CN117721311A - Recovery method and recovery system for metal oxide anode material - Google Patents
Recovery method and recovery system for metal oxide anode material Download PDFInfo
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- 239000010405 anode material Substances 0.000 title claims abstract description 20
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- 150000002500 ions Chemical class 0.000 claims description 15
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- 229910001385 heavy metal Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- -1 iminodiethyl Chemical group 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
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- 229910001428 transition metal ion Inorganic materials 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
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- 238000002386 leaching Methods 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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 provides a recovery method and a recovery system of a metal oxide anode material. Pretreating a metal oxide anode material to prepare slurry, performing acidification and oxidation, fully reacting to form feed liquid, and performing acidification removal, adsorption and desorption on the feed liquid to obtain a recovery liquid containing metal; the invention also provides a recovery system suitable for the method, which comprises a pulping tank, a dissociation column, an acid removal column, an adsorption column and a liquid storage tank which are connected in sequence. The recovery method and the recovery system for the metal oxide anode material provided by the invention can be matched for use, can complete the recovery of the metal anode material under the conditions of low cost and low power consumption, are suitable for various metal oxide anode materials, can recycle pulping dispersing agents for multiple times, are environment-friendly, and have low equipment requirements for the whole process flow and high recovery rate.
Description
Technical Field
The application belongs to the technical field of metal recovery, and particularly relates to a recovery method and a recovery system of a metal oxide anode material.
Background
Lithium Ion Batteries (LIBs) are widely applied to the fields of electronic products, electric automobiles, power grid energy storage and the like due to the advantages of high energy density, good cycle stability, long service life and the like. In recent years, the demand of new energy batteries is rapidly increasing in all countries of the world to accelerate the achievement of the "two carbon" target. Statistics show that the global LIBs market size of 2021 has reached 545 GW.h. The total amount of the national scrapped LIBs in 2021 reaches 51.2 ten thousand tons, and the actual recovery is only 29.9 ten thousand tons, and the total amount of the theoretical scrapped LIBs in 2026 is expected to reach 231.2 ten thousand tons. At the same time, sodium Ion Batteries (SIBs) have also evolved rapidly, with a global market size of up to $5.45 billion in 2022. In the long term, the recycling market of new energy batteries is huge.
The metal layered oxide is one of the most used positive electrode materials of LIBs and SIBs, such as nickel cobalt manganese, nickel cobalt aluminum, nickel iron manganese ternary materials, nickel cobalt manganese copper, nickel iron manganese zinc quaternary materials, and the like. Along with the continuous rising of the price of metal raw materials such as Li, co, ni, mn, cu, the cost of the positive electrode material almost reaches 50% in the total cost of the battery, so that the waste positive electrode material has great recovery value.
The traditional recovery process is mainly divided into a pyrometallurgical method and a hydrometallurgical method. The scrapped lithium/sodium ion battery is disassembled, crushed and the like to obtain the scrapped positive electrode material. And (3) performing fire or wet treatment on the waste positive electrode material to obtain a positive electrode material precursor again, mixing a certain amount of lithium salt, and sintering the mixture again to obtain the positive electrode material. However, the fire method requires high temperature, high process energy consumption and emission, and the wet method requires strong acid or alkali to completely dissolve the components, so that the raw material investment is large, and the later-stage wastewater treatment is troublesome. Although the two methods can realize the recycling of the waste anode material, the energy consumption is high, the pollution is large, and the development path of energy conservation and emission reduction is not met.
The existing common recovery method of the positive electrode of the new energy battery is an oxidation acid leaching combined extraction method for recovering noble metals such as nickel, cobalt, manganese, copper, lithium and the like, as disclosed in Chinese patent No. 108069447A, a method for preparing lithium hydroxide by utilizing the waste positive electrode of the lithium ion battery is disclosed, firstly, aluminum foil, a conductive agent and a binder in the positive electrode are removed to obtain positive active waste, the waste positive electrode is treated by the oxidation acid leaching method to obtain leaching liquid, then an organic phosphorus extractant is adopted for carrying out twice extraction, pH value is adjusted to separate nickel, cobalt and manganese, then a strong acid cation exchange resin is utilized for carrying out deep impurity removal treatment on the extracting liquid to obtain purified lithium-rich solution, and finally, the lithium-rich solution is treated by a bipolar membrane electrodialysis method to obtain lithium hydroxide and an acidic solution. By adopting the method, lithium hydroxide products can be directly obtained, and the value-added treatment of lithium is realized, but the method has complex procedures, positive electrode waste materials are required to be completely separated, and the leaching efficiency of the waste materials is low; the organic phosphorus extractant which is harmful to the environment is used, and the mother liquor is difficult to extract and absorb. The method introduces resin for removing impurities, and the strong acid selective resin has strong adsorption effect on specific impurities, but the resin has limited effect and cannot change the complexity of the process. It is therefore desirable to provide a simpler, high yield metal ion recovery process.
Disclosure of Invention
The invention mainly aims to provide a recovery method and a recovery system for a metal oxide anode material, which are used for solving the problems of complex metal ion recovery process and low yield in the prior art.
In order to achieve the purpose of the invention, the technical scheme provided by the invention is as follows:
the invention provides a recovery method of a metal oxide positive electrode material, which comprises the following steps: performing pulping pretreatment on a metal oxide anode material to prepare a slurry; acidifying and oxidizing the slurry to make the slurry fully react to form feed liquid, and then deacidifying; adsorbing the deacidified feed liquid, and then desorbing to obtain the recovery liquid containing the metal.
Further, the recovery method includes: and crushing the metal oxide anode material, and stirring and mixing the crushed metal oxide anode material and a pulping dispersing agent to prepare the slurry.
And further, conveying the slurry to a dissociation device, introducing air into the dissociation device, stirring the slurry, and fully contacting the slurry with an acidic medium to perform acidification oxidation treatment to obtain the feed liquid.
Further, the feed liquid is introduced into a deacidification device, so that strong acid ions in the feed liquid are fully absorbed, and the pH value of discharged material is regulated to 6-8; the deacidification device is filled with alkaline resin.
Further, the de-acidified feed liquid is subjected to primary adsorption, a device adopted by the primary adsorption is filled with resin, the resin can at least selectively adsorb heavy metal ions, and the heavy metal ions comprise at least one of nickel, cobalt, manganese and copper.
Further, the feed liquid subjected to the primary adsorption is subjected to secondary adsorption, and a device adopted by the secondary adsorption is filled with resin, wherein the resin can at least selectively adsorb lithium ions.
Another aspect of the present invention also provides a recovery system of a metal oxide-based cathode material, which is mainly used in the above recovery method, and the recovery system includes:
the pulping device is at least used for pulping pretreatment of the metal oxide anode material to prepare pulp;
the dissociation device is at least used for carrying out acidification and oxidation treatment on the slurry so as to enable the slurry to fully react to form feed liquid;
a de-acidification device; at least using feed liquid to carry out deacidification treatment;
an adsorption device at least used for adsorbing the deacidified feed liquid and removing metal ions in the feed liquid;
and a liquid storage device.
Further, the adsorption device comprises a primary adsorption device, preferably, the adsorption device further comprises: and a second adsorption device arranged after the first adsorption device.
Compared with the prior art, the invention has the beneficial effects that:
1) The recovery method provided by the invention is suitable for the recovery and reutilization of various metal oxide positive electrode materials, does not need to separate the waste metal oxide positive electrode materials, and can directly enter a recovery flow. The recovery method adopts a multistage adsorption mode to complete the recovery of metals such as nickel, cobalt, manganese, copper, lithium and the like at one time.
2) The recovery method provided by the invention does not need high temperature, has low energy consumption, can be operated at normal temperature and normal pressure, does not use an organic solvent for extraction in the whole process flow, can recycle pulping dispersing agent for multiple times, and has little harm to the environment.
3) The recovery method provided by the invention uses the specific adsorption resin to directly treat the heavy metals and lithium in the waste liquid, and has the advantages of low equipment requirement, simple working procedure and high recovery efficiency.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural view of a recovery system of a metal oxide-based cathode material according to an exemplary embodiment of the present application.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has made a long-term study and a great deal of practice to propose the technical scheme of the present invention, and the technical scheme of the present invention will be clearly and completely described below, which is mainly a recovery method and a recovery system for metal oxide positive electrode materials.
As an aspect of an embodiment of the present invention, a method for recovering a metal oxide-based positive electrode material includes: performing pulping pretreatment on a metal oxide anode material to prepare a slurry; acidifying and oxidizing the slurry to make the slurry fully react to form feed liquid, and then deacidifying; adsorbing the deacidified feed liquid, and then desorbing to obtain the recovery liquid containing the metal.
Further, the recovery method of the metal oxide positive electrode material comprises the following steps: and crushing the positive plate containing the metal oxide positive electrode material, preparing the metal oxide positive electrode material, and stirring and mixing the metal oxide positive electrode material and the pulping dispersing agent to prepare the slurry.
Further, the size of the broken positive plate is smaller than 3cm.
In some preferred embodiments, the pulping dispersant includes, but is not limited to, N-methylpyrrolidone.
In some preferred embodiments, the mass ratio of the metal oxide based cathode material to the pulping dispersant is 0.5-0.8:1.
In some preferred embodiments, the stirring is at a rate of 300-600rpm for a period of 6-12 hours.
In some preferred embodiments, the metal oxide-based positive electrode material is derived from a waste metal oxide-based positive electrode sheet.
And further, conveying the slurry to a dissociation device, introducing air into the dissociation device, stirring the slurry, and fully contacting the slurry with an acidic medium to perform acidification oxidation treatment to obtain the feed liquid.
In some preferred embodiments, the dissociation device comprises a dissociation column having an aspect ratio of 20-25:1.
In some preferred embodiments, a packing is provided in the dissociation device, the packing having a packing volume of 60-90% of the dissociation device volume. Wherein the filler may include asbestos, but is not limited thereto.
In some preferred embodiments, the acidic medium may include a strong acid, for example, preferably any one or a combination of two or more of hydrochloric acid, sulfuric acid, nitric acid, etc., but is not limited thereto.
Further, the concentration of the acidic medium is 1-4mol/L, and the adding volume of the acidic medium is 30-70% of the residual volume of the dissociation device after filling.
In some preferred embodiments, the slurry is fed in an amount of 1/5 to 1/10 of the volume of the dissociation device per hour.
In some preferred embodiments, the air intake per hour is 1/3-2/3 of the dissociation device volume.
In some preferred embodiments, the feed liquid is introduced into a deacidification device, so that strong acid ions in the feed liquid are fully absorbed, and the pH value of the discharged material is adjusted to 6-8; the deacidification device is filled with alkaline resin, can adsorb acidic substances, and controls the feed liquid inlet flow, so that strong acid ions in the feed liquid are fully absorbed.
In some preferred embodiments, the deacidification apparatus is a deacidification column having an aspect ratio of 15-20:1.
In some preferred embodiments, the basic resin is an acid-adsorbing basic anion exchange resin, and the resin model used in the experiments of the present invention is ZGA 307.307 FM type resin.
In some preferred embodiments, the basic resin has a fill volume of 60-90% of the deacidification apparatus volume.
In some preferred embodiments, the feed liquid is fed in an amount of 1/5 to 1/2 of the volume of the de-acidification device per hour.
Further, the deacidified feed liquid is subjected to primary adsorption, and filling resin adopted by the primary adsorption can at least selectively adsorb heavy metal ions, wherein the heavy metal ions comprise at least one of nickel, cobalt, manganese and copper.
In some preferred embodiments, the filling resin used in the primary adsorption is a large-pore-size styrene resin, the functional group is iminodiethyl, and the resin is a D851 type resin which can selectively adsorb heavy metal ions. Wherein the aperture of the styrene resin is 20-100nm.
In some preferred embodiments, the primary adsorption employs a primary adsorption device having an aspect ratio of 15-20:1.
In some preferred embodiments, the packed resin has a volume of 60-90% of the volume of the primary adsorption unit.
In some preferred embodiments, the feed rate per hour of the de-acidified feed solution is 1.5-2 times the volume of the primary adsorption unit (over time, other metal ions may be adsorbed, resulting in reduced purity of the dissociation solution).
Further, the feed liquid after the primary adsorption is subjected to secondary adsorption, and filling resin adopted by the secondary adsorption can at least selectively adsorb lithium ions.
In some preferred embodiments, the secondary adsorption employs a secondary adsorption device having an aspect ratio of 15-20:1.
In some preferred embodiments, the filling resin used in the secondary adsorption is a high-efficiency lithium ion sieve adsorbent, the functional group is a lithium ion sieve, and lithium ions can be selectively adsorbed, and the type of the adsorbent used in the experiment is HPL800.
In some preferred embodiments, the secondary adsorption employs a packed resin volume that is 60-90% of the volume of the secondary adsorption device.
In some preferred embodiments, the feed rate of the feed liquid after the primary adsorption is 2-5 times of the volume of the secondary adsorption device (the adsorption rate is faster, the time is properly shortened under the condition of ensuring the adsorption effect, and the adsorption efficiency is improved).
Further, the primary adsorption device and the secondary adsorption device are desorbed to obtain a recovery liquid containing metal.
In some preferred embodiments, the desorbent in the primary adsorption device is pure water, and the desorbent enters from below, and the water inflow per hour is 5-7 times of the volume of the primary adsorption device at normal temperature and normal pressure.
In some preferred embodiments, the desorbent in the secondary adsorption device is pure water, and the desorbent enters from below, and the water inflow per hour is 4-6 times of the volume of the secondary adsorption device at normal temperature and normal pressure.
Further, the feed liquid after the primary adsorption and the secondary adsorption is recycled as pulping dispersing agent.
In some embodiments, the recycled material is waste metal oxide positive electrode sheet, and the method is a multistage oxidation continuous adsorption method, which comprises the following specific steps:
a. preparation: the medium is filled into each stage of exchange column according to the requirement (the filling volume of the medium is 60-90% of the volume of the exchange column, and the medium is specifically adjusted according to the actual situation). The pulping tank is filled with a certain amount of ultrapure water, and the transport pump is started according to 5-10m 3 The flow rate of/h conveys ultrapure water to the cleaning medium in each exchange column for 30-60min, and each exchange column is filled with ultrapure water (ensuring the wet state of the resin and at least covering the surface of the resin) after the cleaning is finished.
b. Pretreatment: adding N-methyl pyrrolidone (NMP) with the volume of 1/2-2/3 of the pulping tank into the pulping tank, taking positive plates with the mass of 0.5-0.8 times of the NMP, cutting, adding into the pulping tank, starting stirring at the stirring speed of 300-600rpm, starting a circulating pump, stirring for 6-12h in a circulating way, checking and cleaning the filter every hour until the filter is free of aluminum foil fragments.
c. Acidifying and oxidizing: the circulating pump is closed, the transport pump is opened, the slurry is transported to the dissociation column, column body filler of the dissociation column is asbestos, a slurry transmission path is increased, the slurry is fully reacted, two ends of the dissociation column are provided with filtering devices, the aperture is smaller than 300um, fine aluminum sheets are further filtered, the lower end of the column body is continuously introduced with air, an oxidation environment is provided, and the slurry in the column is stirred simultaneously, so that the slurry is fully contacted with the air. The dissociation column is filled with acidic medium, and the air and the feeding flow of the slurry are controlled to make the slurry fully react to form feed liquid (the slurry is changed into feed liquid by an acidification oxidation method, so that the subsequent treatment is convenient).
d. Deacidification: the feed liquid enters the deacidification column through a pipeline. The filler of the deacidification column is alkaline resin, can adsorb acidic substances, controls the inlet flow of the feed liquid, fully absorbs strong acid ions in the feed liquid, and adjusts the pH value of the discharged material to be 6-8.
e. Primary adsorption: the feed liquid enters the first-stage adsorption column through a pipeline. The filler of the first-stage adsorption column is macroporous resin, heavy metal ions can be selectively adsorbed in the multi-ion solution, and the selectivity of the feed liquid with high concentration can be improved. By controlling the feeding speed of the feed liquid, nickel, cobalt, manganese, copper and other ions in the feed liquid are fully absorbed.
f. Secondary adsorption: the feed liquid enters the secondary adsorption column through a pipeline. The filling of the secondary adsorption column is an ion sieve adsorbent, and can selectively adsorb lithium ions in a multi-ion solution. By controlling the feed rate of the feed liquid, lithium ions in the feed liquid are sufficiently adsorbed (this step may be omitted for recovery of the positive electrode of the sodium ion battery).
g. The liquid storage tank is thrown back: the feed liquid after multistage adsorption enters a liquid storage tank, and at the moment, the feed liquid mainly comprises NMP and is returned to a pulping tank for recycling through a pipeline.
h. And (3) desorbing at each stage: desorbing each level of adsorption column with specific desorber to obtain high purity metal solution.
Another aspect of the embodiments of the present invention also provides a recovery system of a metal oxide positive electrode material, which is mainly used in the aforementioned recovery method, and the recovery system includes:
the pulping device is at least used for pulping pretreatment of the metal oxide anode material to prepare pulp;
the dissociation device is at least used for carrying out acidification and oxidation treatment on the slurry so as to enable the slurry to fully react to form feed liquid;
a deacidification device for carrying out deacidification treatment on the feed liquid at least;
an adsorption device at least used for adsorbing the deacidified feed liquid and removing metal ions in the feed liquid;
and a liquid storage device.
Further, the adsorption device comprises a primary adsorption device, preferably, the adsorption device further comprises: and a second adsorption device arranged after the first adsorption device.
In the invention, referring to fig. 1, a recovery system diagram is shown, a pulping tank, a dissociation column, an acid removal column, a primary adsorption column, a secondary adsorption column and a liquid storage tank are sequentially connected, a circulating pump and a filter are arranged at the bottom of the pulping tank, and a transport pump is arranged between the pulping tank and the dissociation column.
In summary, the recovery method provided by the invention does not separate the conductive agent, the binder and the like from the waste battery anode, and adopts the acidification oxidation and multistage adsorption modes to complete the recovery and reuse of the waste metal oxide battery anode material at one time, thereby being applicable to the recovery and reuse of various metal oxide anode materials and also applicable to the anode recovery and reuse of lithium ion batteries and sodium ion batteries.
For further explanation of the present invention, the technical solutions of the present invention will be described in detail with reference to the examples, but it should be understood that these examples are given for detailed implementation and specific operation procedures based on the technical solutions of the present invention, and are only for further explanation of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the examples described below.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
All processes and equipment of the present invention are well known in the art, and each is well known and understood in the art for its associated use, and from the names, one skilled in the art can understand the steps of the process and the corresponding equipment used.
Example 1
The embodiment provides a method for recycling a metal oxide positive electrode material of a lithium ion battery, which comprises the following steps:
a. preparation: media are packed in each stage of exchange columns. Ultra-pure water is filled in a pulping tank, a transport pump is started, and the thickness of the ultra-pure water is 8m 3 The flow rate of/h conveys the ultrapure water to the cleaning medium in each exchange column, the cleaning time is 45min, and each exchange column is filled with ultrapure water after the cleaning is finished.
b. Pretreatment: adding N-methyl pyrrolidone (NMP) with the volume of 1/2 of the pulping tank into the pulping tank, taking fragments with the size of 1cm obtained by shearing positive plates with the mass of 0.5 times of NMP, adding the fragments into the pulping tank, starting stirring at the stirring speed of 500rpm, starting a circulating pump, and circulating stirring for 9 hours, checking and cleaning the filter every hour until the filter is free of aluminum foil fragments to obtain the slurry.
c. Acidifying and oxidizing: and (5) starting a conveying pump, and conveying the slurry to a dissociation column for acidizing and oxidizing. Wherein the height-diameter ratio of the dissociation column is 20:1, the filling material is asbestos, the filling volume is 80% of the volume of the dissociation column, the acidic medium is dilute sulfuric acid with the concentration of 2mol/L, and the addition amount is 50% of the residual volume of the dissociation column after the asbestos is filled. The feeding amount of the slurry per hour is 1/8 of the volume of the dissociation column, the air inflow amount of the air per hour is 1/2 of the volume of the dissociation column, and the acidification and oxidation are completed to form feed liquid.
d. Deacidification: the feed liquid enters the deacidification column through a pipeline. Wherein the height-diameter ratio of the deacidification column is 15:1, the filler is alkaline anion exchange resin ZGA FM, the filling volume is 80% of the volume of the deacidification column, the feeding amount of the feed liquid per hour is 2/5 of the volume of the deacidification column, and the feed liquid is discharged when the pH value of the feed liquid is 7.
e. Primary adsorption: the deacidified feed liquid enters a first-stage adsorption column through a pipeline. The ratio of the height to the diameter of the first-stage adsorption column is 15:1, the filler is large-aperture styrene resin D851 with the aperture of 50nm, the filling volume is 80% of the volume of the first-stage adsorption column, and the feeding amount of feed liquid per hour is 1.5 times of the volume of the first-stage adsorption column.
f. Secondary adsorption: the feed liquid after the primary adsorption enters a secondary adsorption column through a pipeline. The height-diameter ratio of the secondary adsorption column is 15:1, the filler is high-efficiency lithium ion sieve adsorbent HPL800, the filling volume is 80% of the volume of the secondary adsorption column, and the feeding amount of feed liquid per hour is 3 times of the volume of the secondary adsorption column.
g. And (3) desorbing at each stage: pure water is injected into the lower end of each stage of adsorption column, the water inflow per hour of the first stage of adsorption column is 6 times of the volume of the adsorption column, the water inflow per hour of the second stage of adsorption column is 5 times of the volume of the adsorption column, and the high-purity metal solution is obtained, the recovery rate of transition metal ions in the anode is 89.92%, and the recovery rate of lithium ions is 93.46%.
Example 2
The embodiment provides a method for recycling a metal oxide positive electrode material of a lithium ion battery, which comprises the following steps:
a. preparation: and loading the medium into each stage of exchange column according to the requirement. Pulping tank Adding ultrapure water, turning on a transport pump according to 5m 3 The flow rate of/h conveys the ultrapure water to the cleaning medium in each exchange column, the cleaning time is 60min, and each exchange column is filled with ultrapure water after the cleaning is finished.
b. Pretreatment: adding NMP with the volume of 2/3 of the pulping tank into the pulping tank, taking fragments with the mass of 0.8 times of NMP and shearing the fragments into fragments with the size of 2cm, adding the fragments into the pulping tank, starting stirring, wherein the stirring speed is 600rpm, simultaneously starting a circulating pump, circularly stirring for 6 hours, checking and cleaning the filter every hour until the filter is free of aluminum foil fragments.
c. Acidifying and oxidizing: and (5) starting a conveying pump, and conveying the slurry to a dissociation column for acidizing and oxidizing. Wherein the height-diameter ratio of the dissociation column is 25:1, the filling material is asbestos, the filling volume is 70% of the volume of the dissociation column, the adding amount of nitric acid with the acid medium of 3mol/L is 40% of the residual volume of the dissociation column after the asbestos is filled. The feeding amount of the slurry per hour is 1/5 of the volume of the dissociation column, the air inflow per hour is 2/3 of the volume of the dissociation column, and the acidification and oxidation are completed to form the feed liquid.
d. Deacidification: the feed liquid enters the deacidification column through a pipeline. Wherein the height-diameter ratio of the deacidification column is 20:1, the filler is alkaline anion exchange resin ZGA FM, the filling volume is 90% of the volume of the deacidification column, the feeding amount of the feed liquid per hour is 1/2 of the volume of the deacidification column, and the feed liquid is discharged when the pH value of the feed liquid is 6.
e. Primary adsorption: the feed liquid enters the first-stage adsorption column through a pipeline. The ratio of the height to the diameter of the first-stage adsorption column is 20:1, the filler is large-aperture styrene resin D851 with the aperture of 100nm, the filling volume is 70% of the volume of the first-stage adsorption column, and the feeding amount of feed liquid per hour is 2 times of the volume of the first-stage adsorption column.
f. Secondary adsorption: the feed liquid after the primary absorption enters a secondary absorption column through a pipeline. The height-diameter ratio of the secondary adsorption column is 20:1, the filler is high-efficiency lithium ion sieve adsorbent HPL800, the filling volume is 70% of the volume of the secondary adsorption column, and the feeding amount of feed liquid per hour is 5 times of the volume of the secondary adsorption column.
g. And (3) desorbing at each stage: pure water is injected into the lower end of each stage of adsorption column, the water inflow per hour of the first stage of adsorption column is 7 times of the volume of the adsorption column, the water inflow per hour of the second stage of adsorption column is 6 times of the volume of the adsorption column, and the high-purity metal solution is obtained, the recovery rate of transition metal ions in the anode is 87.24%, and the recovery rate of lithium ions is 90.84%.
Example 3
The embodiment provides a method for recycling a metal oxide positive electrode material of a lithium ion battery, which comprises the following steps:
a. preparation: and loading the medium into each stage of exchange column according to the requirement. Filling ultrapure water into a pulping tank, turning on a transport pump according to 10m 3 The flow rate of/h conveys the ultrapure water to the cleaning medium in each exchange column for 30min, and each exchange column is filled with ultrapure water after the cleaning is finished.
b. Pretreatment: adding NMP with 3/5 of the volume of the pulping tank into the pulping tank, taking fragments with the mass of NMP being 0.7 times that of positive plates, cutting the fragments into fragments with the size of 3cm, adding the fragments into the pulping tank, starting stirring, wherein the stirring speed is 300rpm, simultaneously starting a circulating pump, circularly stirring for 12 hours, checking and cleaning the filter every hour until the filter is free of aluminum foil fragments.
c. Acidifying and oxidizing: and (5) starting a conveying pump, and conveying the slurry to a dissociation column for acidizing and oxidizing. Wherein the height-diameter ratio of the dissociation column is 22:1, the filling material is asbestos, the filling volume is 90% of the volume of the dissociation column, hydrochloric acid with the acid medium of 1mol/L is added, and the addition amount is 70% of the residual volume of the dissociation column after the asbestos is filled. The feeding amount of the slurry per hour is 1/10 of the volume of the dissociation column, the air inflow per hour is 1/3 of the volume of the dissociation column, and the acidification and oxidation are completed to form the feed liquid.
d. Deacidification: the feed liquid enters the deacidification column through a pipeline. Wherein the height-diameter ratio of the deacidification column is 18:1, the filling material is alkaline anion exchange resin ZGA FM 307, the filling volume is 70% of the volume of the deacidification column, the feeding amount of the feed liquid per hour is 1/5 of the volume of the deacidification column, and the feed liquid is discharged when the pH value of the feed liquid is 8.
e. Primary adsorption: the deacidified feed liquid enters a first-stage adsorption column through a pipeline. The ratio of the height to the diameter of the first-stage adsorption column is 18:1, the filler is large-aperture styrene resin D851 with the aperture of 20nm, the filling volume is 90% of the volume of the first-stage adsorption column, and the feeding amount of feed liquid per hour is 1.5 times of the volume of the first-stage adsorption column.
f. Secondary adsorption: the feed liquid enters the secondary adsorption column through a pipeline. The height-diameter ratio of the secondary adsorption column is 18:1, the filler is high-efficiency lithium ion sieve adsorbent HPL800, the filling volume is 90% of the volume of the secondary adsorption column, and the feeding amount of feed liquid per hour is 2 times of the volume of the secondary adsorption column.
g. And (3) desorbing at each stage: pure water is injected into the lower end of each stage of adsorption column, the water inflow per hour of the first stage of adsorption column is 5 times of the volume of the adsorption column, the water inflow per hour of the second stage of adsorption column is 4 times of the volume of the adsorption column, and the high-purity metal solution is obtained, the recovery rate of transition metal ions in the anode is 86.62%, and the recovery rate of lithium ions is 91.35%.
Example 4
The embodiment provides a method for recycling a metal oxide positive electrode material of a lithium ion battery, which comprises the following steps:
a. preparation: and loading the medium into each stage of exchange column according to the requirement. Filling ultrapure water into a pulping tank, turning on a transport pump according to 7m 3 The flow rate of/h conveys the ultrapure water to the cleaning medium in each exchange column for 40min, and each exchange column is filled with ultrapure water after the cleaning is finished.
b. Pretreatment: adding NMP with the volume of 1/2 of the pulping tank into the pulping tank, taking fragments with the mass of 0.6 times of NMP and shearing the fragments into fragments with the size of 2cm, adding the fragments into the pulping tank, starting stirring, wherein the stirring speed is 400rpm, simultaneously starting a circulating pump, circularly stirring for 10 hours, checking and cleaning the filter every hour until the filter is free of aluminum foil fragments.
c. Acidifying and oxidizing: and (5) starting a conveying pump, and conveying the slurry to a dissociation column for acidizing and oxidizing. Wherein the height-diameter ratio of the dissociation column is 20:1, the filling material is asbestos, the filling volume is 60% of the volume of the dissociation column, sulfuric acid with the acid medium of 4mol/L is added, and the addition amount is 30% of the residual volume of the dissociation column after the asbestos is filled. The feeding amount of the slurry per hour is 1/6 of the volume of the dissociation column, the air inflow amount per hour is 1/3 of the volume of the dissociation column, and the acidification and oxidation are completed to form the feed liquid.
d. Deacidification: the feed liquid enters the deacidification column through a pipeline. Wherein the height-diameter ratio of the deacidification column is 18:1, the filling material is alkaline anion exchange resin ZGA FM 307, the filling volume is 60% of the volume of the deacidification column, the feeding amount of the feed liquid per hour is 2/5 of the volume of the deacidification column, and the feed liquid is discharged when the pH value of the feed liquid is 6.
e. Primary adsorption: the deacidified feed liquid enters a first-stage adsorption column through a pipeline. The ratio of the height to the diameter of the first-stage adsorption column is 18:1, the filler is large-aperture styrene resin D851 with the aperture of 80nm, the filling volume is 60% of the volume of the first-stage adsorption column, and the feeding amount of feed liquid per hour is 1.7 times of the volume of the first-stage adsorption column.
f. Secondary adsorption: the feed liquid enters the secondary adsorption column through a pipeline. The height-diameter ratio of the secondary adsorption column is 18:1, the filler is high-efficiency lithium ion sieve adsorbent HPL800, the filling volume is 60% of the volume of the secondary adsorption column, and the feed rate of feed liquid per hour is 4 times of the volume of the secondary adsorption column.
g. And (3) desorbing at each stage: pure water is injected into the lower end of each stage of adsorption column, the water inflow per hour of the first stage of adsorption column is 6 times of the volume of the adsorption column, the water inflow per hour of the second stage of adsorption column is 6 times of the volume of the adsorption column, and the high-purity metal solution is obtained, the recovery rate of transition metal ions in the anode is 88.97%, and the recovery rate of lithium ions is 91.57%.
Example 5
The embodiment provides a method for recycling a sodium ion metal oxide positive electrode material, which comprises the following steps:
a. preparation: and loading the medium into each stage of exchange column according to the requirement. Filling ultrapure water into a pulping tank, turning on a transport pump according to 6m 3 The flow rate of/h conveys the ultrapure water to the cleaning medium in each exchange column for 50min, and each exchange column is filled with ultrapure water after the cleaning is finished.
b. Pretreatment: adding NMP with the volume of 2/3 of the pulping tank into the pulping tank, taking fragments with the mass of NMP being 0.7 times that of positive plates, cutting the fragments into fragments with the size of 1cm, adding the fragments into the pulping tank, starting stirring, starting a circulating pump at the stirring speed of 500rpm, and circulating stirring for 8 hours, checking and cleaning the filter every hour until the filter is free of aluminum foil fragments.
c. Acidifying and oxidizing: and (5) starting a conveying pump, and conveying the slurry to a dissociation column for acidizing and oxidizing. Wherein the height-diameter ratio of the dissociation column is 25:1, the filling material is asbestos, the filling volume is 70% of the volume of the dissociation column, and nitric acid with the acid medium of 2mol/L is added, and the addition amount is 40% of the residual volume of the dissociation column after the asbestos is filled. The feeding amount of the slurry per hour is 1/7 of the volume of the dissociation column, the air inflow amount per hour is 1/3 of the volume of the dissociation column, and the acidification and oxidation are completed to form the feed liquid.
d. Deacidification: the feed liquid enters the deacidification column through a pipeline. Wherein the height-diameter ratio of the deacidification column is 20:1, the filling material is alkaline anion exchange resin ZGA FM, the filling volume is 80% of the volume of the deacidification column, the feeding amount of the feed liquid per hour is 1/4 of the volume of the deacidification column, and the feed liquid is discharged when the pH value of the feed liquid is 7.
e. Primary adsorption: the deacidified feed liquid enters a first-stage adsorption column through a pipeline. The height-diameter ratio of the first-stage adsorption column is 20:1, the filler is large-aperture styrene resin D851 with the aperture of 40nm, the filling volume is 90% of the volume of the first-stage adsorption column, and the feeding amount of feed liquid per hour is 1.6 times of the volume of the first-stage adsorption column.
f. And (3) desorption: pure water is injected into the lower end of the first-stage adsorption column, the water inflow per hour is 7 times of the volume of the adsorption column, and the high-purity metal solution is obtained, and the recovery rate of transition metal ions in the anode is 84.68%.
Example 6
The embodiment provides a method for recycling a sodium ion metal oxide positive electrode material, which comprises the following steps:
a. preparation: and loading the medium into each stage of exchange column according to the requirement. Filling ultrapure water into a pulping tank, turning on a transport pump according to 9m 3 The flow rate of/h conveys the ultrapure water to the cleaning medium in each exchange column for 40min, and each exchange column is filled with ultrapure water after the cleaning is finished.
b. Pretreatment: adding NMP with 3/5 of the volume of the pulping tank into the pulping tank, taking fragments with the size of 2cm obtained by shearing positive plates with the mass of 0.5 times of NMP, adding the fragments into the pulping tank, starting stirring, wherein the stirring speed is 600rpm, simultaneously starting a circulating pump, circularly stirring for 7h, checking and cleaning the filter every hour until the filter is free of aluminum foil fragments.
c. Acidifying and oxidizing: and (5) starting a conveying pump, and conveying the slurry to a dissociation column for acidizing and oxidizing. Wherein the height-diameter ratio of the dissociation column is 20:1, the filling material is asbestos, the filling volume is 60% of the volume of the dissociation column, sulfuric acid with the acid medium of 3mol/L is added, and the addition amount is 60% of the residual volume of the dissociation column after the asbestos is filled. The feeding amount of the slurry per hour is 1/9 of the volume of the dissociation column, the air inflow per hour is 1/2 of the volume of the dissociation column, and the acidification and oxidation are completed to form the feed liquid.
d. Deacidification: the feed liquid enters the deacidification column through a pipeline. Wherein the height-diameter ratio of the deacidification column is 18:1, the filling material is alkaline anion exchange resin ZGA FM 307, the filling volume is 70% of the volume of the deacidification column, the feeding amount of the feed liquid per hour is 1/3 of the volume of the deacidification column, and the feed liquid is discharged when the pH value of the feed liquid is 6.
e. Primary adsorption: the deacidified feed liquid enters a first-stage adsorption column through a pipeline. The ratio of the height to the diameter of the first-stage adsorption column is 18:1, the filler is large-aperture styrene resin D851 with the aperture of 60nm, the filling volume is 80% of the volume of the first-stage adsorption column, and the feeding amount of feed liquid per hour is 1.5 times of the volume of the first-stage adsorption column.
f. And (3) desorption: pure water is injected into the lower end of the first-stage adsorption column, the water inflow per hour is 5 times of the volume of the adsorption column, and the high-purity metal solution is obtained, and the recovery rate of transition metal ions in the anode is 90.54%.
Comparative example 1
The recovery method of the metal oxide positive electrode material of the lithium ion battery comprises the following steps:
a. preparation: media are packed in each stage of exchange columns. Filling ultrapure water into a pulping tank, turning on a transport pump according to 8m 3 The flow rate of/h conveys the ultrapure water to the cleaning medium in each exchange column, the cleaning time is 45min, and each exchange column is filled with ultrapure water after the cleaning is finished.
b. Pretreatment: adding NMP with the volume of 1/2 of the pulping tank into the pulping tank, taking fragments with the mass of NMP being 0.5 times that of positive plates, cutting the fragments into fragments with the size of 1cm, adding the fragments into the pulping tank, starting stirring, starting a circulating pump at the stirring speed of 500rpm, and circulating stirring for 9 hours, checking and cleaning the filter every hour until the filter is free of aluminum foil fragments.
c. Acidifying: and (5) starting a conveying pump, and conveying the slurry to a dissociation column for acidification and dissociation. Wherein the height-diameter ratio of the dissociation column is 20:1, the filling material is asbestos, the filling volume is 80% of the volume of the dissociation column, the acidic medium is dilute sulfuric acid with the concentration of 2mol/L, and the addition amount is 50% of the residual volume of the dissociation column after the asbestos is filled. The slurry feed per hour was 1/8 of the dissociation column volume and acidification was completed to form feed liquid (only acidification, no oxidation).
d. Deacidification: the feed liquid enters the deacidification column through a pipeline. Wherein the height-diameter ratio of the deacidification column is 15:1, the filler is alkaline anion exchange resin ZGA FM, the filling volume is 80% of the volume of the deacidification column, the feeding amount of the feed liquid per hour is 2/5 of the volume of the deacidification column, and the feed liquid is discharged when the pH value of the feed liquid is 7.
e. Primary adsorption: the feed liquid enters the first-stage adsorption column through a pipeline. The ratio of the height to the diameter of the first-stage adsorption column is 15:1, the filler is large-aperture styrene resin D851 with the aperture of 50nm, the filling volume is 80% of the volume of the first-stage adsorption column, and the feeding amount of feed liquid per hour is 1.5 times of the volume of the first-stage adsorption column.
f. Secondary adsorption: the feed liquid enters the secondary adsorption column through a pipeline. The height-diameter ratio of the secondary adsorption column is 15:1, the filler is high-efficiency lithium ion sieve adsorbent HPL800, the filling volume is 80% of the volume of the secondary adsorption column, and the feeding amount of feed liquid per hour is 3 times of the volume of the secondary adsorption column.
g. And (3) desorbing at each stage: pure water is injected into the lower end of each stage of adsorption column, the water inflow per hour of the first stage of adsorption column is 6 times of the volume of the adsorption column, the water inflow per hour of the second stage of adsorption column is 5 times of the volume of the adsorption column, and a metal-containing solution is obtained, the recovery rate of transition metal ions in the anode is 65.52%, and the recovery rate of lithium ions is 45.56%.
Comparative example 2
The recovery method of the metal oxide positive electrode material of the lithium ion battery comprises the following steps:
a. preparation: and loading the medium into each stage of exchange column according to the requirement. Filling ultrapure water into a pulping tank, turning on a transport pump according to 8m 3 The flow rate of/h conveys the ultrapure water to the cleaning medium in each exchange column, the cleaning time is 45min, and each exchange column is filled with ultrapure water after the cleaning is finished.
b. Pretreatment: adding NMP with the volume of 1/2 of the pulping tank into the pulping tank, taking fragments with the mass of NMP being 0.5 times that of positive plates, cutting the fragments into 1cm pieces, adding the fragments into the pulping tank, starting stirring, wherein the stirring speed is 500rpm, simultaneously starting a circulating pump, circularly stirring for 9 hours, checking and cleaning the filter every hour until the filter is free of aluminum foil fragments.
c. Oxidizing: and (5) starting a conveying pump to convey the slurry to a dissociation column for dissociation. Wherein the height-diameter ratio of the dissociation column is 20:1, the filling material is asbestos, the filling volume is 80% of the volume of the dissociation column, and no acid medium is added. The slurry feed per hour was 1/8 of the dissociation column volume, and the air intake per hour was 1/2 of the dissociation column volume (oxygen only, not acidified).
d. Primary adsorption: the feed liquid directly enters the first-stage adsorption column without acidification. The ratio of the height to the diameter of the first-stage adsorption column is 15:1, the filler is large-aperture styrene resin D851 with the aperture of 50nm, the filling volume is 80% of the volume of the first-stage adsorption column, and the feeding amount of feed liquid per hour is 1.5 times of the volume of the first-stage adsorption column.
e. Secondary adsorption: the feed liquid enters the secondary adsorption column through a pipeline. The height-diameter ratio of the secondary adsorption column is 15:1, the filler is high-efficiency lithium ion sieve adsorbent HPL800, the filling volume is 80% of the volume of the secondary adsorption column, and the feeding amount of feed liquid per hour is 3 times of the volume of the secondary adsorption column.
f. And (3) desorbing at each stage: pure water is injected into the lower end of each stage of adsorption column, the water inflow per hour of the first stage of adsorption column is 6 times of the volume of the adsorption column, the water inflow per hour of the second stage of adsorption column is 5 times of the volume of the adsorption column, and a metal-containing solution is obtained, the recovery rate of transition metal ions in the anode is 2.29%, and the recovery rate of lithium ions is 26.91%.
Comparative example 3 (in comparison with example 6, oxidative acidification without addition of filler asbestos, reduced oxidative acidification area)
The recovery method of the metal oxide positive electrode material of the sodium ion battery comprises the following steps:
a. preparation: and loading the medium into each stage of exchange column according to the requirement. Filling ultrapure water into a pulping tank, turning on a transport pump according to 9m 3 The flow rate of/h conveys the ultrapure water to the cleaning medium in each exchange column for 40min, and each exchange column is filled with ultrapure water after the cleaning is finished.
b. Pretreatment: adding NMP with 3/5 of the volume of the pulping tank into the pulping tank, taking fragments with the mass of NMP being 0.5 times that of positive plates, cutting the fragments into 2cm pieces, adding the fragments into the pulping tank, starting stirring, wherein the stirring speed is 600rpm, simultaneously starting a circulating pump, circularly stirring for 7h, checking and cleaning the filter every hour until the filter is free of aluminum foil fragments.
c. Dissociation: and (5) starting a conveying pump, and conveying the slurry to a dissociation column for acidolysis. Wherein the height-diameter ratio of the dissociation column is 20:1, sulfuric acid with the acid medium of 3mol/L is directly added without adding the filling material, and the adding volume is 24% of the volume of the dissociation column. The slurry feed per hour was 1/9 of the dissociation column volume, and the air intake per hour was 1/2 of the dissociation column volume.
d. Deacidification: the feed liquid enters the deacidification column through a pipeline. Wherein the height-diameter ratio of the deacidification column is 18:1, the filling material is alkaline anion exchange resin ZGA FM 307, the filling volume is 70% of the volume of the deacidification column, the feeding amount of the feed liquid per hour is 1/3 of the volume of the deacidification column, and the feed liquid is discharged when the pH value of the feed liquid is 6.
e. Primary adsorption: the feed liquid enters the first-stage adsorption column through a pipeline. The ratio of the height to the diameter of the first-stage adsorption column is 18:1, the filler is large-aperture styrene resin D851 with the aperture of 60nm, the filling volume is 80% of the volume of the first-stage adsorption column, and the feeding amount of feed liquid per hour is 1.5 times of the volume of the first-stage adsorption column.
f. And (3) desorption: pure water is injected into the lower end of the first-stage adsorption column, the water inflow per hour is 5 times of the volume of the adsorption column, and a metal-containing solution is obtained, and the recovery rate of transition metal ions in the anode is 53.64%.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
Claims (10)
1. A method for recovering a metal oxide positive electrode material is characterized by comprising the steps of: performing pulping pretreatment on a metal oxide anode material to prepare a slurry; acidifying and oxidizing the slurry to make the slurry fully react to form feed liquid, and then deacidifying; adsorbing the deacidified feed liquid, and then desorbing to obtain the recovery liquid containing the metal.
2. The method for recovering a metal oxide-based positive electrode material according to claim 1, comprising: crushing a positive plate containing a metal oxide positive electrode material, and stirring and mixing the crushed positive plate with a pulping dispersing agent to prepare slurry;
preferably, the size of the broken positive plate is smaller than 3cm;
preferably, the pulping dispersant comprises N-methylpyrrolidone;
preferably, the mass ratio of the metal oxide positive electrode material to the pulping dispersing agent is 0.5-0.8:1;
preferably, the stirring speed is 300-600rpm, and the stirring time is 6-12h;
preferably, the metal oxide positive electrode material is derived from a waste metal oxide positive electrode sheet.
3. The method for recovering a metal oxide-based positive electrode material according to claim 2, comprising: delivering the slurry to a dissociation device, introducing air into the dissociation device, stirring the slurry, and fully contacting the slurry with an acidic medium for acidizing and oxidizing to obtain a feed liquid;
Preferably, the dissociation device comprises a dissociation column with an aspect ratio of 20-25:1;
preferably, the dissociation device is internally provided with a filling material, and the filling volume of the filling material is 60-90% of the volume of the dissociation device; the filler comprises asbestos;
preferably, the acidic medium comprises a strong acid, preferably any one or more than two of hydrochloric acid, sulfuric acid and nitric acid;
preferably, the concentration of the acid medium is 1-4mol/L, and the adding volume of the acid medium is 30-70% of the residual volume after filling;
preferably, the slurry is fed in an amount of 1/5 to 1/10 of the volume of the dissociation device per hour;
preferably, the air intake per hour is 1/3 to 2/3 of the volume of the dissociation device.
4. The method for recovering a metal oxide-based positive electrode material according to claim 3, comprising: introducing the feed liquid into a deacidification device, fully absorbing strong acid ions in the feed liquid, and adjusting the pH value of discharged material to 6-8; the deacidification device is filled with alkaline resin;
preferably, the deacidification device is a deacidification column, and the height-to-diameter ratio is 15-20:1;
preferably, the basic resin is an acid-adsorbing basic anion exchange resin;
Preferably, the filling volume of the alkaline resin is 60-90% of the volume of the deacidification device;
preferably, the feed liquid is fed in an amount of 1/5-1/2 of the volume of the deacidification device per hour.
5. The method for recovering a metal oxide positive electrode material according to claim 4, comprising: carrying out primary adsorption on the deacidified feed liquid, wherein filling resin adopted in the primary adsorption can at least selectively adsorb heavy metal ions, and the heavy metal ions comprise at least one of nickel, cobalt, manganese and copper;
preferably, the filling resin adopted in the primary adsorption is styrene resin, the functional group is iminodiethyl, and the aperture is 20-100nm;
preferably, the height-diameter ratio of the primary adsorption device adopted by the primary adsorption is 15-20:1;
preferably, the volume of the filling resin is 60-90% of the volume of the primary adsorption device;
preferably, the feeding amount of the deacidified feed liquid per hour is 1.5-2 times of the volume of the primary adsorption device.
6. The method for recovering a metal oxide-based positive electrode material according to claim 5, further comprising: carrying out secondary adsorption on the feed liquid subjected to primary adsorption, wherein filling resin adopted by the secondary adsorption can at least selectively adsorb lithium ions;
Preferably, the height-diameter ratio of the secondary adsorption device adopted by the secondary adsorption is 15-20:1;
preferably, the filling resin adopted by the secondary adsorption is a lithium ion sieve adsorbent, and the functional group is a lithium ion sieve;
preferably, the volume of the filling resin adopted by the secondary adsorption is 60-90% of the volume of the secondary adsorption device;
preferably, the feed rate of the feed liquid after the primary adsorption per hour is 2-5 times of the volume of the secondary adsorption device.
7. The method for recovering a metal oxide-based positive electrode material according to claim 6, comprising: desorbing the primary adsorption device and the secondary adsorption device to obtain a recovery liquid containing metal;
preferably, the desorbing agent in the primary adsorption device is pure water, and the water inflow per hour is 5-7 times of the volume of the primary adsorption device;
preferably, the desorbent in the secondary adsorption device is pure water, and the water inflow per hour is 4-6 times of the volume of the secondary adsorption device.
8. The method for recovering a metal oxide-based positive electrode material according to claim 6, wherein: and recycling the feed liquid after the primary adsorption and the secondary adsorption as pulping dispersing agent for recycling.
9. A recovery system of a metal oxide-based cathode material, which is mainly used for the recovery method according to any one of claims 1 to 8, and which comprises:
the pulping device is at least used for pulping pretreatment of the metal oxide anode material to prepare pulp;
the dissociation device is at least used for carrying out acidification and oxidation treatment on the slurry so as to enable the slurry to fully react to form feed liquid;
a deacidification device for carrying out deacidification treatment on the feed liquid at least;
an adsorption device at least used for adsorbing the deacidified feed liquid and removing metal ions in the feed liquid;
and a liquid storage device.
10. The recovery system of metal oxide based positive electrode material according to claim 9, wherein: the adsorption device comprises a primary adsorption device, preferably, the adsorption device further comprises: and a second adsorption device arranged after the first adsorption device.
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