CN113913612A - Method and system for recovering cobalt lithium battery material by gas acidification method - Google Patents

Method and system for recovering cobalt lithium battery material by gas acidification method Download PDF

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CN113913612A
CN113913612A CN202010658838.5A CN202010658838A CN113913612A CN 113913612 A CN113913612 A CN 113913612A CN 202010658838 A CN202010658838 A CN 202010658838A CN 113913612 A CN113913612 A CN 113913612A
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lithium
cobalt
carbonate
reactor
liquid separation
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周小舟
赵黄经
李雨思
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Mining Environmental Protection Technology Shanghai Co ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/06—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/005—Preliminary treatment of scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • 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
    • 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
    • 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

Abstract

The application discloses a method and a system for recovering cobalt lithium battery materials by a gas acidification method, wherein the method comprises the following steps: obtaining a raw material containing cobalt and lithium and grinding the raw material into powder; adding raw materials, water and an auxiliary solvent into a pulping device to prepare mixed slurry; inputting the mixed slurry into a first-stage reactor, and continuously introducing acid gas into the first-stage reactor; performing solid-liquid separation for the first time, and circulating the raw materials which are not subjected to the dissolution reaction to a pulping device; adding the primary filtrate into a secondary reactor, and adding an auxiliary reagent to participate in a chemical reaction; and (5) performing solid-liquid separation for the second time, and circulating the secondary filtrate to the pulping device. The system, comprising: the system comprises an acquisition unit, a slurrying device, a primary reactor, a first solid-liquid separation unit, a secondary reactor and a second solid-liquid separation unit. The method and the device can recover the valuable metals containing cobalt and lithium from the metal of the anode material of the waste lithium ion battery, and simultaneously can reduce carbon emission, realize low energy consumption and material consumption, and can also realize maximum recycling of the waste battery material containing cobalt and lithium ions.

Description

Method and system for recovering cobalt lithium battery material by gas acidification method
Technical Field
The application relates to a method and a system for recovering cobalt lithium battery materials by a gas acidification method.
Background
Chinese invention patent publication No. CN 110139832 a, which discloses a process for obtaining cobalt sulfate/cobalt dithionate and lithium sulfate/lithium dithionate from processing of a cobalt-lithium containing resource material, and specifically discloses a process for removing water and/or recycling from a liquor containing sodium sulfate and/or sodium dithionate obtained from processing of a cobalt-lithium containing resource material, comprising the steps of: cobalt and lithium are precipitated as cobalt carbonate and lithium carbonate or cobalt hydroxide and lithium hydroxide, which are then removed from the liquor, sodium sulfate and sodium dithionate are crystallized and the crystals are separated from the liquor, after which the crystals are heated to anhydrous sodium sulfate, sulfur dioxide and water, and the anhydrous sodium sulfate is then separated. Which is applied, for example, to the recovery of cobalt-lithium containing lithium-ion battery positive electrode materials by leaching cobalt and lithium in raw materials with sulfur dioxide and sulfuric acid, a process which involves the treatment and recovery of sulfate and dithionate solutions; meanwhile, sodium carbonate still needs to be used in the precipitation process, and the method belongs to a process flow for recovering cobalt and lithium with higher energy consumption and material consumption. Also, it does not disclose how the cobalt-lithium containing solution reacts with carbon dioxide gas together and is recovered in such a way that a mixture of cobalt carbonate, lithium carbonate and cobalt-lithium carbonate precipitates.
Disclosure of Invention
In view of the above disadvantages, the present application provides a method and system for recovering cobalt lithium battery material by gas acidification, which extracts cobalt carbonate and lithium carbonate or cobalt hydroxide and lithium hydroxide from a solution containing cobalt and lithium by leaching reaction using an acid gas and an auxiliary solvent, thereby recovering cobalt lithium and other elements from the waste material.
In order to solve the technical problem, the application is realized by the following technical scheme:
the application provides a method for recovering a cobalt lithium battery material by a gas acidification method, which comprises the following steps:
obtaining a raw material containing cobalt and lithium and grinding the raw material into powder;
the raw materials, water and auxiliary solvents are added into a pulping machine to prepare mixed pulp, wherein the auxiliary solvents include but are not limited to: citrate, gluconate, glutamate, propionate, butyrate phosphate and combinations thereof;
inputting the mixed slurry into a primary reactor, and continuously introducing an acid gas into the primary reactor, wherein the acid gas is mainly derived from industrial waste gas and comprises but is not limited to: CO 22、SOx、NOxAnd other acid gases;
carrying out first solid-liquid separation treatment on the reaction product in the primary reactor, and separating and extracting raw materials which are not subjected to dissolution reaction and recycling the raw materials to the pulping device;
adding the primary filtrate after the primary solid-liquid separation into a secondary reactor, and adding an auxiliary reagent into the secondary reactor to participate in a chemical reaction;
and obtaining cobalt carbonate, lithium carbonate and lithium cobalt carbonate, a mixture of cobalt hydroxide, lithium hydroxide and lithium cobalt hydroxide and secondary filtrate through secondary solid-liquid separation, and recycling the secondary filtrate to the pulping machine.
Further, the method for recovering a cobalt lithium battery material by a gas acidification method, wherein the primary filtrate after the first solid-liquid separation is added into a secondary reactor, and an auxiliary reagent is added into the secondary reactor to participate in a chemical reaction, comprises the following steps: adjusting the stirring speed of the stirrer, adjusting the reaction temperature and adjusting the proportion of auxiliary reagents.
Further, the method for recovering a cobalt lithium battery material by a gas acidification method, wherein the adjusting the stirring speed of the stirrer comprises: the stirring is accelerated.
Further, the method for recovering a cobalt lithium battery material by a gas acidification method, wherein the adjusting of the reaction temperature comprises: the primary filtrate is heated.
Further, the method for recovering a cobalt lithium battery material by a gas acidification method, wherein the adjusting of the proportion of the auxiliary reagent comprises: adding NaOH or simultaneously adding acid gas and NaOH.
Further, the above method for recovering a cobalt lithium battery material by a gas acidification method, wherein the above cobalt carbonate, lithium carbonate and lithium cobalt carbonate obtained by the second solid-liquid separation, and a mixture of cobalt hydroxide, lithium hydroxide and lithium cobalt hydroxide and a secondary filtrate, comprises: sintering the mixture to obtain the oxide containing cobalt and lithium with higher purity.
The application also provides a recovery system of cobalt lithium battery material by gas acidification method, including:
an obtaining unit for obtaining a raw material containing cobalt and lithium and grinding into powder;
the pulping device is used for preparing mixed slurry by adding the raw materials, water and an auxiliary solvent into the pulping device;
the primary reactor is used for inputting the mixed slurry into the primary reactor and continuously introducing acid gas into the primary reactor;
a first solid-liquid separation unit for subjecting the reaction product in the primary reactor to a first solid-liquid separation treatment, and separating and extracting raw materials which are not subjected to a dissolution reaction and recycling the raw materials to the slurrying device;
the primary filtrate after solid-liquid separation by the first solid-liquid separation unit is added into the secondary reactor, and an auxiliary reagent is added into the secondary reactor to participate in chemical reaction;
and the second solid-liquid separation unit is used for performing solid-liquid separation to obtain cobalt carbonate, lithium carbonate and lithium cobalt carbonate, a mixture of cobalt hydroxide, lithium hydroxide and lithium cobalt hydroxide and secondary filtrate, and the secondary filtrate is circulated to the pulping device.
Further, the above recovery system for cobalt lithium battery material by gas acidification method, wherein the above second-stage reactor further comprises: the stirrer is used for adjusting the stirring speed of the stirrer, adjusting the reaction temperature and adjusting the proportion of auxiliary reagents so as to improve the reaction efficiency.
Further, the recovery system of the cobalt lithium battery material by the gas acidification method, wherein the secondary reactor further comprises: and the acceleration stirring unit is used for accelerating the stirring of the stirrer.
Further, the recovery system of the cobalt lithium battery material by the gas acidification method, wherein the secondary reactor further comprises: and a heating unit for heating the primary filtrate.
Further, the above recovery system for cobalt lithium battery material by gas acidification method, wherein the above second-stage reactor further comprises: and the NaOH conveying channel is used for adding NaOH into the secondary reactor.
Further, the above recovery system for cobalt lithium battery material by gas acidification method, wherein the above second-stage reactor further comprises: an acid gas delivery passage for delivering acid gas into the secondary reactor.
Further, the recovery system of the cobalt lithium battery material by the gas acidification method further comprises: and a sintering unit for sintering the above cobalt carbonate, lithium carbonate and lithium cobalt carbonate and cobalt hydroxide, lithium hydroxide and lithium cobalt hydroxide mixture to obtain a higher purity cobalt and lithium containing oxide.
Compared with the prior art, the method has the following technical effects:
the method comprises the steps of leaching and recovering cobalt carbonate, lithium carbonate and lithium cobalt carbonate and a mixture of cobalt hydroxide, lithium hydroxide and lithium cobalt hydroxide in a one-stop manner by using an acid gas and an auxiliary agent; in addition, the waste lithium battery material mainly containing lithium cobalt oxide reacts with acid gas and auxiliary reagent, and the filtrate is recycled and recycled in a closed loop manner, so that compared with the prior art, the energy consumption and material consumption are obviously reduced, and the recycling rate of cobalt and lithium in circulation and the utilization rate of acid gas (especially industrial waste gas) emission are improved;
the method can recover the valuable metals containing cobalt and lithium from the metal of the anode material of the waste lithium ion battery, and simultaneously can reduce the exhaust emission, and can realize the maximized green clean recycling of the waste battery material containing cobalt and lithium ions while realizing low energy consumption and material consumption.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the following detailed description of non-limiting embodiments thereof, made with reference to the accompanying drawings in which:
FIG. 1: the flow chart of the recovery method of the cobalt lithium battery material by the gas acidification method is provided;
FIG. 2: the application discloses a schematic diagram of a recovery system of a cobalt lithium battery material by a gas acidification method.
Detailed Description
The conception, specific structure and technical effects of the present application will be further described in conjunction with the accompanying drawings to fully understand the purpose, characteristics and effects of the present application.
In one embodiment of the present application, as shown in fig. 1, a method for recovering a cobalt lithium battery material by a gas acidification method includes the following steps:
the method comprises the following steps: obtaining a raw material 101 containing cobalt and lithium and grinding the raw material into powder;
step two: adding the raw material 101, water and an auxiliary solvent 102 (or a circulating solvent 28 obtained after a secondary separation device) into a pulping device 10 to prepare mixed slurry;
step three: inputting the mixed slurry into a primary reactor 12, and continuously introducing an acid gas 121 into the primary reactor 12;
step four: carrying out primary solid-liquid separation 14 treatment on the reaction product in the primary reactor 12, and separating and extracting raw materials 16 which are not subjected to dissolution reaction and recycling the raw materials to the pulping device 10;
step five: adding the primary filtrate 18 after the primary solid-liquid separation 14 into a secondary reactor 20, and adding an auxiliary reagent 201 into the secondary reactor 20 to participate in a chemical reaction;
step six: a mixture of cobalt carbonate, lithium carbonate and lithium cobalt carbonate and a mixture 24 of cobalt hydroxide, lithium hydroxide and lithium cobalt hydroxide and a secondary filtrate 28 are obtained by the second solid-liquid separation 22, which secondary filtrate 28 is recycled to the pulp maker 10.
In the first step, the material 101 containing cobalt and lithium is separated from the deposit.
In this embodiment, the raw material 101 containing cobalt and lithium may be any waste containing cobalt and lithium ions, and mainly includes: the chemical formula and the hazard related to the material of the positive electrode material of the lithium ion battery are shown in the following table:
Figure BDA0002577746000000051
in the fifth step, the primary filtrate 18 after the first solid-liquid separation is added into the secondary reactor 20, and the auxiliary reagent 201 is added into the secondary reactor 20 to participate in the chemical reaction, including: by adjusting the stirring speed of the stirrer 202, adjusting the reaction temperature and adjusting the proportion of the auxiliary reagent 201, a mixture 24 of cobalt carbonate, lithium carbonate and lithium cobalt carbonate and a mixture 24 of cobalt hydroxide, lithium hydroxide and lithium cobalt hydroxide are precipitated.
Wherein, the above-mentioned secondary reactor 20 can be adjusted as follows:
(1) accelerating stirring to leach the cobalt and lithium precipitates;
(2) heating the primary filtrate 18 to leach the cobalt and lithium precipitate;
(3) NaOH is added, so that the precipitation rate of cobalt and lithium ions is improved;
(4) and simultaneously, a small amount of NaOH and acid gas are added, so that the precipitation rate of cobalt and lithium ions is further improved.
In this embodiment, the solid-liquid separation may include a centrifugal or pressure filtration method.
In the sixth step, the obtaining of the mixture of cobalt carbonate, lithium carbonate and lithium cobalt carbonate, the mixture 24 of cobalt hydroxide, lithium hydroxide and lithium cobalt hydroxide and the secondary filtrate 28 by the second solid-liquid separation 22 further includes: the above-mentioned cobalt carbonate, lithium carbonate and lithium cobalt carbonate mixture and cobalt hydroxide, lithium hydroxide and lithium cobalt hydroxide mixture 24 are sintered to obtain a higher purity cobalt and lithium containing oxide 26 for use in the manufacture of a positive electrode material for a lithium ion battery.
In one embodiment of the present application, as shown in fig. 2, a recycling system for cobalt lithium battery material by gas acidification method comprises:
an obtaining unit for obtaining a raw material 101 containing cobalt and lithium and grinding into powder;
a pulper 10 for preparing a mixed slurry by adding the raw material 101, water and an auxiliary solvent 102 into the pulper 10;
a primary reactor 12, inputting the mixed slurry into the primary reactor 12, and continuously introducing an acid gas 121 into the primary reactor 12;
a first solid-liquid separation unit 14 for subjecting the reaction product in the primary reactor 12 to a first solid-liquid separation treatment, and separating and extracting a raw material 16 that has not undergone a dissolution reaction and recycling the raw material to the slurrying device 10;
a secondary reactor 20, wherein the primary filtrate 18 after solid-liquid separation in the first solid-liquid separation unit 14 is added into the secondary reactor 20, and an auxiliary reagent 201 is added into the secondary reactor 20 to participate in chemical reaction;
and a second solid-liquid separation unit 22 for performing solid-liquid separation by the second solid-liquid separation unit 22 to obtain a mixture of cobalt carbonate, lithium carbonate and lithium cobalt carbonate, a mixture 24 of cobalt hydroxide, lithium hydroxide and lithium cobalt hydroxide and a secondary filtrate 28, and recycling the secondary filtrate 28 to the pulp maker 10.
In the above-described extraction unit, the raw material 101 containing cobalt and lithium is separated from the deposit and pulverized.
In this example, LiCoO is shown as the chemical formula2To represent cobalt and lithium containing materials, water and an auxiliary solvent 102 are added and a mixed slurry is prepared to flow into the primary reactor 12.
The acid gas 121 is continuously introduced into the primary reactor 12 and circulated into the secondary filtrate 28 filtered out in the final stage of the process, which may contain cobalt and lithium ions that have not been completely recovered in the previous final stage, to be mixed with the slurry of the raw material 101.
In this example, carbon dioxide CO is used2Gas means acid gas.
Part of the cobalt and lithium will dissolve in the solution in the form of ions and react to form a leachate containing cobalt ions, lithium ions and carbonate. The dissolution reaction is as follows:
Li+Co+CO2+H2O＝Li++Co3++CO3 2-+2H+
the leachate flows into the first solid-liquid separation unit 14, the raw material 16 that has not undergone the dissolution reaction with the acid gas 121 is separated by filtration or centrifuge, and the separated raw material 16 is recycled to the pulp maker 10.
The system further comprises: an agitator 202. The leaching rate is increased by adjusting the stirring speed of the stirrer 202, adjusting the reaction temperature or adding a proportioned auxiliary reagent 201, precipitating the mixture of cobalt carbonate, lithium carbonate and lithium cobalt carbonate and the mixture 24 of cobalt hydroxide, lithium hydroxide and lithium cobalt hydroxide, and adding the auxiliary reagent 201 (such as adding NaOH to the secondary reactor 20 through a NaOH conveying channel) and/or inputting acid gas through an acid gas conveying channel under the condition of low precipitation rate.
The above-mentioned stirrer 202 is further provided with an acceleration stirring unit for accelerating the stirring by the above-mentioned stirrer 202, and a heating unit for heating the above-mentioned primary filtrate 18.
The slurry containing solids and liquid is fed to a secondary solid-liquid separation unit to separate cobalt carbonate, lithium carbonate and cobalt lithium carbonate mixtures and cobalt hydroxide, lithium hydroxide and lithium cobalt hydroxide mixtures 24 precipitate, collect the resulting precipitate and recover a secondary filtrate 28, which may contain cobalt and lithium ions that have not been completely recovered in the previous final stage.
Wherein the precipitation reaction is as follows:
Li++Co3++2CO3 2-+H2O＝CoCO3+Li2CO3；
Li++Co3++4CO2+2NaOH＝CoCO3+Li2CO3+Na2CO3+H2O；
Li++Co3++4NaOH＝Co(OH)3+LiOH+4Na+；
the secondary filtrate 28 is recycled to the pulp maker 10 to reduce water consumption and maximize the cobalt and lithium recovery in the overall process.
Further, the precipitate 24 is calcined by a calcining unit to form a high-purity cobalt-and lithium-containing oxide 26, which is used for manufacturing a positive electrode material of a lithium ion battery.
The working principle of the embodiment is as follows:
in this example, carbon dioxide CO is used2Gas means acid gas. Carbon dioxide CO2After the gas is dissolved in water, part of the carbon dioxide CO2Reaction of gas and water to produce H carbonate2CO3Partial carbonic acid H2CO3Unstable, decomposed into carbonate ion HCO3 -And hydrogen ion H+Dissolved carbon dioxide CO2The water is weakly acidic.
CO2+H2O→H2CO3；
H2CO3→H++HCO3 -；
While low-valence cobalt can be leached from high-valence cobalt, such as trivalent cobalt oxide Co contained in positive electrode material of rechargeable lithium ion battery2O3Carbon dioxide CO may be used2Gas and auxiliary solvent 102 leachingAnd (6) taking. Using carbon dioxide CO2The gas combines with a reducing agent such as the auxiliary solvent 102 and the cobalt oxide to produce cobalt carbonate, CoCO3And (4) precipitating. The leaching reaction equation is as follows:
Co2O3+6H+→2Co3++3H2O；
the precipitation reaction equation is as follows:
Co3++CO2+H2O＝CoCO3；
Co3++2CO2+2NaOH＝CoCO3+Na2CO3+H2O；
lithium cobalt oxides, e.g. lithium cobalt LiCoO oxide2Is a typical positive electrode material in high-energy lithium ion batteries, and is generally used for personal electronic equipment. The following reactions will occur during leaching:
LiCoO2+4H+＝Li++Co3++2H2O；
the precipitation reaction equation is as follows:
Li++Co3++2CO3 2-+H2O＝CoCO3+Li2CO3；
Li++Co3++4CO2+2NaOH＝CoCO3+Li2CO3+Na2CO3+H2O；
nickel manganese cobalt oxides, e.g. LiNi0.33Mn0.33Co0.33O2The lithium ion battery is a novel anode material with high energy and high power, and is suitable for the electric automobile industry. The following reactions will occur during leaching:
LiNi0.33Mn0.33Co0.33O2+4H+＝Li++(Ni，Co，Mn)3++2H2O；
the precipitation reaction equation is as follows:
2Li++(Ni，Co，Mn)3++2CO3 2-+H2O＝Li2C03+(Ni，Co，Mn)CO3；
2LiNi0.33Mn0.33Co0.33O2+4CO2+2NaOH＝Li2C03+2(Ni，Co，Mn)CO3+Na2CO3+H2O；
(Ni，Co，Mn)CO3represents a nickel manganese cobalt mixed metal carbonate.
Lithium nickel cobalt aluminum oxides, e.g. LiNi0.8Co0.15Al0.05 O2Is another emerging anode material with high energy and high power, and is suitable for the electric automobile industry. The following reactions will occur during leaching:
LiNi0.8Co0.15Al0.05 O2+4H+＝Li++(Ni，Co，Al)3++H2O；
the precipitation reaction equation is as follows:
Li++(Ni，Co，Al)3++2CO3 2-+H2O＝Li2CO3+(Ni，Co，Al)CO3+H2O；
LiNi0.8Co0.15Al0.05 O2+3CO2+2NaOH＝Li2CO3+(Ni，Co，Al)CO3+Na2CO3+H2O；
(Ni，Co，Al)CO3represents a nickel cobalt aluminum mixed metal carbonate.
The cobalt and lithium containing compounds such as cobalt carbonate, lithium carbonate and cobalt lithium carbonate compounds, which can be precipitated as the above positive electrode material of the spent batteries containing cobalt and lithium ions, are used to manufacture the positive electrode material of the lithium ion battery. This is usually done by combining the desired proportions of cobalt and lithium containing compounds and then heat treating the mixture.
Among them, the above-mentioned recycling method of the cobalt and lithium containing compounds such as cobalt carbonate, lithium carbonate and cobalt lithium carbonate compounds precipitated from the positive electrode material of the waste battery containing cobalt and lithium ions for manufacturing the positive electrode material of the lithium ion battery can be referred to the following prior arts: for example, "Li" published by Jonec et alxCoO2(0<x<1): novel battery positive with high energy densityPole material "," solid ion ", volume 3, phase 4, 1981, pages 171-174: a process for the preparation of lithium cobaltate LiCoO by treating a compound containing cobalt and lithium is described2A processing method for battery anode material. US patent publication No. US8685565 discloses a treatment process for processing lithium nickel manganese cobalt oxides by treatment of lithium nickel manganese cobalt compounds. Published by Kim et al ("synthesis of high density nickel cobalt aluminum hydroxide by sequential co-precipitation", ACC applications and interfaces, 4 th, 2012, pages 586-.
The method comprises the steps of leaching and recovering cobalt carbonate, lithium carbonate and lithium cobalt carbonate and a mixture of cobalt hydroxide, lithium hydroxide and lithium cobalt hydroxide in a one-stop manner by using an acid gas and an auxiliary agent; in addition, the waste lithium battery material mainly containing lithium cobalt oxide reacts with acid gas and auxiliary reagent, and the filtrate is recycled and recycled in a closed loop manner, so that compared with the prior art, the energy consumption and material consumption are obviously reduced, and the recycling rate of cobalt and lithium in circulation and the utilization rate of acid gas (especially industrial waste gas) emission are improved; the method and the device can recover the valuable metals containing cobalt and lithium from the metal of the anode material of the waste lithium ion battery, and can reduce the discharge, realize low energy consumption and material consumption, and realize the maximized green clean recycling of the waste battery material containing cobalt and lithium ions.
The above embodiments are merely to illustrate the technical solutions of the present application and are not limitative, and the present application is described in detail with reference to preferred embodiments. It will be understood by those skilled in the art that various modifications and equivalent arrangements may be made in the present invention without departing from the spirit and scope of the present invention and shall be covered by the appended claims.

Claims (12)

1. A method for recovering a cobalt lithium battery material by a gas acidification method is characterized by comprising the following steps:
obtaining a raw material containing cobalt and lithium and grinding the raw material into powder;
adding the raw materials, water and an auxiliary solvent into a pulping device to prepare mixed slurry;
inputting the mixed slurry into a primary reactor, and continuously introducing acid gas into the primary reactor;
carrying out first solid-liquid separation treatment on the reaction product in the primary reactor, and separating and extracting raw materials which are not subjected to dissolution reaction and recycling the raw materials to the pulping device;
adding the primary filtrate after the primary solid-liquid separation into a secondary reactor, and adding an auxiliary reagent into the secondary reactor to participate in a chemical reaction;
and obtaining cobalt carbonate, lithium carbonate and lithium cobalt carbonate, a mixture of cobalt hydroxide, lithium hydroxide and lithium cobalt hydroxide and secondary filtrate through secondary solid-liquid separation, and recycling the secondary filtrate to the pulping machine.
2. The method as claimed in claim 1, wherein the step of adding the first filtrate after the first solid-liquid separation into a secondary reactor and adding an auxiliary reagent into the secondary reactor to participate in a chemical reaction comprises: adjusting the stirring speed of the stirrer, adjusting the reaction temperature and adjusting the proportion of auxiliary reagents.
3. The method as claimed in claim 2, wherein the adjusting the stirring speed of the stirrer comprises: the stirring is accelerated.
4. The method as claimed in claim 2, wherein the adjusting the reaction temperature comprises: heating the primary filtrate.
5. The method as claimed in claim 2, 3 or 4, wherein the adjusting the ratio of the auxiliary solvent comprises: adding NaOH or simultaneously adding acid gas and NaOH.
6. The method as claimed in claim 1, wherein the second solid-liquid separation is performed to obtain cobalt carbonate, lithium carbonate and lithium cobalt carbonate, and a mixture of cobalt hydroxide, lithium hydroxide and lithium cobalt hydroxide and a secondary filtrate, and further comprises: the above cobalt carbonate, lithium carbonate and lithium cobalt carbonate and cobalt hydroxide, lithium hydroxide and lithium cobalt hydroxide mixture are sintered to obtain cobalt and lithium containing oxides of higher purity.
7. A recovery system of cobalt lithium battery materials by a gas acidification method is characterized by comprising the following steps:
an obtaining unit for obtaining a raw material containing cobalt and lithium and grinding into powder;
the pulping device is used for preparing mixed slurry by adding the raw materials, water and an auxiliary solvent into the pulping device;
the primary reactor is used for inputting the mixed slurry into the primary reactor and continuously introducing acid gas into the primary reactor;
a first solid-liquid separation unit for subjecting the reaction product in the primary reactor to a first solid-liquid separation treatment, and separating and extracting raw materials which are not subjected to a dissolution reaction and recycling the raw materials to the slurrying device; the primary filtrate after solid-liquid separation by the first solid-liquid separation unit is added into the secondary reactor, and an auxiliary reagent is added into the secondary reactor to participate in chemical reaction;
and the second solid-liquid separation unit is used for performing solid-liquid separation to obtain cobalt carbonate, lithium carbonate and lithium cobalt carbonate, a mixture of cobalt hydroxide, lithium hydroxide and lithium cobalt hydroxide and secondary filtrate, and the secondary filtrate is circulated to the pulping device.
8. The system of claim 7, wherein the secondary reactor further comprises: and the stirrer is used for adjusting the stirring speed of the stirrer, adjusting the reaction temperature and adjusting the proportion of the auxiliary solvent so as to improve the reaction efficiency and the reaction efficiency.
9. The system of claim 8, wherein the secondary reactor further comprises: and a heating unit for heating the primary filtrate.
10. The system of claim 8, wherein the secondary reactor comprises: and the NaOH conveying channel is used for adding NaOH into the secondary reactor.
11. The system of claim 10, wherein the secondary reactor further comprises: an acid gas delivery passage for delivering acid gas into the secondary reactor.
12. The system for recycling a gas acidification cobalt lithium battery material as claimed in any one of claims 8 to 11, further comprising: and a sintering unit for sintering the above cobalt carbonate, lithium carbonate and cobalt lithium carbonate mixture to obtain a higher purity cobalt and lithium containing oxide.
CN202010658838.5A 2020-07-09 2020-07-09 Method and system for recovering cobalt lithium battery material by gas acidification method Pending CN113913612A (en)

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