WO2024254856A1 - 基于提锂电池粉的回收处理方法 - Google Patents

基于提锂电池粉的回收处理方法 Download PDF

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Publication number
WO2024254856A1
WO2024254856A1 PCT/CN2023/100733 CN2023100733W WO2024254856A1 WO 2024254856 A1 WO2024254856 A1 WO 2024254856A1 CN 2023100733 W CN2023100733 W CN 2023100733W WO 2024254856 A1 WO2024254856 A1 WO 2024254856A1
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Prior art keywords
leaching
residue
acid
reducing agent
lithium battery
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PCT/CN2023/100733
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English (en)
French (fr)
Inventor
付堂新
邓开伟
安辉
陈若葵
阮丁山
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Application filed by Hunan Brunp Recycling Technology Co Ltd, Guangdong Brunp Recycling Technology Co Ltd filed Critical Hunan Brunp Recycling Technology Co Ltd
Priority to PCT/CN2023/100733 priority Critical patent/WO2024254856A1/zh
Priority to CN202380009535.2A priority patent/CN117044009B/zh
Publication of WO2024254856A1 publication Critical patent/WO2024254856A1/zh
Anticipated expiration legal-status Critical
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • 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

Definitions

  • the process of producing battery-grade nickel, cobalt and manganese from lithium battery powder generally uses a wet method.
  • the wet method generally uses a leaching-impurity removal-extraction-lithium extraction process to treat battery powder.
  • Most battery powder impurities are removed by adjusting the pH of the solution using soda ash/calcium carbonate to remove iron and aluminum from the solution.
  • the amount of residual acid introduced into the solution during the impurity removal process increases, which increases the consumption of auxiliary materials.
  • a recycling method based on lithium battery powder extraction comprises the following steps:
  • the battery powder after lithium extraction is subjected to slurrying operation to obtain slurry;
  • a first leaching and filtering operation is performed to obtain a first leaching solution and a first leaching residue
  • the first leachate is subjected to a P204 extraction and impurity removal operation to obtain a battery-grade nickel-cobalt-manganese solution;
  • the sulfuric acid, the reducing agent and the first leaching residue are mixed and then subjected to a second leaching and filtering operation to obtain a second leaching solution and a second leaching residue;
  • the pH value in the first stage of leaching and filtration operation is 4-6;
  • the pH value in the second stage leaching and filtration operation is 1-2.
  • FIG1 is a schematic flow diagram of a recycling method for lithium battery powder in one embodiment
  • FIG. 2 is a process flow chart of a recycling method based on lithium battery powder extraction.
  • a recycling method for lithium battery powder includes some or all of the following steps:
  • the lithium extraction slag after lithium extraction is the lithium extraction battery powder, and the battery powder is subjected to a slurrying operation to obtain a slurry to facilitate subsequent recycling and processing work.
  • the battery powder after lithium extraction mainly contains metal elements of iron, aluminum, copper, nickel, cobalt and manganese.
  • the first stage of leaching and filtering is performed in a leaching tank after mixing sulfuric acid, a reducing agent and a slurry.
  • the pH value of the first stage of leaching and filtering is controlled at 4 to 6.
  • the metal elements of iron, aluminum and copper are easy to form precipitation under the action of the reducing agent and the pH value of 4 to 6. In this way, nickel, cobalt and manganese can be separated from iron, aluminum and copper, so as to recover the metal elements of nickel, cobalt and manganese.
  • the battery powder after lithium extraction is doped with calcium, and the calcium is added to the first leachate after the first leaching and filtering operation.
  • the calcium ions in the first leachate are extracted by adding the P204 extractant, so as to remove impurities from the first leachate to obtain a battery-grade nickel-cobalt-manganese solution, and therefore, there is no need to perform a full extraction process on the leachate, thereby effectively reducing the consumption of auxiliary materials, and at the same time, the preparation method of the battery-grade nickel-cobalt-manganese solution can be greatly simplified, thereby simplifying the recovery and processing steps of the lithium-extracted battery powder.
  • nickel + cobalt + manganese is 100g/L ⁇ 120g/L, which is a battery-grade nickel-cobalt-manganese solution.
  • sulfuric acid, a reducing agent and a first leaching residue are mixed and then a second leaching and filtering operation is performed in a second leaching tank, and the pH value of the second leaching and filtering operation is controlled at 1 to 2.
  • a second leaching residue is formed at a pH value of 1 to 2 and under the action of the reducing agent, and the iron, aluminum and copper elements in the first leaching residue are leached to form a second leachate, so that the iron, aluminum and copper elements can be recovered.
  • the second leachate is subjected to impurity removal and filtration operations, and the filtered residue is iron-aluminum-copper residue, thereby realizing the recovery of iron, aluminum and copper elements.
  • the second leaching residue is rich in graphite
  • battery-grade graphite raw materials can be obtained by performing high-acid leaching and filtration operations on the second leaching residue, thereby realizing the recycling and reuse of graphite, and saving the cost of disposing the second leaching residue as solid waste or hazardous waste.
  • battery-grade graphite raw materials only need to be graphitized once to obtain battery-grade graphite, and battery-grade graphite raw materials can only be obtained when the content of nickel, cobalt and manganese in the leached slag is less than 0.08%, and there is no need for secondary impurity removal.
  • high acid here refers to acid with an acidity of more than 100 g/L, while the acidity of the first-stage filtration operation and the second-stage filtration operation are both below 100 g/L.
  • the pH value in the first stage of leaching and filtration operation is 4-6; the pH value in the second stage of leaching and filtration operation is 1-2.
  • Battery-grade nickel-cobalt-manganese solution does not need to be subjected to a full extraction process to complete the preparation of the battery-grade nickel-cobalt-manganese solution, which can effectively reduce the consumption of auxiliary materials, and can also greatly simplify the preparation method of the battery-grade nickel-cobalt-manganese solution, thereby simplifying the recovery and processing steps of lithium battery powder, thereby effectively improving the recovery and processing efficiency of lithium battery powder and reducing the recovery and processing cost of lithium battery powder.
  • sulfuric acid, a reducing agent and the first leaching residue are mixed and then subjected to a second leaching and filtering operation, while the pH value is strictly controlled between 1 and 2 and a second leaching residue is formed under the action of the reducing agent, and at the same time, the iron, aluminum and copper elements in the first leaching residue are leached and a second leaching liquid is formed, and the second leaching residue and the second leaching liquid are separated by filtration. Then, the second leaching liquid is subjected to an impurity removal and filtration operation to obtain a filter residue, and the filter residue is a mixed precipitate of iron, aluminum and copper, thereby achieving a better impurity removal and recovery effect.
  • the second leaching residue is rich in graphite
  • a battery-grade graphite raw material can be obtained by performing a high-acid leaching and filtration operation on the second leaching residue, thereby realizing the recycling and reuse of graphite, and at the same time, the cost of disposing the second leaching residue as solid waste or hazardous waste can be saved.
  • the specific operation steps of slurrying the lithium-extracted battery powder to obtain the slurry are: adding pure water to the lithium-extracted battery powder to perform slurrying operation to obtain the slurry with a solid content of 20% to 30%. It should be noted that the battery powder after lithium extraction is slurried with pure water to obtain a slurry with a solid content of 20% to 30%.
  • the recovery method further includes the following steps: dissolving the first leaching residue. It should be noted that the first leaching residue obtained by filtration needs to be formed into a liquid form first, and the first leaching residue is dissolved by adding pure water to facilitate the subsequent second leaching filtration operation.
  • the recovery method further includes the following steps:
  • the reducing agent and the first leaching residue are mixed and then subjected to a second leaching and filtering operation;
  • the sulfuric acid, the reducing agent, the first leaching residue and the slurry are mixed and then a first stage leaching and filtering operation is performed.
  • the impurity content in the first leaching residue can be obtained.
  • the mass percentage of the impurity content is less than 5%
  • the first leaching residue is returned to a leaching tank and the first leaching and filtration operation is circulated, which can effectively increase the impurity content in the second leachate, facilitate impurity removal, and reduce the waste of auxiliary materials for multiple impurity removals, thereby effectively reducing the use of impurity removal auxiliary materials, and further effectively reducing the recovery and processing costs of lithium battery powder.
  • the first leachate is subjected to a P204 extraction and impurity removal operation to obtain a battery-grade nickel-cobalt-manganese solution in the following specific steps:
  • the specific operation steps of performing impurity removal and filtration operation on the second leachate are:
  • an alkaline salt is added to the second leaching solution to perform filtering operation to obtain filter residue and filtrate.
  • the copper ions in the second leachate can be replaced.
  • the pH value of the second leachate is between 3 and 4, at which time both iron and aluminum can form corresponding metal salt precipitations, and then filtering operation is performed to obtain filter residues and filter liquid, wherein the filter residues are iron-aluminum-copper slag, so that the iron, aluminum and copper metal elements can be effectively recovered.
  • the active metal is one of iron powder, manganese powder or nickel powder. It should be noted that according to the metal activity sequence table, the copper ions in the second leaching solution can be replaced by selecting an active metal with an activity greater than that of copper.
  • the alkaline salt is industrial grade sodium carbonate or industrial grade sodium hydroxide. It should be noted that the use of high-purity raw materials such as industrial-grade sodium carbonate and industrial-grade sodium hydroxide as alkaline salts can effectively reduce the incorporation of impurities, thereby reducing the use of impurity removal auxiliary materials, and further effectively reducing the recycling and processing costs of lithium battery powder.
  • the specific operation steps of performing high acid leaching and filtering operation on the second leached residue to obtain battery-grade graphite raw material are:
  • the sulfuric acid, the reducing agent and the second leaching residue are mixed and then subjected to a first high-acid leaching filtration operation to obtain a first high-acid leaching residue and a first high-acid leaching solution;
  • the sulfuric acid, the reducing agent and the first high-acid leaching residue are mixed and then subjected to a second high-acid leaching filtration operation to obtain the battery-grade graphite raw material.
  • the metal content in the second leaching residue after the first leaching and filtering operation and the second leaching and filtering operation is relatively low.
  • the metal in the second leaching residue is first leached by a high acid leaching method with an acidity greater than 100 g/L through the first high acid leaching and filtering operation, that is, by increasing the acidity of sulfuric acid and increasing the number of back and forth collisions between sulfuric acid and the metal to be leached in the second leaching residue, the metal to be leached in the second leaching residue can be dissolved in sulfuric acid, so that the metal content in the first high acid leaching residue can be effectively reduced.
  • the metal content in the first high-acid leaching slag after the first high-acid leaching filtration operation is less than the metal content in the second leaching slag.
  • the acidity of the second high-acid leaching filtration operation is greater than the acidity of the first high-acid leaching filtration operation, that is, further increasing the acidity of sulfuric acid, thereby further increasing the number of back-and-forth collisions between sulfuric acid and the metal to be leached in the first high-acid leaching slag
  • the metal to be leached in the first high-acid leaching slag can be dissolved in sulfuric acid, so that the second high-acid leaching slag can meet the standard of battery-grade graphite raw materials.
  • the recovery and treatment method further includes the following steps: the sulfuric acid, the reducing agent, the first high-acid leaching liquid and the first leaching residue are mixed and then subjected to a second-stage leaching filtration operation.
  • the sulfuric acid, the reducing agent and the first high acid leaching slag are After the step of performing a second high-acid leaching and filtering operation after mixing to obtain the battery-grade graphite raw material, the recycling method further includes the following steps: mixing the sulfuric acid, the reducing agent, the second high-acid leaching solution and the second leaching residue and performing a first high-acid leaching and filtering operation.
  • the acidity of the first high-acid leaching and filtering operation is 200 g/L to 300 g/L. It is understandable that, at an acidity of 200 g/L to 300 g/L, the number of back-and-forth collisions between sulfuric acid and the metal to be leached in the second leaching residue can be increased, so that the metal to be leached can be dissolved in sulfuric acid, that is, the metal in the second leaching residue is leached into the first high-acid leaching solution.
  • the acidity of the second high-acid leaching and filtering operation is 300 g/L to 500 g/L. It is understandable that at an acidity of 300 g/L to 500 g/L, the number of back-and-forth collisions between sulfuric acid and the metal to be leached in the first high-acid leaching slag can be further increased, and the metal to be leached can be further dissolved in sulfuric acid, so that the second high-acid leaching slag can meet the standards of battery-grade graphite raw materials, which can not only save the cost of disposing the leaching slag as hazardous waste or solid waste, but also realize the recycling of graphite.
  • the temperature of the first high acid leaching filtration operation and the second high acid leaching filtration operation are both 80° C. to 100° C. It can be understood that at a temperature of 80° C. to 100° C., the first high acid leaching filtration operation and the second high acid leaching filtration operation can both leach the metal in the leached residue to the greatest extent, thereby achieving a better impurity removal effect.
  • the temperature of the first leaching and filtering operation is 80°C to 100°C. It should be noted that when the temperature is 80°C to 100°C and the pH value is strictly controlled between 4 and 6, the impurity content of iron, aluminum, copper and the like in the first leachate is less than 2ppm, that is, when the impurity content is less than 2ppm, the first leachate can meet the requirements of P204 extraction without further impurity removal, and the first leachate is subjected to extraction and impurity removal operation by the P204 extractant, so that a battery-grade nickel-cobalt-manganese solution can be obtained.
  • a battery-grade nickel-cobalt-manganese solution can be prepared without a full extraction process, which can greatly simplify the preparation process of a battery-grade nickel-cobalt-manganese solution, thereby simplifying the recovery and processing steps of lithium battery powder, and further improving the recovery and processing efficiency of lithium battery powder.
  • the reducing agent is at least one of hydrogen peroxide, sulfur dioxide and sodium sulfite. It should be noted that by adding a reducing agent, the metal elements such as iron, aluminum, copper, nickel, cobalt, and manganese in the lithium battery powder are reduced to corresponding metal ions, so as to facilitate the impurity removal and recycling process.
  • Pure water is added to the lithium battery powder to obtain a slurry with a solid content of 20%.
  • Sulfuric acid, a reducing agent and a slurry are mixed and the pH value is adjusted to 4.3, and then the first stage of leaching and filtering operation is performed to obtain a first leachate and a first leach residue.
  • the first leachate is subjected to a P204 extraction and impurity removal operation to obtain a battery-grade nickel-cobalt-manganese solution.
  • Sulfuric acid, a reducing agent and the first leach residue are mixed and the pH is adjusted to 1.5, and then the second stage of leaching and filtering operation is performed to obtain a second leachate and a second leach residue.
  • the second leachate is subjected to an impurity removal and filtering operation to obtain a filtrate and a filter residue.
  • the second leaching residue is subjected to a high acid leaching and filtering operation to obtain a battery-grade graphite raw material.
  • the first leaching solution is shown in Table 1:
  • the first leaching solution after P204 extraction and impurity removal is shown in Table 2:
  • Pure water is added to the lithium battery powder to obtain a slurry with a solid content of 20%.
  • Sulfuric acid, a reducing agent and a slurry are mixed and the pH value is adjusted to 4.8, and then the first stage of leaching and filtering operation is performed to obtain a first leachate and a first leach residue.
  • the first leachate is subjected to a P204 extraction and impurity removal operation to obtain a battery-grade nickel-cobalt-manganese solution.
  • Sulfuric acid, a reducing agent and the first leach residue are mixed and the pH is adjusted to 1.5, and then the second stage of leaching and filtering operation is performed to obtain a second leachate and a second leach residue.
  • the second leachate is subjected to an impurity removal and filtering operation to obtain a filtrate and a filter residue.
  • the second leaching residue is subjected to a high acid leaching and filtering operation to obtain a battery-grade graphite raw material.
  • Pure water is added to the lithium battery powder to obtain a slurry with a solid content of 20%.
  • the sulfuric acid, reducing agent and slurry are mixed and the pH value is adjusted to 5.7, the first stage of leaching and filtering operation is performed to obtain the first leachate and the first leach residue.
  • the first leachate is subjected to a P204 extraction and impurity removal operation to obtain a battery-grade nickel-cobalt-manganese solution.
  • the second stage of leaching and filtering operation is performed to obtain the second leachate and the second leach residue.
  • the second leachate is subjected to an impurity removal and filtering operation to obtain a filtrate and a filter residue.
  • the second leaching residue is subjected to a high acid leaching and filtering operation to obtain a battery-grade graphite raw material.
  • Pure water is added to the lithium battery powder to obtain a slurry with a solid content of 20%.
  • the sulfuric acid, reducing agent and slurry are mixed and the pH value is adjusted to 6.0, the first stage of leaching and filtering operation is performed to obtain the first leachate and the first leach residue.
  • the first leachate is subjected to a P204 extraction and impurity removal operation to obtain a battery-grade nickel-cobalt-manganese solution.
  • the sulfuric acid, reducing agent and first leach residue are mixed and the pH is adjusted to 1.5
  • the second stage of leaching and filtering operation is performed to obtain the second leachate and the second leach residue.
  • the second leachate is subjected to an impurity removal and filtering operation to obtain a filtrate and a filter residue.
  • the second leaching residue is subjected to a high acid leaching and filtering operation to obtain a battery-grade graphite raw material.
  • Pure water is added to the lithium battery powder to obtain a slurry with a solid content of 20%.
  • the sulfuric acid, reducing agent and slurry are mixed and the pH value is adjusted to 4.0, the first stage of leaching and filtering operation is performed to obtain the first leachate and the first leach residue.
  • the first leachate is subjected to a P204 extraction and impurity removal operation to obtain a battery-grade nickel-cobalt-manganese solution.
  • the second stage of leaching and filtering operation is performed to obtain the second leachate and the second leach residue.
  • the second leachate is subjected to an impurity removal and filtering operation to obtain a filtrate and a filter residue.
  • the second leaching residue is subjected to a high acid leaching and filtering operation to obtain a battery-grade graphite raw material.
  • Pure water is added to the lithium battery powder to obtain a slurry with a solid content of 20%.
  • the sulfuric acid, reducing agent and slurry are mixed and the pH value is adjusted to 2.0, the first stage of leaching and filtering operation is performed to obtain the first leachate and the first leach residue.
  • the first leachate is subjected to a P204 extraction and impurity removal operation to obtain a battery-grade nickel-cobalt-manganese solution.
  • the sulfuric acid, reducing agent and the first leach residue are mixed and the pH is adjusted to 1.5, the second stage of leaching and filtering operation is performed to obtain the second leachate and the second leach residue.
  • the second leachate is subjected to an impurity removal and filtering operation to obtain a filtrate and a filter residue.
  • the second leaching residue is subjected to a high acid leaching and filtering operation to obtain a battery-grade graphite raw material.
  • Pure water is added to the lithium battery powder to obtain a slurry with a solid content of 20%.
  • the sulfuric acid, reducing agent and slurry are mixed and the pH value is adjusted to 2.5, the first stage of leaching and filtering operation is performed to obtain the first leachate and the first leach residue.
  • the first leachate is subjected to a P204 extraction and impurity removal operation to obtain a battery-grade nickel-cobalt-manganese solution.
  • the sulfuric acid, reducing agent and the first leach residue are mixed and the pH is adjusted to 1.5, the second stage of leaching and filtering operation is performed to obtain the second leachate and the second leach residue.
  • the second leachate is subjected to an impurity removal and filtering operation to obtain a filtrate and a filter residue.
  • the second leaching residue is subjected to a high acid leaching and filtering operation to obtain a battery-grade graphite raw material.
  • Pure water is added to the lithium battery powder to obtain a slurry with a solid content of 20%.
  • the sulfuric acid, reducing agent and slurry are mixed and the pH value is adjusted to 3.0, the first stage of leaching and filtering operation is performed to obtain the first leachate and the first leach residue.
  • the first leachate is subjected to a P204 extraction and impurity removal operation to obtain a battery-grade nickel-cobalt-manganese solution.
  • the second stage of leaching and filtering operation is performed to obtain the second leachate and the second leach residue.
  • the second leachate is subjected to an impurity removal and filtering operation to obtain a filtrate and a filter residue.
  • the second leaching residue is subjected to a high acid leaching and filtering operation to obtain a battery-grade graphite raw material.
  • the recycling and processing method of battery powder based on lithium extraction of the present application is to mix sulfuric acid, a reducing agent and a slurry and then perform the first stage of leaching and filtering operation.
  • the pH value is strictly controlled between 4-6 and under the action of the reducing agent, the iron, aluminum and copper elements in the battery powder after lithium extraction form a precipitate, namely the first leaching residue.
  • the first leaching residue and the first leachate are separated by filtration, and then the first leachate is subjected to a P204 extraction and impurity removal operation, that is, the calcium ions in the first leachate are extracted and impurities are removed by the P204 extractant, so that a battery-grade nickel-cobalt-manganese solution can be prepared. Therefore, there is no need to carry out a full extraction process to complete the preparation of a battery-grade nickel-cobalt-manganese solution, which can effectively reduce the consumption of auxiliary materials and also greatly simplify the battery-grade process.
  • the method for preparing the nickel-cobalt-manganese solution can simplify the recovery and processing steps of lithium battery powder, thereby effectively improving the recovery and processing efficiency of lithium battery powder and reducing the recovery and processing cost of lithium battery powder.
  • the recycling method based on lithium battery powder extraction of the present application is to mix sulfuric acid, a reducing agent and a first leaching residue and then perform a second leaching and filtering operation.
  • the pH value is strictly controlled between 1-2 and a second leaching residue is formed under the action of a reducing agent.
  • the iron, aluminum and copper elements in the first leaching residue are leached and a second leaching liquid is formed.
  • the second leaching residue and the second leaching liquid are separated by filtration.
  • the filter residue is obtained by performing an impurity removal and filtration operation on the second leaching liquid, and the filter residue is a mixed precipitate of iron, aluminum and copper, thereby achieving a better impurity removal and recovery effect.
  • the second leaching residue is rich in graphite
  • a battery-grade graphite raw material can be obtained, and the graphite can be recycled and reused, and the cost of disposing the second leaching residue as solid waste or hazardous waste can be saved.

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Abstract

一种基于提锂电池粉的回收处理方法，包括以下步骤：将提锂后的电池粉进行浆化操作，得到浆料；将硫酸、还原剂及所述浆料混合后进行第一段浸出过滤操作，得到第一浸出液和第一浸出渣；将所述第一浸出液进行P204萃取除杂操作，得到电池级镍钴锰溶液；将所述硫酸、所述还原剂及所述第一浸出渣混合后进行第二段浸出过滤操作，得到第二浸出液和第二浸出渣；对所述第二浸出液进行除杂过滤操作，得到过滤液和过滤渣；对所述第二浸出渣进行高酸浸出过滤操作，得到电池级石墨原料；其中，所述第一段浸出过滤操作中的pH值为4-6；所述第二段浸出过滤操作中的pH值为1-2。

Description

基于提锂电池粉的回收处理方法 技术领域
本申请涉及一种基于提锂电池粉的回收处理方法。
背景技术
新能源行业快速发展，配套新能源行业废旧电池回收产业越来越大，但是如何高效、绿色回收依然存在技术瓶颈。
目前锂电池粉生产电池级镍钴锰工艺有火法和湿法两种，火法工艺采用优先提锂-烘干-熔炼-球磨-浸出-提纯工艺，在火法生产过程中能耗高、污染大，优点是经过火法除杂后，在提纯过程中只需要萃杂即可产出电池级镍钴锰溶液，节约了大量酸碱消耗，节约成本。但是为了符合绿色回收的理念，锂电池粉生产电池级镍钴锰工艺一般采用湿法，湿法一般是采用浸出-除杂-萃取-提锂工艺处理电池粉，电池粉除杂大多采用纯碱/碳酸钙等调节溶液pH除去溶液中的铁铝，为了达到较好的除杂效果，导致在除杂过程中因溶液引入的残酸量加大而增加了辅料消耗。然后在萃取工序中为了浸出的镍钴锰溶液能达到电池级标准，大多采用P507萃镍钴，P507萃镍钴需要把浸出液中镍、钴全部萃到有机相中然后用硫酸或盐酸反萃，在反萃中有多少镍钴离子，就需要2倍氢离子反萃，反萃后的有机相再用液碱皂化，导致硫酸和液碱的辅料消耗过大，而且全萃的工艺会导致整个回收过程复杂化。同时的，目前废旧锂电池粉的回收方法一般对浸出渣作固废或危废处置，然而浸出渣中含有大量的石墨，从而造成石墨资源的浪费。
因此，亟需一种流程简化、辅料消耗少、除杂效果好、能够制备电池级镍钴锰溶液以及电池级石墨原料的电池粉回收处理方法。
发明内容
基于此，有必要提供流程简化、辅料消耗少、除杂效果好、能够制备电池级镍钴锰溶液以及电池级石墨原料的基于提锂电池粉的回收处理方法。
一种基于提锂电池粉的回收处理方法，包括以下步骤：
将提锂后的电池粉进行浆化操作，得到浆料；
将硫酸、还原剂及所述浆料混合后进行第一段浸出过滤操作，得到第一浸出液和第一浸出渣；
将所述第一浸出液进行P204萃取除杂操作，得到电池级镍钴锰溶液；
将所述硫酸、所述还原剂及所述第一浸出渣混合后进行第二段浸出过滤操作，得到第二浸出液和第二浸出渣；
对所述第二浸出液进行除杂过滤操作，得到过滤液和过滤渣；
对所述第二浸出渣进行高酸浸出过滤操作，得到电池级石墨原料；
其中，所述第一段浸出过滤操作中的pH值为4-6；
所述第二段浸出过滤操作中的pH值为1-2。
本申请的一个或多个实施例的细节在下面的附图和描述中提出。本申请的其它特征、目的和优点将从说明书、附图以及权利要求书变得明显。
附图说明
为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他实施例的附图。
图1为一实施例中基于提锂电池粉的回收处理方法的流程示意图；
图2为基于提锂电池粉的回收处理方法的工艺流程图。
具体实施方式
为了便于理解本申请，下面将参照相关附图对本申请进行更全面的描述。附图中给出了本申请的较佳实施方式。但是，本申请可以以许多不同的形式来实现，并不限于本文所描述的实施方式。相反地，提供这些实施方式的目的是使对本申请的公开内容理解的更加透彻全面。
需要说明的是，当元件被称为“固定于”另一个元件，它可以直接在另一个元件上或者也可以存在居中的元件。当一个元件被认为是“连接”另一个元件，它可 以是直接连接到另一个元件或者可能同时存在居中元件。本文所使用的术语“垂直的”、“水平的”、“左”、“右”以及类似的表述只是为了说明的目的，并不表示是唯一的实施方式。
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同。本文中在本申请的说明书中所使用的术语只是为了描述具体的实施方式的目的，不是旨在于限制本申请。本文所使用的术语“及/或”包括一个或多个相关的所列项目的任意的和所有的组合。
请参阅图1，一实施方式的基于提锂电池粉的回收处理方法，包括以下步骤的部分或全部：
S100，将提锂后的电池粉进行浆化操作，得到浆料。
在本实施例中，经过提锂后的提锂渣即为提锂电池粉，对电池粉进行浆化操作后得到浆料，以便于后续的回收处理工作的进行。
S200，将硫酸、还原剂及所述浆料混合后进行第一段浸出过滤操作，得到第一浸出液和第一浸出渣。
在本实施例中，经过提锂后的电池粉主要包含有铁、铝、铜、镍、钴、锰的金属元素，通过将硫酸、还原剂及浆料混合后在一段浸出槽内进行第一段浸出过滤操作，同时第一段浸出过滤操作的pH值控制在4～6，而在pH值4～6之间以及还原剂的作用下铁、铝、铜的金属元素均容易形成沉淀。如此能够将镍钴锰和铁铝铜分离出来，以便于回收镍钴锰金属元素。
S300，将所述第一浸出液进行P204萃取除杂操作，得到电池级镍钴锰溶液。
在本实施例中，由于提锂后的电池粉掺杂有钙元素，而钙元素随着第一段浸出过滤操作后掺入至第一浸出液。根据P204萃取剂在萃取钙离子的效果较好的特性，通过加入P204萃取剂将第一浸出液中的钙离子萃取出来，以对第一浸出液进行除杂得到电池级镍钴锰溶液，因此无需对浸出液进行全萃工艺，从而能够有效地减少辅料的消耗量，同时也能够较大程度地简化电池级镍钴锰溶液的制备方法，进而能够简化了提锂电池粉的回收处理步骤。
进一步地，通过设计电池粉先提锂后回收的处理方式，使得在制备电池级镍钴锰溶液时无需额外在萃取锂离子，能够进一步地简化电池级镍钴锰溶液的 制备过程。
还需要特别说明的是，镍+钴+猛的含量在100g/L～120g/L即为电池级镍钴锰溶液。
S400，将所述硫酸、所述还原剂及所述第一浸出渣混合后进行第二段浸出过滤操作，得到第二浸出液和第二浸出渣。
在本实施例中，通过将硫酸、还原剂及第一浸出渣混合后在二段浸出槽内进行第二段浸出过滤操作，同时第二段浸出过滤操作的pH值控制在1～2，而在pH值1～2以及在还原剂的作用下形成有第二浸出渣，而第一浸出渣中铁、铝、铜元素均浸出形成第二浸出液，如此能够将铁、铝、铜元素进行回收。
S500，对所述第二浸出液进行除杂过滤操作，得到过滤液和过滤渣。
在本实施例中，通过对第二浸出液进行除杂过滤操作，而过滤渣为铁铝铜渣，如此实现对铁、铝、铜元素的回收。
S600，对所述第二浸出渣进行高酸浸出过滤操作，得到电池级石墨原料。
在本实施例中，由于第二浸出渣内富含石墨，通过对第二浸出渣进行高酸浸出过滤操作，如此能够得到电池级石墨原料，从而实现了石墨的回收再利用，，同时节省了第二浸出渣作为固废或危废处置的成本。
需要说明的是，电池级石墨原料只需进行一次石墨化即得到电池级石墨，而只有当浸出渣内的镍钴锰的含量小于0.08％才能达到电池级石墨原料，也无需进行二次除杂。
还需要特别说明的是，这里高酸指的是酸度在100g/L以上的酸，而一段过滤操作和二段过滤操作的酸度均在100g/L以下。
其中，所述第一段浸出过滤操作中的pH值为4-6；所述第二段浸出过滤操作中的pH值为1-2。
上述的基于提锂电池粉的回收处理方法，将硫酸、还原剂及浆料混合后进行第一段浸出过滤操作，同时pH值严格控制在4-6之间以及在还原剂的作用下，使得提锂后的电池粉中铁、铝、铜元素均形成有沉淀，即第一浸出渣。通过过滤使得第一浸出渣和第一浸出液分离出来，再使第一浸出液进行P204萃取除杂操作，即通过P204萃取剂将第一浸出液中的钙离子萃取除杂，从而能够制备出 电池级镍钴锰溶液，因此也无需进行全萃工艺即可完成电池级镍钴锰溶液的制备，能够有效地减少辅料的消耗量，同时也能够较大程度地简化电池级镍钴锰溶液的制备方法，从而能够简化了提锂电池粉的回收处理步骤，进而有效地提高了提锂电池粉的回收处理效率以及减少了提锂电池粉的回收处理成本。
进一步地，将硫酸、还原剂及第一浸出渣混合后进行第二段浸出过滤操作，同时pH值严格控制在1-2之间以及在还原剂的作用下形成有第二浸出渣，同时使得第一浸出渣中铁、铝、铜元素均浸出并形成有第二浸出液，通过过滤使得第二浸出渣和第二浸出液分离出来。再通过对第二浸出液进行除杂过滤操作得到过滤渣，而过滤渣为铁铝铜混合沉淀物，从而达到较好的除杂回收效果。进一步地，由于第二浸出渣内富含石墨，通过对第二浸出渣进行高酸浸出过滤操作，如此能够得到电池级石墨原料，实现石墨的回收再利用，同时能够节省第二浸出渣作为固废或危废处置的成本。
在其中一个实施例中，将提锂电池粉进行浆化操作，得到浆料的具体操作步骤为：对所述提锂电池粉中加入纯水进行浆化操作，得到固含量为20％～30％的所述浆料。需要说明的是，采用纯水将提锂后的电池粉进行浆化操作，如此能够得到固含量为20％～30％的浆料。
在其中一个实施例中，在将所述第一浸出液进行P204萃取除杂操作，得到电池级镍钴锰溶液的步骤之后，以及在将所述硫酸、所述还原剂及所述第一浸出渣混合后进行第二段浸出过滤操作，得到第二浸出液和第二浸出渣的步骤之前，所述回收处理方法还包括如下步骤：对所述第一浸出渣进行溶解操作。需要说明的是，经过过滤得到第一浸出渣需要先形成液体形态，通过加入纯水将第一浸出渣进行溶解操作，以便于后续进行第二段浸出过滤操作。
在其中一个实施例中，在对所述第一浸出渣进行溶解操作的步骤之后，以及在将所述第一浸出液进行P204萃取除杂操作，得到电池级镍钴锰溶液的步骤之前，所述回收处理方法还包括如下步骤：
对溶解后的所述第一浸出渣进行含量检测操作；
对所述第一浸出渣的含量结果进行判定操作，具体判定操作如下：
当所述第一浸出渣中的铁铝含量的质量百分数大于或等于5％时，将所述硫 酸、所述还原剂及所述第一浸出渣混合后进行第二段浸出过滤操作；
当所述第一浸出渣中的铁铝含量的质量百分数小于5％时，将所述硫酸、所述还原剂、所述第一浸出渣及所述浆料混合后进行第一段浸出过滤操作。
需要说明的是，通过对第一浸出渣的铁铝含量进行检测，即可得到第一浸出渣中的杂质含量，当杂质含量的质量百分数小于5％时，将第一浸出渣返投至一段浸出槽内并循环进行第一段浸出过滤操作，能够有效地提高第二浸出液中杂质含量，便于除杂的同时减少多次除杂的辅料浪费，从而有效地减少除杂辅料的使用量，进而有效地减少提锂电池粉的回收处理成本。
在其中一个实施例中，将所述第一浸出液进行P204萃取除杂操作，得到电池级镍钴锰溶液的具体操作步骤为：
对所述第一浸出液中加入P204萃取剂后进行萃取操作，得到所述电池级镍钴锰溶液。
需要说明的是，通过将第一浸出液中其他杂质离子萃取至P204萃取剂中，从而达到一个较好的除杂效果，同时也能够制备电池级镍钴锰溶液。
在其中一个实施例中，对所述第二浸出液进行除杂过滤操作的具体操作步骤为：
对所述第二浸出液中加入活性金属进行除铜操作；
对除铜后的所述第二浸出液中加入碱性盐进行过滤操作，得到过滤渣和过滤液。
需要说明的是，通过对第二浸出液中加入活性金属进行置换除铜操作，能够将第二浸出液中铜离子置换出来。再通过加入碱性盐，使得第二浸出液的pH值为3～4之间，此时铁和铝均能够形成相应的金属盐沉淀，再通过过滤操作得到过滤渣和过滤液，其中过滤渣为铁铝铜渣，如此能够有效地回收铁铝铜金属元素。
在其中一个实施例中，所述活性金属为铁粉、锰粉或镍粉中的一种。需要说明的是，根据金属活性顺序表，选用活性大于铜的活性金属，即可将第二浸出液中铜离子置换出来。
在其中一个实施例中，所述碱性盐为工业级碳酸钠或工业级氢氧化钠。需 要说明的是，选用工业级的碳酸钠和工业级氢氧化钠的高纯度原料作为碱性盐，能够有效地减少杂质的掺入，从而减少除杂辅料的使用，进而有效地减少提锂电池粉的回收处理成本。
在其中一个实施例中，对所述第二浸出渣进行高酸浸出过滤操作，得到电池级石墨原料的具体操作步骤为：
将所述硫酸、所述还原剂及所述第二浸出渣混合后进行第一高酸浸出过滤操作，得到第一高酸浸出渣和第一高酸浸出液；
将所述硫酸、所述还原剂及所述第一高酸浸出渣混合后进行第二高酸浸出过滤操作，得到所述电池级石墨原料。
需要说明的是，通过第一段浸出过滤操作和第二段浸出过滤操作后的第二浸出渣内金属含量较低。为了满足电池级石墨原料的浸出要求，首先通过第一高酸浸出过滤操作，采用酸度大于100g/L的高酸浸出的方式将第二浸出渣内的金属浸出，即通过提高硫酸的酸度而增大硫酸与第二浸出渣中待浸出金属的来回碰撞次数，使得第二浸出渣内的待浸出金属能够溶解在硫酸内，如此能够有效地降低第一高酸浸出渣内的金属含量。其次，经过第一高酸浸出过滤操作后的第一高酸浸出渣内的金属含量相较于第二浸出渣的金属含量更少了，通过设置第二高酸浸出过滤操作的酸度大于第一高酸浸出过滤操作的酸度，即进一步地提高硫酸的酸度，从而进一步地增大硫酸与第一高酸浸出渣中待浸出金属的来回碰撞次数，使得第一高酸浸出渣内的待浸出金属能够溶解在硫酸内，从而使得第二高酸浸出渣能够达到电池级石墨原料的标准。
在其中一个实施例中，在将所述硫酸、所述还原剂及所述第二浸出渣混合后进行第一高酸浸出过滤操作，得到第一高酸浸出渣和第一高酸浸出液的之后，所述回收处理方法还包括如下步骤：将所述硫酸、所述还原剂、所述第一高酸浸出液及所述第一浸出渣混合后进行第二段浸出过滤操作。需要说明的是，通过将第一高酸浸出液返投至二段浸出槽内，能够减少第二段浸出过滤操作中的硫酸加入量，实现辅料的回收再利用，从而能够有效地减少辅料的消耗量，进而有效地减少提锂电池粉的回收处理成本。
在其中一个实施例中，在将所述硫酸、所述还原剂及所述第一高酸浸出渣 混合后进行第二高酸浸出过滤操作，得到所述电池级石墨原料的步骤之后，所述回收处理方法还包括如下步骤：将所述硫酸、所述还原剂、所述第二高酸浸出液及所述第二浸出渣混合后进行第一高酸浸出过滤操作。需要说明的是，通过将第二高酸浸出液返投至第一高酸浸出槽内，能够减少第一高酸浸出过滤操作中的硫酸加入量，实现辅料的回收再利用，从而能够有效地减少辅料的消耗量，进而有效地减少提锂电池粉的回收处理成本。
在其中一个实施例中，所述第一高酸浸出过滤操作的酸度为200g/L～300g/L。可以理解的是，在酸度为200g/L～300g/L下，能够增大硫酸与第二浸出渣中待浸出金属的来回碰撞次数，使得待浸出金属能够溶解在硫酸中，即将第二浸出渣中的金属浸出在第一高酸浸出液中。
在其中一个实施例中，所述第二高酸浸出过滤操作的酸度为300g/L～500g/L。可以理解的是，在酸度为300g/L～500g/L下，能够进一步地增大硫酸与第一高酸浸出渣中待浸出金属的来回碰撞次数，进一步地将待浸出金属溶解在硫酸中，使得第二高酸浸出渣能够符合电池级石墨原料的标准，不仅能够节省浸出渣作为危废或固废处置的成本，同时还能够实现石墨的回收利用。
在其中一个实施例中，所述第一高酸浸出过滤操作和所述第二高酸浸出过滤操作的温度均为80℃～100℃。可以理解的是，在温度为80℃～100℃，第一高酸浸出过滤操作和第二高酸浸出过滤操作均能够最大程度地将浸出渣内的金属浸出，从而达到较好的除杂效果。
在其中一个实施例中，所述第一段浸出过滤操作的温度为80℃～100℃。需要说明的是，在温度为80℃～100℃，且pH值严格控制在4～6之间，使得第一浸出液中铁、铝、铜等杂质含量小于2ppm，即当杂质含量小于2ppm时，第一浸出液无需继续除杂即可满足P204萃取的要求，通过P204萃取剂对第一浸出液进行萃取除杂操作，如此能够得到电池级镍钴锰溶液。因此无需全萃工艺即可制备得到电池级镍钴锰溶液，能够较大程度地简化电池级镍钴锰溶液的制备工艺，进而简化了提锂电池粉的回收处理步骤，进一步地提高了提锂电池粉的回收处理效率。
在其中一个实施例中，所述还原剂为双氧水、二氧化硫及亚硫酸钠中的至 少一种。需要说明的是，通过加入还原剂使得提锂电池粉内铁、铝、铜、镍、钴、锰等金属元素还原成相应的金属离子，以便于进行除杂回收处理。
以下列举实施例，但需注意的是，下列实施例并没有穷举所有可能的情况，并且下述实施例中所用的材料如无特殊说明，均可从商业途径得到。
实施例1
对提锂电池粉中加入纯水得到固含量20％的浆料。将硫酸、还原剂及浆料混合并调节pH值为4.3后进行第一段浸出过滤操作，得到第一浸出液和第一浸出渣。将第一浸出液进行P204萃取除杂操作，得到电池级镍钴锰溶液。将硫酸、还原剂及第一浸出渣混合并调节pH至为1.5后进行第二段浸出过滤操作，得到第二浸出液和第二浸出渣。对第二浸出液进行除杂过滤操作，得到过滤液和过滤渣。对第二浸出渣进行高酸浸出过滤操作，得到电池级石墨原料。
第一浸出液情况如表1：
P204萃取除杂后的第一浸出液情况如表2：
将第一浸出渣循环3次第一段浸出过滤操作后，在进行第二段浸出过滤操作得到的第二浸出液情况如表3：
第二高酸浸出渣(电池级石墨原料)的情况如表4：
实施例2
对提锂电池粉中加入纯水得到固含量20％的浆料。将硫酸、还原剂及浆料混合并调节pH值为4.8后进行第一段浸出过滤操作，得到第一浸出液和第一浸出渣。将第一浸出液进行P204萃取除杂操作，得到电池级镍钴锰溶液。将硫酸、还原剂及第一浸出渣混合并调节pH至为1.5后进行第二段浸出过滤操作，得到第二浸出液和第二浸出渣。对第二浸出液进行除杂过滤操作，得到过滤液和过滤渣。对第二浸出渣进行高酸浸出过滤操作，得到电池级石墨原料。
第一浸出液的元素含量如表5：
P204萃取除杂后的萃余液的元素含量如表6：
将第一浸出渣循环3次第一段浸出过滤操作后，在进行第二段浸出过滤操作得到的第二浸出液的元素含量如表7：
第二高酸浸出渣(电池级石墨原料)的元素含量如表8：
实施例3
配置180g/L硫酸溶液。对提锂电池粉中加入纯水得到固含量20％的浆料。将硫酸、还原剂及浆料混合并调节pH值为5.2后进行第一段浸出过滤操作，得到第一浸出液和第一浸出渣。将第一浸出液进行P204萃取除杂操作，得到电池级镍钴锰溶液。将硫酸、还原剂及第一浸出渣混合并调节pH至为1.5后进行第二段浸出过滤操作，得到第二浸出液和第二浸出渣。对第二浸出液进行除杂过滤操作，得到过滤液和过滤渣。对第二浸出渣进行高酸浸出过滤操作，得到电 池级石墨原料。
第一浸出液的元素含量如表9：
P204萃取除杂后的萃余液的元素含量如表10：
将第一浸出渣循环3次第一段浸出过滤操作后，在进行第二段浸出过滤操作得到的第二浸出液的元素含量如表11：
第二高酸浸出渣(电池级石墨原料)的元素含量如表12：
实施例4
对提锂电池粉中加入纯水得到固含量20％的浆料。将硫酸、还原剂及浆料混合并调节pH值为5.7后进行第一段浸出过滤操作，得到第一浸出液和第一浸出渣。将第一浸出液进行P204萃取除杂操作，得到电池级镍钴锰溶液。将硫酸、还原剂及第一浸出渣混合并调节pH至为1.5后进行第二段浸出过滤操作，得到第二浸出液和第二浸出渣。对第二浸出液进行除杂过滤操作，得到过滤液和过滤渣。对第二浸出渣进行高酸浸出过滤操作，得到电池级石墨原料。
第一浸出液的元素含量如表13：
P204萃取除杂后的萃余液的元素含量如表14：
将第一浸出渣循环3次第一段浸出过滤操作后，在进行第二段浸出过滤操作得到的第二浸出液的元素含量如表15：
第二高酸浸出渣(电池级石墨原料)的元素含量如表16：
实施例5
对提锂电池粉中加入纯水得到固含量20％的浆料。将硫酸、还原剂及浆料混合并调节pH值为6.0后进行第一段浸出过滤操作，得到第一浸出液和第一浸出渣。将第一浸出液进行P204萃取除杂操作，得到电池级镍钴锰溶液。将硫酸、还原剂及第一浸出渣混合并调节pH至为1.5后进行第二段浸出过滤操作，得到第二浸出液和第二浸出渣。对第二浸出液进行除杂过滤操作，得到过滤液和过滤渣。对第二浸出渣进行高酸浸出过滤操作，得到电池级石墨原料。
第一浸出液的元素含量如表17：
P204萃取除杂后的萃余液的元素含量如表18：
将第一浸出渣循环3次第一段浸出过滤操作后，在进行第二段浸出过滤操作得到的第二浸出液的元素含量如表19：

第二高酸浸出渣(电池级石墨原料)的元素含量如表20：
实施例6
对提锂电池粉中加入纯水得到固含量20％的浆料。将硫酸、还原剂及浆料混合并调节pH值为4.0后进行第一段浸出过滤操作，得到第一浸出液和第一浸出渣。将第一浸出液进行P204萃取除杂操作，得到电池级镍钴锰溶液。将硫酸、还原剂及第一浸出渣混合并调节pH至为1.5后进行第二段浸出过滤操作，得到第二浸出液和第二浸出渣。对第二浸出液进行除杂过滤操作，得到过滤液和过滤渣。对第二浸出渣进行高酸浸出过滤操作，得到电池级石墨原料。
第一浸出液的元素含量如表21：
P204萃取除杂后的萃余液的元素含量如表22：
将第一浸出渣循环3次第一段浸出过滤操作后，在进行第二段浸出过滤操作得到的第二浸出液的元素含量如表23：
第二高酸浸出渣(电池级石墨原料)的元素含量如表24：
对比例1
对提锂电池粉中加入纯水得到固含量20％的浆料。将硫酸、还原剂及浆料混合并调节pH值为2.0后进行第一段浸出过滤操作，得到第一浸出液和第一浸出渣。将第一浸出液进行P204萃取除杂操作，得到电池级镍钴锰溶液。将硫酸、还原剂及第一浸出渣混合并调节pH至为1.5后进行第二段浸出过滤操作，得到第二浸出液和第二浸出渣。对第二浸出液进行除杂过滤操作，得到过滤液和过滤渣。对第二浸出渣进行高酸浸出过滤操作，得到电池级石墨原料。
第一浸出液的元素含量如表25：
P204萃取除杂后的萃余液的元素含量如表26：
将第一浸出渣循环3次第一段浸出过滤操作后，在进行第二段浸出过滤操作得到的第二浸出液的元素含量如表27：
第二高酸浸出渣(电池级石墨原料)的元素含量如表28：
对比例2
对提锂电池粉中加入纯水得到固含量20％的浆料。将硫酸、还原剂及浆料混合并调节pH值为2.5后进行第一段浸出过滤操作，得到第一浸出液和第一浸出渣。将第一浸出液进行P204萃取除杂操作，得到电池级镍钴锰溶液。将硫酸、还原剂及第一浸出渣混合并调节pH至为1.5后进行第二段浸出过滤操作，得到第二浸出液和第二浸出渣。对第二浸出液进行除杂过滤操作，得到过滤液和过滤渣。对第二浸出渣进行高酸浸出过滤操作，得到电池级石墨原料。
第一浸出液的元素含量如表29：
P204萃取除杂后的萃余液的元素含量如表30：
将第一浸出渣循环3次第一段浸出过滤操作后，在进行第二段浸出过滤操作得到的第二浸出液的元素含量如表31：
第二高酸浸出渣(电池级石墨原料)的元素含量如表32：
对比例3
对提锂电池粉中加入纯水得到固含量20％的浆料。将硫酸、还原剂及浆料混合并调节pH值为3.0后进行第一段浸出过滤操作，得到第一浸出液和第一浸出渣。将第一浸出液进行P204萃取除杂操作，得到电池级镍钴锰溶液。将硫酸、还原剂及第一浸出渣混合并调节pH至为1.5后进行第二段浸出过滤操作，得到第二浸出液和第二浸出渣。对第二浸出液进行除杂过滤操作，得到过滤液和过滤渣。对第二浸出渣进行高酸浸出过滤操作，得到电池级石墨原料。
第一浸出液的元素含量如表33：
P204萃取除杂后的萃余液的元素含量如表34：

将第一浸出渣循环3次第一段浸出过滤操作后，在进行第二段浸出过滤操作得到的第二浸出液的元素含量如表35：
第二高酸浸出渣(电池级石墨原料)的元素含量如表36：
由表1至表36可得知，当第一段浸出过滤操作的pH值不在4～6之间时，第一浸出液中铁铝铜元素的含量明显增多，从而导致P204萃取除杂后的萃余液不符合电池级镍钴锰的要求。这说明在第一段浸出过滤操作中严格控制pH值在4～6之间，使得第一浸出液中铁铝铜元素含量较少，且P204萃取除杂后的萃余液符合电池级镍钴锰的要求，不仅能够较大程度地简化了电池级镍钴锰的回收工艺，而且还能够节省辅料的消耗，同时还使得提锂电池粉的回收处理步骤简化以及符合绿色回收的理念。同时地，通过第一高酸浸出过滤操作和第二高酸浸出过滤操作后的浸出渣均能够符合电池级石墨原料的标准。这说明通过设置有第一高酸浸出过滤操作和第二高酸浸出过滤操作，不仅能够回收电池级石墨原料，而且还能够节省浸出渣作为危废或固废处置的成本。
与现有技术相比，本申请至少具有以下优点：
1、本申请的基于提锂电池粉的回收处理方法，将硫酸、还原剂及浆料混合后进行第一段浸出过滤操作，同时pH值严格控制在4-6之间以及在还原剂的作用下，使得提锂后的电池粉中铁、铝、铜元素均形成有沉淀，即第一浸出渣。通过过滤使得第一浸出渣和第一浸出液分离出来，再使第一浸出液进行P204萃取除杂操作，即通过P204萃取剂将第一浸出液中的钙离子萃取除杂，从而能够制备出电池级镍钴锰溶液，因此也无需进行全萃工艺即可完成电池级镍钴锰溶液的制备，能够有效地减少辅料的消耗量，同时也能够较大程度地简化电池级 镍钴锰溶液的制备方法，从而能够简化了提锂电池粉的回收处理步骤，进而有效地提高了提锂电池粉的回收处理效率以及减少了提锂电池粉的回收处理成本。
2、本申请的基于提锂电池粉的回收处理方法，将硫酸、还原剂及第一浸出渣混合后进行第二段浸出过滤操作，同时pH值严格控制在1-2之间以及在还原剂的作用下形成有第二浸出渣，同时使得第一浸出渣中铁、铝、铜元素均浸出并形成有第二浸出液，通过过滤使得第二浸出渣和第二浸出液分离出来。再通过对第二浸出液进行除杂过滤操作得到过滤渣，而过滤渣为铁铝铜混合沉淀物，从而达到较好的除杂回收效果。进一步地，由于第二浸出渣内富含石墨，通过对第二浸出渣进行高酸浸出过滤操作，如此能够得到电池级石墨原料，实现石墨的回收再利用，同时能够节省第二浸出渣作为固废或危废处置的成本。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准。

Claims (16)

  1. 一种基于提锂电池粉的回收处理方法，其特征在于，包括以下步骤：
    将提锂后的电池粉进行浆化操作，得到浆料；
    将硫酸、还原剂及所述浆料混合后进行第一段浸出过滤操作，得到第一浸出液和第一浸出渣；
    将所述第一浸出液进行P204萃取除杂操作，得到电池级镍钴锰溶液。
    将所述硫酸、所述还原剂及所述第一浸出渣混合后进行第二段浸出过滤操作，得到第二浸出液和第二浸出渣；
    对所述第二浸出液进行除杂过滤操作，得到过滤液和过滤渣；
    其中，所述第一段浸出过滤操作中的pH值为4-6；
    所述第二段浸出过滤操作中的pH值为1-2。
  2. 根据权利要求1所述的基于提锂电池粉的回收处理方法，其特征在于，将提锂电池粉进行浆化操作的具体操作步骤为：
    对所述提锂电池粉中加入纯水进行浆化操作，得到固含量为20％～30％的所述浆料。
  3. 根据权利要求1所述的基于提锂电池粉的回收处理方法，其特征在于，在将所述第一浸出液进行P204萃取除杂操作的步骤之后，以及在将所述硫酸、所述还原剂及所述第一浸出渣混合后进行第二段浸出过滤操作的步骤之前，所述回收处理方法还包括如下步骤：
    对所述第一浸出渣进行溶解操作。
  4. 根据权利要求3所述的基于提锂电池粉的回收处理方法，其特征在于，在对所述第一浸出渣进行溶解操作的步骤之后，以及在将所述第一浸出液进行P204萃取除杂操作的步骤之前，所述回收处理方法还包括如下步骤：
    对溶解后的所述第一浸出渣进行含量检测操作；
    对所述第一浸出渣的含量结果进行判定操作，具体判定操作如下：
    当所述第一浸出渣中的铁铝含量的质量百分数大于或等于5％时，将所述硫酸、所述还原剂及所述第一浸出渣混合后进行第二段浸出过滤操作；
    当所述第一浸出渣中的铁铝含量的质量百分数小于5％时，将所述硫酸、所述还原剂、所述第一浸出渣及所述浆料混合后进行第一段浸出过滤操作。
  5. 根据权利要求1所述的基于提锂电池粉的回收处理方法，其特征在于，将所述第一浸出液进行P204萃取除杂操作，得到电池级镍钴锰溶液的具体操作步骤为：
    对所述第一浸出液中加入P204萃取剂后进行萃取操作，得到所述电池级镍钴锰溶液。
  6. 根据权利要求1所述的基于提锂电池粉的回收处理方法，其特征在于，对所述第二浸出液进行除杂过滤操作的具体操作步骤为：
    对所述第二浸出液中加入活性金属进行除铜操作；
    对除铜后的所述第二浸出液中加入碱性盐进行过滤操作，得到过滤渣和过滤液。
  7. 根据权利要求6所述的基于提锂电池粉的回收处理方法，其特征在于，所述活性金属为铁粉、锰粉或镍粉中的一种。
  8. 根据权利要求6所述的基于提锂电池粉的回收处理方法，其特征在于，所述碱性盐为工业级碳酸钠或工业级氢氧化钠。
  9. 根据权利要求1所述的基于提锂电池粉的回收处理方法，其特征在于，对所述第二浸出渣进行高酸浸出过滤操作的具体操作步骤为：
    将所述硫酸、所述还原剂及所述第二浸出渣混合后进行第一高酸浸出过滤操作，得到第一高酸浸出渣和第一高酸浸出液；
    将所述硫酸、所述还原剂及所述第一高酸浸出渣混合后进行第二高酸浸出过滤操作，得到所述电池级石墨原料。
  10. 根据权利要求9所述的基于提锂电池粉的回收处理方法，其特征在于，在将所述硫酸、所述还原剂及所述第二浸出渣混合后进行第一高酸浸出过滤操作的步骤之后，以及在将所述硫酸、所述还原剂及所述第一高酸浸出渣混合后进行第二高酸浸出过滤操作的步骤之前，所述回收处理方法还包括如下步骤：
    将所述硫酸、所述还原剂、所述第一高酸浸出液及所述第一浸出渣混合后进行第二段浸出过滤操作。
  11. 根据权利要求9所述的基于提锂电池粉的回收处理方法，其特征在于，在将所述硫酸、所述还原剂及所述第一高酸浸出渣混合后进行第二高酸浸出过滤操作，得到所述电池级石墨原料的步骤之后，所述回收处理方法还包括如下 步骤：
    将所述硫酸、所述还原剂、所述第二高酸浸出液及所述第二浸出渣混合后进行第一高酸浸出过滤操作。
  12. 根据权利要求9所述的基于提锂电池粉的回收处理方法，其特征在于，所述第一高酸浸出过滤操作的酸度为200g/L～300g/L。
  13. 根据权利要求9所述的基于提锂电池粉的回收处理方法，其特征在于，所述第一高酸浸出过滤操作的酸度为300g/L～500g/L。
  14. 根据权利要求9所述的基于提锂电池粉的回收处理方法，其特征在于，所述第一高酸浸出过滤操作和所述第二高酸浸出过滤操作的温度均为80℃～100℃
  15. 根据权利要求1所述的基于提锂电池粉的回收处理方法，其特征在于，所述第一段浸出过滤操作的温度为80℃～100℃。
  16. 根据权利要求1所述的基于提锂电池粉的回收处理方法，其特征在于，所述还原剂为双氧水、二氧化硫及亚硫酸钠中的至少一种。
PCT/CN2023/100733 2023-06-16 2023-06-16 基于提锂电池粉的回收处理方法 Ceased WO2024254856A1 (zh)

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