball grinder;
(2) adding waste lithium battery powder after ball milling into pure water, wherein the waste lithium battery powder comprises the following components in parts by weight: the solid-to-liquid ratio of water is 1:2g/ml, the floating impurities are removed by stirring, and sodium oleate is added until the density of the flotation liquid is about 2.44g/cm3Recovering the floating material;
(3) leaching the floating material by using 0.78mol/L calcium hydroxide, controlling the leaching time to be 19min, controlling the solid-to-liquid ratio during leaching to be 20g/L, controlling the temperature of a reaction system to be about 87 ℃, rapidly filtering until no gas is generated, obtaining filter residue a and filter liquor b, ventilating to discharge the generated gas, and monitoring the concentration of the hydrogen at an exhaust port by using a rapid hydrogen detector;
(4) washing the filter residue a with pure water for 3 times on the basis of the step (3), filtering and collecting a washing liquid d, separating to obtain a filter residue c, leaching the filter residue c with 4.78mol/L tartaric acid and 8.0% hydrogen peroxide by volume ratio, wherein the solid-to-liquid ratio is 15g/L during leaching, controlling the temperature of a leaching reaction system at 94 ℃, and filtering after leaching to obtain the Li-containing material+、Co2+、Mn2+、Ni2+Mixing the acid solution, the residue f, the filtrate b and the water washing liquid d according to the volume ratio of 1:2.3, and using the mixed liquid for leaching in the step (3).
Comparative example 1
A method for leaching a waste battery comprises the following specific steps:
the difference from example 1 is that: flotation is not carried out in the step (2).
Comparative example 2
A method for leaching a waste battery comprises the following specific steps:
the difference from example 1 is that: and (4) leaching without adding sodium hydroxide in the step (3).
Comparative example 3
The difference from example 1 is that: and (4) leaching by adopting sulfuric acid, wherein other reaction conditions are consistent. The method comprises the following steps: 1.3mol/L sulfuric acid and 1.5 percent hydrogen peroxide are leached, the solid-to-liquid ratio is 5g/L during leaching, and the temperature of a leaching reaction system is controlled at 60 ℃.
Analytical comparison of examples 1, 2, 3, 4 with comparative examples 1, 2, 3:
in table 1, aluminum is measured by spectrophotometry, hydrogen concentration is the concentration of hydrogen at the exhaust port measured by a rapid hydrogen meter, the mass fraction (%) of aluminum in the waste lithium battery powder is the mass fraction (%) of aluminum in the waste battery powder/the mass of waste battery powder 100 in step (1), the mass fraction (%) of aluminum in the floating material is the mass of aluminum in the floating material/the mass of the floating material, and the mass fraction (%) of aluminum in the filter residue c is the mass of aluminum in the filter residue c/the mass of filter residue c 100.
As shown in table 1, in examples 1, 2, 3 and 4, the mass of aluminum in the residue c in step (3) is reduced by 0.53%, 0.16%, 0.60% and 0.26% respectively compared with the mass of aluminum in the waste lithium battery powder in step (1); comparing example 1 with comparative example 1, step (2) reduces the hydrogen concentration by 0.23% through flotation; comparing the example 1 with the comparative example 2, in the step (3), the aluminum is leached by alkali, so that the aluminum mass in the filter residue c is reduced by 0.11%; comparative example 3, where sulfuric acid was used for leaching, the reaction was vigorous, whereas examples 1, 2, 3, 4 and ratios 1, 2, where the leaching reaction was mild. Therefore, the steps (2) and (3) can effectively reduce the aluminum content in the waste lithium battery powder, reduce the generation amount of hydrogen and improve the safety during leaching.
TABLE 1 aluminum and hydrogen test values for examples and comparative examples
Compared with leaching of inorganic acids such as sulfuric acid and the like, the leaching reaction of the organic acid tartaric acid is relatively mild while the leaching rate of valuable metal elements is ensured, and adverse effects of generated gas on environment and equipment are avoided.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A method for leaching a waste battery is characterized by comprising the following steps:
(1) discharging, roasting and screening the waste lithium battery to obtain copper-aluminum foil and battery powder;
(2) adding the battery powder into water, and adding a flotation agent for flotation to obtain a floating material and a precipitate;
(3) leaching the floating material with alkali liquor, and filtering to obtain filtrate b and filter residue a;
(4) washing the filter residue a, filtering to obtain filter residue c, adding a leaching agent and a reducing agent for leaching to obtain the Li-containing material+、Co2+、Mn2+、Ni2+An acid solution of (a).
2. The method according to claim 1, wherein in the step (1), the roasting temperature is 240-580 ℃, the roasting time is 1.5-5 h, and the roasting temperature rise speed is 5-30 ℃/min.
3. The method of claim 1, wherein in step (2), the flotation agent is one of oxidized paraffin soap, sodium oleate or dodecylamine.
4. The method according to claim 1, wherein in the step (3), the alkali solution is at least one of sodium hydroxide, magnesium hydroxide, potassium hydroxide or calcium hydroxide.
5. The method according to claim 1, wherein in the step (3), the solid-to-liquid ratio in the leaching is 5-15 g/L; in the step (4), the solid-to-liquid ratio during leaching is 2-30 g/L.
6. The method of claim 1, wherein in step (4), the leaching agent is an organic acid.
7. The method according to claim 6, wherein in the step (4), the organic acid is tartaric acid.
8. The method according to claim 1, wherein in the step (4), the reducing agent is hydrogen peroxide.
9. The method as claimed in claim 1, wherein in the step (4), the washed water washing liquid d and the filtrate b of the step (3) are mixed according to the ratio of (1-2) to 1 to obtain a mixed liquid, and the mixed liquid can be used as the alkali liquor in the step (3) for recycling.
10. Use of a process for the safe leaching of spent batteries according to any one of claims 1 to 9 for the recovery of valuable metals.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110601341.4A CN113502396A (en) | 2021-05-31 | 2021-05-31 | Method for safely leaching waste battery and application |
| HU2200293A HUP2200293A1 (en) | 2021-05-31 | 2021-12-30 | Procedure for the safe leaching and reuse of spent batteries |
| PCT/CN2021/142932 WO2022252602A1 (en) | 2021-05-31 | 2021-12-30 | Method for safely leaching waste battery and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115367732A (en) * | 2022-09-20 | 2022-11-22 | 中南大学 | Method for recycling industrial sulfate solid waste and waste nickel-cobalt-manganese-lithium battery in synergic manner |
| WO2022252602A1 (en) * | 2021-05-31 | 2022-12-08 | 广东邦普循环科技有限公司 | Method for safely leaching waste battery and application |
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| HUP2200293A1 (en) | 2023-05-28 |
| WO2022252602A1 (en) | 2022-12-08 |
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