CN115109934B - Method for separating and extracting valuable metals from waste batteries - Google Patents
Method for separating and extracting valuable metals from waste batteries Download PDFInfo
- Publication number
- CN115109934B CN115109934B CN202211050220.6A CN202211050220A CN115109934B CN 115109934 B CN115109934 B CN 115109934B CN 202211050220 A CN202211050220 A CN 202211050220A CN 115109934 B CN115109934 B CN 115109934B
- Authority
- CN
- China
- Prior art keywords
- roasting
- leaching
- slag
- electrode powder
- positive electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
-
- 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
-
- 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
- C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
-
- 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
-
- 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
- H01M10/54—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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a method for separating and extracting valuable metals from waste batteries, which comprises the following steps: (1) Pretreating waste lithium iron phosphate batteries and waste nickel cobalt lithium manganate batteries to obtain positive electrode powder and negative electrode powder, and mixing the two kinds of positive electrode powder and an additive to obtain mixed positive electrode powder; the additive is a mixture of aluminum sulfate and phosphoric acid; (2) Carrying out primary roasting on the mixed anode powder to obtain primary roasting slag; (3) Leaching the first-stage roasting slag to obtain a lithium-rich leaching solution and leaching slag; (4) Adding a reducing agent into the leaching slag, carrying out secondary roasting, and collecting to obtain secondary roasting slag and roasting smoke; (5) And (3) carrying out roasting flue gas post-treatment on the second-stage roasting slag to obtain a nickel-iron alloy, cobalt-containing slag, manganese-containing slag and elemental phosphorus. The method realizes the step-by-step and efficient extraction of elements in the waste power battery, avoids the adverse effect of lithium fluoride on the subsequent leaching recovery rate of lithium, and has the advantages of high resource utilization rate, small reagent addition amount, good environmental protection benefit and the like.
Description
Technical Field
The invention relates to the field of battery material recycling, in particular to a method for separating and extracting valuable metals from waste batteries.
Background
In recent years, the electric automobile industry is vigorously developed, and the demand and the maintenance quantity of lithium batteries are increased day by day. However, the service life of the power battery is often only 3-5 years, which results in the generation of a large amount of waste power batteries, and the power batteries contain a large amount of lithium, nickel, cobalt, iron, organic matters and the like, and have the dual properties of resource and environmental hazard. The resource bad utilization is performed, which is very important. At present, the recovery of waste power batteries mainly comprises the steps of dismantling, crushing, sorting, chemically treating and recovering valuable elements and the like. The patent with the application number of CN201610095291.6 discloses a method for preparing a ternary cathode material precursor by utilizing a recycled lithium ion battery material, the method comprises the steps of dissolving the recycled lithium ion battery cathode material by sulfuric acid and hydrogen peroxide to obtain a leaching solution, removing impurities from the leaching solution, adding nickel sulfate, cobalt sulfate and/or manganese sulfate into the leaching solution, and then adding an ammonia complexing precipitator into the solution to obtain a nickel-cobalt-manganese ternary material precursor precipitate. The patent with the application number of CN202110980730.2 discloses a method for recovering lithium iron phosphate from waste lithium iron phosphate batteries, application of the method and lithium iron phosphate, and the method is mainly characterized in that waste lithium iron phosphate is roasted by adopting microwave reinforcement under protective gas to obtain recrystallized lithium iron phosphate, and the effect of purifying the lithium iron phosphate is achieved by recrystallization. The patent with the application number of CN202110691068.9 discloses a method for recycling lithium, nickel, cobalt and manganese in waste ternary lithium battery materials, which is used for recycling the lithium, nickel, cobalt and manganese in the waste ternary lithium battery materials through the steps of sulfuric acid curing transformation type reduction roasting, alkaline oxidation lithium leaching, micro-acid nickel and cobalt leaching and acid reduction manganese leaching.
The above patent only aims at recovering one waste battery material, and a large amount of reducing agent, precipitator, complexing agent and the like are needed to be added in the treatment process. Meanwhile, the differences of the redox property, the difficulty degree of reducing the anode material into a simple substance and the like of different anode materials are ignored. In addition, in the pretreatment of the waste batteries, because the electrolyte of the power electric batteries is lithium hexafluorophosphate, the lithium hexafluorophosphate is easily decomposed in the pretreatment process and then enters the anode powder and the cathode powder. Fluorine enters into the anode powder obtained by pretreatment, lithium fluoride is easily formed in the roasting process, and the formation of the lithium fluoride seriously influences the leaching recovery rate of subsequent lithium.
Disclosure of Invention
The invention provides a method for separating and extracting valuable metals from waste batteries, which is used for solving the technical problems of more additives, high cost and unsatisfactory leaching recovery rate in the existing waste battery recovery process.
In order to solve the technical problem, the invention adopts the following technical scheme:
a method for separating and extracting valuable metals from waste batteries comprises the following steps:
(1) Pretreating waste lithium iron phosphate batteries to obtain positive electrode powder A and negative electrode powder A, pretreating the waste lithium nickel cobalt manganese batteries to obtain positive electrode powder B and negative electrode powder B, and mixing the positive electrode powder A, the positive electrode powder B and the additive A to obtain mixed positive electrode powder; the additive A is a mixture of aluminum sulfate and phosphoric acid;
(2) Carrying out primary roasting on the mixed anode powder to obtain primary roasting slag;
(3) Leaching the first-stage roasting slag to obtain a lithium-rich leaching solution and leaching slag;
(4) Adding a reducing agent into the leached slag, carrying out secondary roasting, and collecting secondary roasting slag and roasting flue gas; the reducing agent is at least one of the negative electrode powder A and the negative electrode powder B;
(5) Post-treating the second-stage roasting slag to obtain a nickel-iron alloy and cobalt-and manganese-containing slag; and condensing the roasting flue gas to obtain elemental phosphorus, namely completing the separation and extraction of valuable metals in the waste batteries.
The design idea of the technical scheme is that the technical scheme comprises the steps of firstly extracting lithium in mixed positive electrode powder of two batteries by controlling reduction, and then combining nickel and iron in the mixed positive electrode powder to form a nickel-iron alloy by deep reduction, and forming reducing slag together with cobalt and manganese; meanwhile, phosphorus in the mixed positive electrode powder is reduced and enters flue gas, and a phosphorus simple substance is obtained after cooling, so that the stepwise and efficient extraction of different elements in the waste battery is realized; in the separation and extraction process, the technical scheme not only makes full use of the difference of the bonding capacities of the elements contained in the anode materials of different types of power batteries and the difference of the difficulty degree of reducing the anode materials into metal, but also cooperatively treats the waste nickel-cobalt lithium manganate battery and the waste lithium iron phosphate battery, and utilizes the reducibility of the cathode powder, so that substances added in the treatment process are reduced as much as possible, the maximum recycling degree of the waste batteries is realized, and the treatment cost is obviously reduced. In addition, the additive consisting of aluminum sulfate and phosphoric acid is added in the process of roasting at a low temperature, so that the conversion and volatilization of lithium fluoride in the anode material are realized, the formation of the lithium fluoride is effectively avoided (fluorine volatilizes in the form of hydrogen fluoride), the formed lithium fluoride is converted and converted into easily-soluble lithium sulfate, the adverse effect of fluorine element on the subsequent lithium leaching efficiency and effect is avoided, and the reactions related to the additive mainly comprise the following two steps:
F - +Al 2 (SO 4 ) 3 +H 3 PO 4 →HF↑+AlPO 4 ↓+SO 4 2- 、
LiF+Al 2 (SO 4 ) 3 →AlF 3 +Li 2 SO 4 、LiF+Al 2 (SO 4 ) 3 +H 3 PO 4 →HF↑+AlPO 4 ↓+Li 2 SO 4 。
as a further preferable mode of the above-described aspect, in the mixed positive electrode powder, a mass ratio of the iron element in the positive electrode powder a to the nickel element in the positive electrode powder B is (2 to 6): 1. the positive electrode powder A and the positive electrode powder B in the proportion can ensure that the nickel-iron alloy is formed in the subsequent treatment process.
As a further optimization of the technical scheme, the temperature of the first-stage roasting is 400-700 ℃, and the time is 15-90 min.
In a further preferred embodiment of the present invention, the additive a is added in an amount of 2 to 6% by mass of the mixed positive electrode powder, and the mass ratio of phosphoric acid to aluminum sulfate in the additive a is (3 to 4.5): (5.5 to 7).
As a further preferable mode of the above technical solution, when the leaching treatment is performed on the first-stage roasting slag in the step (3), the pH is controlled to be 6.5 to 9.5, the leaching temperature is 25 to 70 ℃, and the leaching time is 30 to 150min.
Preferably, in the step (3), the pH value during the water immersion treatment is controlled by using sulfuric acid with a concentration of 50 to 120g/L or sodium hydroxide with a concentration of 20 to 60g/L.
As a further optimization of the technical scheme, the temperature of the second-stage roasting is 1200-1500 ℃, and the time is 30-120 min.
As a further optimization of the technical scheme, the mass of carbon in the reducing agent added in the two-stage roasting is 8-15% of the mass of the leaching residue.
As a further preference of the above technical scheme, an additive B is further added in the secondary roasting, and the additive B is subjected to secondary roasting together with the leaching residue and the reducing agent; the additive B comprises at least one of calcium oxide, silicon dioxide and manganese dioxide.
In a further preferred embodiment of the present invention, the additive B is added in an amount of 2 to 8% by mass based on the weight of the leached residues.
As a further preferable mode of the above technical solution, the post-treatment operation on the secondary roasting slag in step (5) includes ball milling and magnetic separation processes performed in sequence, the particle size of the secondary roasting slag after ball milling is less than 50 μm, and the magnetic field strength of the magnetic separation process is 100-120 kA/m.
Compared with the prior art, the invention has the advantages that:
(1) The invention fully utilizes the oxidation-reduction potential difference of the anode materials of different power batteries and the reduction property of the cathode material to realize the step-by-step and high-efficiency extraction of elements in the waste power batteries;
(2) The invention realizes the conversion and volatilization of the lithium fluoride in the anode material, and avoids the adverse effect of the lithium fluoride on the subsequent leaching recovery rate of lithium;
(3) The invention has the advantages of high resource utilization rate, less reagent addition, good environmental protection benefit and the like.
Drawings
Fig. 1 is a process flow chart of a method for separating and extracting valuable metals from waste lithium iron phosphate batteries and waste lithium nickel cobalt manganese batteries in example 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1:
the method for separating and extracting valuable metals from waste power batteries comprises the following steps:
(1) Pretreating the waste lithium iron phosphate battery and the waste lithium nickel cobalt manganese oxide battery to obtain lithium iron phosphate positive electrode powder, lithium iron phosphate negative electrode powder, lithium nickel cobalt manganese oxide positive electrode powder and lithium nickel cobalt manganese oxide negative electrode powder;
(2) Mixing the two kinds of positive electrode powder obtained in the step (1), adding an additive A accounting for 4% of the mass of the mixed positive electrode powder, and uniformly mixing to obtain mixed positive electrode powder, wherein the mass ratio of iron in the positive electrode powder of the ferric phosphate lithium battery to nickel in the positive electrode powder of the nickel cobalt lithium manganate in the mixed positive electrode powder is 3:1 (mFe: mNi = 3:1), the additive A is composed of phosphoric acid and aluminum sulfate, the mass of the phosphoric acid is 35%, and the mass of the aluminum sulfate is 65%;
(3) Carrying out primary roasting treatment on the mixed anode powder, wherein the roasting condition is that the roasting temperature is 650 ℃ and the roasting time is 45min, and naturally cooling to room temperature after the reaction is finished to obtain primary roasted sand slag;
(4) Leaching the first-stage roasting slag, wherein the leaching condition is that the leaching temperature is 50 ℃, the solid-to-liquid ratio (g/mL) is 1:5, the leaching time is 60min, the pH value is controlled to be 7.5 in the leaching process (the pH value is controlled by sodium hydroxide of 20-60g/L), filtering treatment is carried out after the leaching is finished, a lithium-rich leaching solution and leaching slag are obtained, and the representation of the lithium and cobalt contents in the leaching solution and the leaching slag shows that the leaching rate of lithium is 95.71%;
(5) Adding a reducing agent into the leaching slag, mixing, and then carrying out secondary roasting to obtain secondary roasting slag and roasting flue gas; the reducing agent is selected from lithium iron phosphate negative electrode powder and nickel cobalt lithium manganate negative electrode powder, and the carbon content in the system is 16% after the reducing agent is added; adding 5% calcium oxide (additive B) into the system, wherein the temperature of the second stage roasting is 1450 ℃, and the roasting time is 60min;
(6) Cooling the roasting flue gas to obtain a solid phosphorus simple substance, and calculating to obtain a phosphorus recovery rate of 78.93%; ball-milling the second-stage roasting slag to ensure that the grain size is less than 106 microns (sieving the second-stage roasting slag by a 150-mesh sieve), and then carrying out magnetic separation under the magnetic field intensity of 115 kA/m to obtain the ferro-nickel alloy and the cobalt-manganese-containing slag, wherein the representation of iron, nickel, manganese and cobalt in each material shows that the recovery rate of iron is 95.27 percent, the recovery rate of nickel is 87.03 percent (the recovery amount is the metal phase amount of nickel and iron entering the material), the recovery rate of cobalt is 92.01 percent, and the recovery rate of manganese is 78.11 percent (the recovery amount is the cobalt and manganese entering the second-stage roasting slag).
Example 2:
as shown in fig. 1, the method for separating and extracting valuable metals from waste power batteries of this embodiment includes the following steps:
(1) Pretreating the waste lithium iron phosphate battery and the waste lithium nickel cobalt manganese oxide battery to obtain lithium iron phosphate positive electrode powder, lithium iron phosphate negative electrode powder, lithium nickel cobalt manganese oxide positive electrode powder and lithium nickel cobalt manganese oxide negative electrode powder;
(2) Mixing the two kinds of positive electrode powder obtained in the step (1), adding an additive A accounting for 4% of the mass of the mixed positive electrode powder, and uniformly mixing to obtain mixed positive electrode powder, wherein the mass ratio of iron in the positive electrode powder of the ferric phosphate lithium battery to nickel in the positive electrode powder of the nickel cobalt lithium manganate in the mixed positive electrode powder is 5:1 (mFe: mNi = 5:1), the additive A is composed of phosphoric acid and aluminum sulfate, the mass of the phosphoric acid is 35%, and the mass of the aluminum sulfate is 65%;
(3) Carrying out primary roasting treatment on the mixed anode powder, wherein the roasting condition is that the roasting temperature is 600 ℃, the roasting time is 45min, and naturally cooling to room temperature after the reaction is finished to obtain primary roasted sand slag;
(4) Leaching the first-stage roasting slag, wherein the leaching conditions comprise a leaching temperature of 50 ℃, a solid-to-liquid ratio (g/mL) of 1:5, a leaching time of 60min and a leaching process pH of 7.5 (controlled by sodium hydroxide of 20-60g/L), filtering after leaching is finished to obtain a lithium-rich leaching solution and leaching slag, and the representation of the lithium and cobalt contents in the leaching solution and leaching slag shows that the leaching rate of lithium is 92.08%;
(5) Adding a reducing agent into the leached slag, mixing, and then carrying out secondary roasting to obtain secondary roasting slag and roasting flue gas; the reducing agent is selected from lithium iron phosphate negative electrode powder and nickel cobalt lithium manganate negative electrode powder, and the carbon content in the system is 16% after the reducing agent is added; adding 3% of calcium oxide and 2% of manganese dioxide (additive B) into the system, wherein the temperature of the second-stage roasting is 1400 ℃, and the roasting time is 60min;
(6) Cooling the roasting flue gas to obtain a solid phosphorus simple substance, and calculating to obtain a phosphorus recovery rate of 78.93%; ball-milling the second-stage roasting slag to ensure that the grain size is smaller than 106 microns (sieving the second-stage roasting slag by a 150-mesh sieve), and then carrying out magnetic separation under the magnetic field intensity of 115 kA/m to obtain the ferro-nickel alloy and the cobalt-manganese-containing slag, wherein the representation of iron, nickel, manganese and cobalt in each material shows that the recovery rate of iron is 95.27 percent, the recovery rate of nickel is 89.63 percent (the recovery rate is the metal phase amount of nickel and iron entering the material), the recovery rate of cobalt is 82.43 percent, and the recovery rate of manganese is 70.15 percent (the recovery rate is the cobalt and manganese entering the second-stage roasting slag).
Example 3:
the method for separating and extracting valuable metals from waste power batteries comprises the following steps:
(1) Pretreating the waste lithium iron phosphate battery and the waste nickel cobalt lithium manganate battery to obtain lithium iron phosphate positive electrode powder, lithium iron phosphate negative electrode powder, lithium nickel cobalt manganese oxide positive electrode powder and lithium nickel cobalt manganese oxide negative electrode powder;
(2) Mixing the two kinds of positive electrode powder obtained in the step (1), adding an additive A accounting for 4% of the mass of the mixed positive electrode powder, and uniformly mixing to obtain mixed positive electrode powder, wherein the mass ratio of iron in the positive electrode powder of the ferric phosphate lithium battery to nickel in the positive electrode powder of the nickel cobalt lithium manganate in the mixed positive electrode powder is 3:1 (mFe: mNi = 3:1), the additive A is composed of phosphoric acid and aluminum sulfate, the mass of the phosphoric acid is 40%, and the mass of the aluminum sulfate is 60%;
(3) Carrying out primary roasting treatment on the mixed anode powder, wherein the roasting condition is that the roasting temperature is 600 ℃, the roasting time is 45min, and naturally cooling to room temperature after the reaction is finished to obtain primary roasted sand slag;
(4) Leaching the first-stage roasting slag, wherein the leaching condition is that the leaching temperature is 60 ℃, the solid-to-liquid ratio (g/mL) is 1:5, the leaching time is 60min, the pH value in the leaching process is controlled to be 7.5 (the pH value is controlled by sodium hydroxide of 20-60g/L), filtering treatment is carried out after the leaching is finished, a lithium-rich leaching solution and leaching slag are obtained, and the representation of the lithium and cobalt contents in the leaching solution and the leaching slag shows that the leaching rate of lithium is 95.47%;
(5) Adding a reducing agent into the leaching slag, mixing, and then carrying out secondary roasting to obtain secondary roasting slag and roasting flue gas; the reducing agent is selected from lithium iron phosphate negative electrode powder and nickel cobalt lithium manganate negative electrode powder, and the carbon content in the system is 20% after the reducing agent is added; adding 4% of silicon dioxide and 3% of manganese dioxide (additive B) into the system; the temperature of the second stage roasting is 1450 ℃, and the roasting time is 60min;
(6) Cooling the roasting flue gas to obtain a solid phosphorus simple substance, and calculating to obtain a phosphorus recovery rate of 89.61%; ball-milling the second-stage roasting slag to ensure that the particle size of the second-stage roasting slag is smaller than 106 micrometers (sieving the second-stage roasting slag by a 150-mesh sieve), and then carrying out magnetic separation under the condition that the magnetic field intensity is 115 kA/m to obtain the ferro-nickel alloy and the slag containing cobalt and manganese, wherein the representation of iron, nickel, manganese and cobalt in each material shows that the recovery rate of iron is 93.08%, the recovery rate of nickel is 96.57% (the metal phase quantity of entering nickel and iron is used as the recovery quantity), the recovery rate of cobalt is 87.91%, and the recovery rate of manganese is 82.49% (the recovery quantity of entering second-stage roasting slag of cobalt and manganese is used as the recovery quantity).
Comparative example 1:
the comparative example is mainly used for explaining the difference between the independent treatment of the waste lithium iron phosphate anode powder and the embodiment, and specifically comprises the following steps:
(1) Pretreating the waste lithium iron phosphate battery to obtain positive electrode powder of the waste lithium iron phosphate battery;
(2) Roasting the waste lithium iron phosphate anode powder under the roasting condition of 600 ℃ and 45min, and naturally cooling to room temperature after the reaction is finished to obtain roasted sand slag;
(3) Leaching the roasting slag under the following conditions: the leaching temperature is 50 ℃, the solid-to-liquid ratio (g/mL) is 1:5, the leaching time is 60min, the pH value in the leaching process is controlled to be 7.5 (the pH value is controlled by sodium hydroxide of 20-60g/L), filtering treatment is carried out after leaching is finished, lithium-rich leachate and leaching residues are obtained, and the representation of the lithium and iron contents in the leachate and the leaching residues shows that the leaching rate of lithium is 32.03%.
Comparative example 2:
the comparative example is mainly used for explaining the difference between the method for independently processing the waste lithium nickel cobalt manganese oxide positive electrode powder and the embodiment, and specifically comprises the following steps:
(1) Pretreating the waste lithium cobaltate battery to obtain waste lithium cobaltate battery positive electrode powder;
(2) Carrying out low-temperature roasting treatment on the waste lithium cobaltate positive electrode powder under the roasting condition that the roasting temperature is 600 ℃ and the roasting time is 45min, and naturally cooling to room temperature after the reaction is finished to obtain roasted sand slag;
(3) Leaching the roasting slag under the conditions of 50 ℃ of leaching temperature, 1:5 of solid-to-liquid ratio (g/mL) and 60min of leaching time, controlling the pH value to be 7.5 in the leaching process (controlling by adopting 20-60g/L of sodium hydroxide), filtering after leaching to obtain a lithium-rich leaching solution and leaching slag, and representing the lithium and cobalt contents in the leaching solution and the leaching slag to show that the leaching rate of lithium is 44.57%.
Comparative example 3:
the comparative example is mainly used for explaining the influence of aluminum sulfate and phosphoric acid on the lithium leaching rate in the first-stage roasting process, and specifically comprises the following steps:
(1) Pretreating the waste lithium iron phosphate battery and the waste lithium nickel cobalt manganese oxide battery to obtain lithium iron phosphate positive electrode powder, lithium iron phosphate negative electrode powder, lithium nickel cobalt manganese oxide positive electrode powder and lithium nickel cobalt manganese oxide negative electrode powder;
(2) Mixing the two kinds of positive electrode powder obtained in the step (1) to obtain mixed positive electrode powder, wherein the mass ratio of iron in the positive electrode powder of the iron phosphate lithium battery in the mixed positive electrode powder to nickel in the positive electrode powder of the nickel cobalt lithium manganate is 3:1 (mFe: mNi = 3:1);
(3) Carrying out primary roasting treatment on the mixed anode powder, wherein the roasting condition is that the roasting temperature is 600 ℃, the roasting time is 45min, and naturally cooling to room temperature after the reaction is finished to obtain roasted sand slag;
(4) Leaching the first-stage roasting slag under the conditions of 50 ℃ of leaching temperature, 1:5 of solid-to-liquid ratio (g/mL) and 60min of leaching time, controlling the pH value to be 7.5 in the leaching process (by adopting sodium hydroxide of 20-60g/L), filtering after the leaching is finished to obtain a lithium-rich leaching solution and leaching slag, and representing the lithium and cobalt contents in the leaching solution and the leaching slag to show that the leaching rate of lithium is 74.57%. The lithium leaching rate was significantly higher than that of comparative examples 1 and 2, but significantly lower than that of each of the above examples.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit of the invention.
Claims (7)
1. A method for separating and extracting valuable metals from waste batteries is characterized by comprising the following steps:
(1) Pretreating waste lithium iron phosphate batteries to obtain positive electrode powder A and negative electrode powder A, pretreating the waste lithium nickel cobalt manganese batteries to obtain positive electrode powder B and negative electrode powder B, and mixing the positive electrode powder A, the positive electrode powder B and the additive A to obtain mixed positive electrode powder; the additive A is a mixture of aluminum sulfate and phosphoric acid, the addition amount of the additive A is 2-6% of the mass of the mixed positive electrode powder, and the mass ratio of the phosphoric acid to the aluminum sulfate in the additive A is (3-4.5): (5.5 to 7); in the mixed positive electrode powder, the mass ratio of the iron element in the positive electrode powder A to the nickel element in the positive electrode powder B is (2~6): 1;
(2) Carrying out primary roasting on the mixed anode powder to obtain primary roasting slag; the temperature of the first-stage roasting is 400 to 700 ℃, and the time is 15 to 90min;
(3) Leaching the first-stage roasting slag to obtain a lithium-rich leaching solution and leaching slag; when the first-stage roasting slag is leached, controlling the pH value to be 6.5 to 9.5;
(4) Adding a reducing agent into the leaching slag, carrying out secondary roasting, and collecting to obtain secondary roasting slag and roasting smoke; the reducing agent is at least one of the negative electrode powder A and the negative electrode powder B; the temperature of the second-stage roasting is 1200 to 1500 ℃, and the time is 30 to 120min;
(5) Post-treating the second-stage roasting slag to obtain a nickel-iron alloy and cobalt-and manganese-containing slag; and condensing the roasting flue gas to obtain elemental phosphorus, namely completing the separation and extraction of valuable metals in the waste batteries.
2. The method for separating and extracting valuable metals from waste batteries according to claim 1, wherein when the primary roasting slag is leached in the step (3), the leaching temperature is 25 to 70 ℃, and the leaching time is 30 to 150min.
3. The method for separating and extracting valuable metals from waste batteries according to claim 2, characterized in that in the step (3), the pH in the leaching process is controlled by adopting sulfuric acid with the concentration of 50 to 120g/L or sodium hydroxide with the concentration of 20 to 60g/L.
4. The method for separating and extracting valuable metals from waste batteries according to claim 1, wherein the mass of carbon in the reducing agent added in the two-stage roasting is 8-20% of the total mass of the leaching residues and the reducing agent.
5. The method for separating and extracting valuable metals from waste batteries according to any one of claims 1 to 4, characterized in that an additive B is further added in the secondary roasting, and the additive B, leached residues and a reducing agent are subjected to the secondary roasting together; the additive B comprises at least one of calcium oxide, silicon dioxide and manganese dioxide.
6. The method for separating and extracting valuable metals from waste batteries according to claim 5, wherein the additive B is added in an amount of 2-8% by mass of leaching residues.
7. The method for separating and extracting valuable metals from waste batteries according to any one of claims 1 to 4, wherein the post-treatment operation of the secondary-stage roasting slag in the step (5) comprises ball milling and magnetic separation processes which are sequentially carried out, the particle size of the secondary-stage roasting slag after ball milling is less than 50 μm, and the magnetic field strength of the magnetic separation process is 100 to 120kA/m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211050220.6A CN115109934B (en) | 2022-08-31 | 2022-08-31 | Method for separating and extracting valuable metals from waste batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211050220.6A CN115109934B (en) | 2022-08-31 | 2022-08-31 | Method for separating and extracting valuable metals from waste batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115109934A CN115109934A (en) | 2022-09-27 |
| CN115109934B true CN115109934B (en) | 2022-12-27 |
Family
ID=83335174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211050220.6A Active CN115109934B (en) | 2022-08-31 | 2022-08-31 | Method for separating and extracting valuable metals from waste batteries |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115109934B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104241724A (en) * | 2014-09-02 | 2014-12-24 | 湖南邦普循环科技有限公司 | Method for preparing battery-grade lithium carbonate from recycled lithium ion battery material |
| KR101682217B1 (en) * | 2016-09-02 | 2016-12-05 | 주식회사 재영텍 | A Method Of Manufacturing A Lithium Carbonate With High Purity By Recycling A Lithium From A Anode Material Of Used Lithium Ion Secondary Battery |
| CN108631017A (en) * | 2018-04-09 | 2018-10-09 | 惠州亿纬锂能股份有限公司 | The recovery method of waste and old lithium ionic cell electrolyte |
| CN110643814A (en) * | 2018-06-26 | 2020-01-03 | 中南大学 | Method for removing aluminum and recycling waste lithium iron phosphate batteries |
| CN111118294A (en) * | 2020-01-15 | 2020-05-08 | 北京矿冶科技集团有限公司 | Method for recycling valuable metals from waste lithium ion battery materials step by step |
| CN111254294A (en) * | 2020-03-11 | 2020-06-09 | 中南大学 | Method for selectively extracting lithium from waste lithium ion battery powder and recovering manganese dioxide through electrolytic separation |
| KR102350008B1 (en) * | 2021-07-05 | 2022-01-11 | 주식회사 에코프로이노베이션 | Method for recovering lithium and valuable metals from waste electrode materials |
| CN113930619A (en) * | 2021-11-03 | 2022-01-14 | 金川集团股份有限公司 | Method for preferentially extracting lithium from waste ternary lithium ion battery anode material and recovering valuable metal |
| CN114574705A (en) * | 2022-04-08 | 2022-06-03 | 江苏大学 | Method for leaching and separating lithium and valuable metals from waste lithium ion battery |
-
2022
- 2022-08-31 CN CN202211050220.6A patent/CN115109934B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104241724A (en) * | 2014-09-02 | 2014-12-24 | 湖南邦普循环科技有限公司 | Method for preparing battery-grade lithium carbonate from recycled lithium ion battery material |
| KR101682217B1 (en) * | 2016-09-02 | 2016-12-05 | 주식회사 재영텍 | A Method Of Manufacturing A Lithium Carbonate With High Purity By Recycling A Lithium From A Anode Material Of Used Lithium Ion Secondary Battery |
| CN108631017A (en) * | 2018-04-09 | 2018-10-09 | 惠州亿纬锂能股份有限公司 | The recovery method of waste and old lithium ionic cell electrolyte |
| CN110643814A (en) * | 2018-06-26 | 2020-01-03 | 中南大学 | Method for removing aluminum and recycling waste lithium iron phosphate batteries |
| CN111118294A (en) * | 2020-01-15 | 2020-05-08 | 北京矿冶科技集团有限公司 | Method for recycling valuable metals from waste lithium ion battery materials step by step |
| CN111254294A (en) * | 2020-03-11 | 2020-06-09 | 中南大学 | Method for selectively extracting lithium from waste lithium ion battery powder and recovering manganese dioxide through electrolytic separation |
| KR102350008B1 (en) * | 2021-07-05 | 2022-01-11 | 주식회사 에코프로이노베이션 | Method for recovering lithium and valuable metals from waste electrode materials |
| CN113930619A (en) * | 2021-11-03 | 2022-01-14 | 金川集团股份有限公司 | Method for preferentially extracting lithium from waste ternary lithium ion battery anode material and recovering valuable metal |
| CN114574705A (en) * | 2022-04-08 | 2022-06-03 | 江苏大学 | Method for leaching and separating lithium and valuable metals from waste lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115109934A (en) | 2022-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wei et al. | Spent lithium ion battery (LIB) recycle from electric vehicles: A mini-review | |
| CN110835682B (en) | Method for cooperatively treating positive and negative active materials of waste lithium ion battery | |
| CN109082522B (en) | Method for recovering anode powder of waste ternary lithium battery | |
| CN110459828B (en) | Comprehensive recovery method of waste lithium iron phosphate battery positive electrode material | |
| CN110592384B (en) | Novel process for simultaneously recovering valuable metal and iron from mixed type waste lithium ion battery | |
| CN109022793B (en) | Method for selectively leaching lithium from waste powder of cathode material containing at least one of cobalt, nickel and manganese | |
| CN108023134A (en) | The recovery method of valuable element in a kind of waste lithium ion battery electrode material | |
| WO2016141875A1 (en) | Method of recycling and processing waste battery | |
| CN106834703A (en) | A kind of leaching method of waste lithium ion cell anode active material | |
| CN113415813A (en) | Method for recovering lithium nickel cobalt manganese from waste ternary battery material | |
| CN111961857A (en) | Method for synchronously defluorinating valuable metals leached from waste lithium ion batteries | |
| CN115109936B (en) | Method for recovering valuable metals from waste batteries | |
| CN111807423A (en) | Method for preparing battery anode material by leaching waste lithium battery with sulfur dioxide gas | |
| Duan et al. | Recycling and direct-regeneration of cathode materials from spent ternary lithium-ion batteries by hydrometallurgy: Status quo and recent developments: Economic recovery methods for lithium nickel cobalt manganese oxide cathode materials | |
| CN115652077A (en) | Method for selectively separating and recovering lithium and manganese from waste lithium manganate battery | |
| JP6314730B2 (en) | Method for recovering valuable metals from waste nickel metal hydride batteries | |
| CN115109934B (en) | Method for separating and extracting valuable metals from waste batteries | |
| CN115072688B (en) | Method for recycling all components of waste lithium iron phosphate battery | |
| CN116837213A (en) | Method for comprehensively utilizing valuable metals in waste ternary lithium ion battery electrode powder | |
| CN111129488A (en) | Preparation method of lithium ion battery nickel-cobalt binary oxide positive electrode material precursor | |
| CN115196609A (en) | Method for recovering iron phosphate from lithium iron phosphate lithium extraction slag and application thereof | |
| JP6201905B2 (en) | Method for recovering valuable metals from waste nickel metal hydride batteries | |
| CN114231744A (en) | Method for recovering lithium, cobalt, nickel and manganese from waste lithium batteries | |
| CN113363609A (en) | Method for recycling waste lithium battery anode material by fluid gradual solidification method | |
| CN115924879B (en) | Method for recycling lithium iron phosphate from scrapped lithium iron phosphate material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 410000 No. 068 Jinsha West Road, Jinzhou New District, Ningxiang, Changsha City, Hunan Province Patentee after: Hunan Wuchuang Recycling Technology Co.,Ltd. Address before: 410600 No. 068, Jinsha West Road, Jinzhou new area, Ningxiang, Changsha, Hunan Patentee before: Hunan Wuchuang Circulation Technology Co.,Ltd. |
|
| CP03 | Change of name, title or address | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A Method for Separating and Extracting Valuable Metals from Waste Batteries Effective date of registration: 20230418 Granted publication date: 20221227 Pledgee: Ningxiang sub branch of Bank of Changsha Co.,Ltd. Pledgor: Hunan Wuchuang Recycling Technology Co.,Ltd. Registration number: Y2023980038384 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |