WO2024001716A1 - Synergistic extraction method for selectively separating lithium and transition metals from waste batteries by using hydrophobic deep eutectic solvent - Google Patents

Synergistic extraction method for selectively separating lithium and transition metals from waste batteries by using hydrophobic deep eutectic solvent Download PDF

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WO2024001716A1
WO2024001716A1 PCT/CN2023/099256 CN2023099256W WO2024001716A1 WO 2024001716 A1 WO2024001716 A1 WO 2024001716A1 CN 2023099256 W CN2023099256 W CN 2023099256W WO 2024001716 A1 WO2024001716 A1 WO 2024001716A1
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extraction
lithium
organic phase
cobalt
nickel
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PCT/CN2023/099256
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French (fr)
Chinese (zh)
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陈标华
郭宇
于刚强
代成娜
刘宁
徐瑞年
王宁
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北京工业大学
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • C22B23/0469—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods by chemical substitution, e.g. by cementation
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00—Obtaining manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 invention belongs to the technical field of hydrometallurgy, and in particular relates to a hydrophobic deep eutectic solvent and tributyl phosphate synergistic extraction agent and a method for extracting and separating lithium and transition metals in waste lithium battery leachate.
  • lithium-ion batteries are widely used in electronic equipment, electric vehicles, renewable energy storage, etc. due to their excellent energy storage capabilities. Reduce transportation’s dependence on fossil fuels.
  • lithium-ion batteries As a key metal element in lithium-ion batteries, lithium has attracted widespread attention due to its light weight. It is expected that the demand for lithium carbonate will exceed 5 million tons by 2025.
  • RC global average recyclable content
  • transition metals rank first among all recycled elements (especially nickel and cobalt), which will lead to the depletion of natural resources.
  • the total market for automotive lithium-ion batteries alone is expected to reach $221 billion by 2024.
  • lithium-ion batteries have not only led to serious shortages of lithium, nickel and cobalt. Used lithium-ion batteries will also seriously pollute the environment, and the content and purity of valuable metals in them are higher than those in nature. If not recycled, it will cause It is a huge waste of resources and does not conform to the concept of clean energy and resource utilization.
  • the common recycling methods of waste lithium batteries are mainly pyrometallurgy and hydrometallurgy processes.
  • the hydrometallurgical process has the characteristics of high selectivity, low energy consumption, and no harmful gases. It is more in line with the concept of green environmental protection than the pyrometallurgical process.
  • the battery is first pretreated by various physical methods, and then various metals are dissolved in acid, and the acid leachate of Li, Co, Ni and Mn is obtained after purification.
  • Hydrochloric acid or sulfuric acid is more economical than other leaching agents and is commonly used for acid reduction leaching of metals in lithium-ion batteries during hydrometallurgical processes.
  • solvent extraction is widely used for metal separation due to its simple operation, high recovery rate, and good adjustability.
  • CN112442596A discloses a method for separating nickel, cobalt and manganese from batteries containing nickel, cobalt and manganese. Nickel, cobalt and manganese are separated step by step through multi-stage countercurrent extraction using a carboxylic acid extractant.
  • CN111850302B discloses a method for separating metals from waste lithium batteries using diketone compounds as extraction agents and organic phosphine compounds as co-extraction agents. After multi-stage countercurrent extraction, the extraction rate of nickel, cobalt and manganese reaches more than 99%. However, most of these extraction processes require multi-stage extraction, which increases the loss of the extraction agent to a certain extent, which not only increases the cost, but also causes a waste of resources.
  • the present invention uses a hydrophobic eutectic and tributyl phosphate to collaboratively extract nickel, cobalt and manganese in waste lithium batteries, leaving lithium in the raffinate.
  • Single-stage extraction can achieve higher extraction and separation effects. , which is environmentally friendly and has low operating costs.
  • step (3) Add the organic phase obtained in step (3) to the aqueous phase obtained in step (1) for mixing and extraction, and centrifuge to separate the phases to obtain a nickel-cobalt-manganese-loaded organic phase and a lithium-containing raffinate;
  • lidocaine and n-decanoic acid in the hydrophobic deep eutectic solvent prepared in step (2) are combined through hydrogen bonding, and the ratio of the amounts of substances is 1:1. Heat and melt n-decanoic acid, add it to lidocaine, and mix under 50°C water bath heating conditions to obtain a hydrophobic deep eutectic solvent.
  • organic phase prepared in step (3) contains three of the following structural formulas:
  • the ratio of the volume of tributyl phosphate to the hydrophobic eutectic in the organic phase prepared in step (3) 6:4 ⁇ 4:6;
  • the mixing time is 20 ⁇ 30min
  • the mixing speed is 200 ⁇ 500r/min
  • the aqueous phase and the organic phase are fully mixed and placed in a centrifuge
  • the centrifugation speed is 6000 ⁇ 8000r/min
  • the centrifugation time is 10
  • the phases are separated for ⁇ 30 minutes to obtain the nickel-cobalt-manganese-loaded organic phase and the lithium-containing raffinate.
  • the precipitant added in step (5) is 1.5 mol/sodium carbonate solution, and the ratio of the volume of the added sodium carbonate to the lithium-containing raffinate is 2.
  • the temperature is 24°C
  • the back-extraction level is level 1
  • the mixing time is 30 minutes
  • the mixing speed is 300r/min
  • the centrifugation speed is 8000r/min
  • the centrifugation time is 10min
  • the phases are then separated to obtain the nickel-cobalt-manganese stripping solution and the regenerated organic phase.
  • Figure 1 is a process flow chart of the extraction and separation method of valuable metals in waste lithium battery leachate provided by the present invention.
  • This embodiment provides a synergistic extraction agent between a hydrophobic deep eutectic solvent and tributyl phosphate and its method for extracting and separating lithium and transition metals in waste lithium battery leachate, as shown in Figure 1.
  • lidocaine and n-decanoic acid in the prepared hydrophobic deep eutectic solvent are combined through hydrogen bonding, and the ratio of the amounts of substances is 1:1.
  • the configured hydrophobic deep eutectic solvent is added to tributyl phosphate,
  • the volume ratio of the added tributyl phosphate to the hydrophobic eutectic is 6:4 to obtain an organic phase;
  • the configured organic phase is added to the aqueous phase.
  • the extraction level is level 1.
  • the mixing time is 20 minutes and the rotation speed is 200 r/min. After thorough mixing, place it in a centrifuge at a centrifugal speed of 6000 r/min. After centrifugation for 10 minutes, the phases are separated to obtain the nickel-cobalt-manganese-loaded organic phase and the lithium-containing extract. Remaining liquid.
  • a sodium carbonate solution with a concentration of 1.5 mol/L is added to the lithium-containing raffinate.
  • the volume ratio of the added sodium carbonate solution to the lithium-containing raffinate is 2:1, and the precipitation is sufficient. After washing, a lithium carbonate solution is obtained.
  • the back-extraction process uses 2 mol/L HCl as the back-extraction agent.
  • the stripping temperature is 24°C
  • the stripping level is 1
  • the mixing time is 30min
  • the rotation speed is 300r/min
  • the centrifugation speed is 8000r/min
  • the centrifugation time is After 10 minutes, the phases were separated to obtain the nickel-cobalt-manganese stripping solution and the regenerated organic phase.
  • Example 1 The extraction experimental results of Example 1 are as follows:
  • the extraction rate of nickel, cobalt and manganese reached more than 92%.
  • a high-purity lithium salt solution was obtained in the raffinate, achieving effective separation of lithium and transition metals in spent lithium batteries. .
  • This embodiment provides a synergistic extraction agent between a hydrophobic deep eutectic solvent and tributyl phosphate and its method for extracting and separating lithium and transition metals in waste lithium battery leachate, as shown in Figure 1.
  • lidocaine and n-decanoic acid in the prepared hydrophobic deep eutectic solvent are combined through hydrogen bonding, and the ratio of the amounts of substances is 1:1.
  • the configured hydrophobic deep eutectic solvent is added to tributyl phosphate, where the volume ratio of the added tributyl phosphate to the hydrophobic deep eutectic is 4:6, to obtain The organic phase;
  • the configured organic phase is added to the aqueous phase.
  • the extraction level is level 1.
  • the mixing time is 30 minutes and the rotation speed is 500 r/min. After thorough mixing, it is placed in a centrifuge at a centrifugal speed of 8000 r/min. After centrifugation for 30 minutes, the phases are separated to obtain the nickel-cobalt-manganese-loaded organic phase and lithium-containing organic phase. raffinate.
  • a sodium carbonate solution with a concentration of 1.5 mol/L is added to the lithium-containing raffinate.
  • the volume ratio of the added sodium carbonate solution to the lithium-containing raffinate is 2:1, and the precipitation is sufficient. After washing, a lithium carbonate solution is obtained.
  • the back-extraction process uses 2 mol/L HCl as the back-extraction agent.
  • the stripping temperature is 24°C
  • the stripping level is 1
  • the mixing time is 30min
  • the rotation speed is 300r/min
  • the centrifugation speed is 8000r/min
  • the centrifugation time is After 15 minutes, the phases were separated to obtain the nickel-cobalt-manganese stripping solution and the regenerated organic phase.
  • Example 2 The extraction experimental results of Example 2 are as follows:
  • the extraction rate of nickel, cobalt and manganese reaches 98%.
  • a high-purity lithium salt solution is obtained in the raffinate, achieving effective separation of lithium and transition metals in spent lithium batteries.
  • This embodiment provides a synergistic extraction agent between a hydrophobic deep eutectic solvent and tributyl phosphate and its method for extracting and separating lithium and transition metals in waste lithium battery leachate, as shown in Figure 1.
  • lidocaine and n-decanoic acid in the prepared hydrophobic deep eutectic solvent are combined through hydrogen bonding, and the ratio of the amounts of substances is 1:1.
  • Heat and melt n-decanoic acid add it to lidocaine, and heat it in a 50°C water bath. Mix under heating conditions to obtain a hydrophobic deep eutectic solvent;
  • the configured hydrophobic deep eutectic solvent is added to tributyl phosphate, where the volume ratio of the added tributyl phosphate to the hydrophobic deep eutectic is 4:6, to obtain The organic phase;
  • the configured organic phase is added to the aqueous phase.
  • the extraction level is level 1.
  • the mixing time is 30 minutes and the rotation speed is 300 r/min. Mix thoroughly and place it in a centrifuge. The centrifugation speed is 8000 r/min. Centrifuge for 10 minutes and then separate the phases.
  • the nickel-cobalt-manganese-loaded organic phase and lithium-containing raffinate are obtained.
  • a sodium carbonate solution with a concentration of 1.5 mol/L is added to the lithium-containing raffinate.
  • the volume ratio of the added sodium carbonate solution to the lithium-containing raffinate is 2:1, and the precipitation is sufficient. After washing, a lithium carbonate solution is obtained.
  • the back-extraction process uses 2 mol/L HCl as the back-extraction agent.
  • the stripping temperature is 24°C
  • the stripping level is 1
  • the mixing time is 30min
  • the rotation speed is 300r/min
  • the centrifugation speed is 8000r/min
  • the centrifugation time is After 10 minutes, the phases were separated to obtain the nickel-cobalt-manganese stripping solution and the regenerated organic phase.
  • the extraction rate of nickel, cobalt and manganese reaches 93%.
  • a high-purity lithium salt solution is obtained in the raffinate, achieving effective separation of lithium and transition metals in spent lithium batteries.
  • This embodiment provides a synergistic extraction agent between a hydrophobic deep eutectic solvent and tributyl phosphate and its method for extracting and separating lithium and transition metals in waste lithium battery leachate, as shown in Figure 1.
  • lidocaine and n-decanoic acid in the prepared hydrophobic deep eutectic solvent are passed through hydrogen
  • the bonding effect combines, and the ratio of the amounts of substances is 1:1.
  • Heat and melt n-decanoic acid add it to lidocaine, and mix under 50°C water bath heating conditions to obtain a hydrophobic deep eutectic solvent;
  • the configured hydrophobic deep eutectic solvent is added to tributyl phosphate, where the volume ratio of the added tributyl phosphate to the hydrophobic deep eutectic is 4:6, to obtain The organic phase;
  • the configured organic phase is added to the aqueous phase.
  • the extraction level is level 1.
  • the mixing time is 30 minutes and the rotation speed is 300 r/min. After thorough mixing, it is placed in a centrifuge at a centrifugal speed of 8000 r/min. After centrifugation for 10 minutes, the phases are separated to obtain the nickel-cobalt-manganese-loaded organic phase and lithium-containing organic phase. raffinate.
  • a sodium carbonate solution with a concentration of 1.5 mol/L is added to the lithium-containing raffinate.
  • the volume ratio of the added sodium carbonate solution to the lithium-containing raffinate is 2:1, and the precipitation is sufficient. After washing, a lithium carbonate solution is obtained.
  • the back-extraction process uses 2 mol/L HCl as the back-extraction agent.
  • the stripping temperature is 24°C
  • the stripping level is 1
  • the mixing time is 30min
  • the rotation speed is 300r/min
  • the centrifugation speed is 8000r/min
  • the centrifugation time is After 10 minutes, the phases were separated to obtain the nickel-cobalt-manganese stripping solution and the regenerated organic phase.
  • the extraction rate of nickel, cobalt and manganese reaches 99%.
  • a high-purity lithium salt solution is obtained in the raffinate, achieving effective separation of lithium and transition metals in spent lithium batteries.
  • This embodiment provides a synergistic extraction agent between a hydrophobic deep eutectic solvent and tributyl phosphate and its method for extracting and separating lithium and transition metals in waste lithium battery leachate, as shown in Figure 1.
  • lidocaine and n-decanoic acid in the prepared hydrophobic deep eutectic solvent are combined through hydrogen bonding, and the ratio of the amounts of substances is 1:1.
  • the configured hydrophobic deep eutectic solvent is added to tributyl phosphate, where the volume ratio of the added tributyl phosphate to the hydrophobic deep eutectic is 4:6, to obtain The organic phase;
  • the configured organic phase is added to the aqueous phase.
  • the extraction level is level 1.
  • the mixing time is 30 minutes and the rotation speed is 300 r/min. After thorough mixing, it is placed in a centrifuge at a centrifugal speed of 8000 r/min. After centrifugation for 10 minutes, the phases are separated to obtain the nickel-cobalt-manganese-loaded organic phase and lithium-containing organic phase. raffinate.
  • a sodium carbonate solution with a concentration of 1.5 mol/L is added to the lithium-containing raffinate.
  • the volume ratio of the added sodium carbonate solution to the lithium-containing raffinate is 2:1, and the precipitation is sufficient. After washing, a lithium carbonate solution is obtained.
  • the back-extraction process uses 2 mol/L HCl as the back-extraction agent.
  • the back-extraction temperature is 24°C
  • the back-extraction level is level 1
  • the mixing time is 30 minutes
  • the rotation speed is 300 r/min
  • the centrifugation speed is 8000 r/min
  • the centrifugation time is After 10 minutes, the phases were separated to obtain the nickel-cobalt-manganese stripping solution and the regenerated organic phase.
  • the extraction rate of nickel, cobalt and manganese reaches 98%.
  • a high-purity lithium salt solution is obtained in the raffinate, achieving effective separation of lithium and transition metals in spent lithium batteries.

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Abstract

A synergistic extraction method for selectively separating lithium and transition metals from waste batteries by using a hydrophobic deep eutectic solvent, relating to the technical field of hydrometallurgy. Provided is a synergistic extraction method having a good separation and extraction effect. Specifically disclosed are a hydrophobic deep eutectic solvent and tributyl phosphate (TBP) synergistic extractant and a method for separating lithium and transition metals from a waste lithium battery leachate. The hydrophobic deep eutectic solvent provided in the present application comprises n-decanoic acid (a hydrogen bond donor) and lidocaine (a hydrogen bond acceptor). The method comprises the following steps: (1) preparation of a hydrophobic deep eutectic solvent; (2) preparation of an organic phase for extraction; (3) co-extraction of nickel, cobalt and manganese; (4) stripping of nickel, cobalt and manganese; and (5) lithium precipitation. According to the present invention, the extraction effect on transition metals: nickel, cobalt and manganese, is good, the purity of lithium in the remaining water phase is high, efficient recovery of valuable metals in a waste lithium battery positive electrode material leachate is implemented, and the used deep eutectic solvent is a "novel green" solvent that is small in pollution, simple and convenient to synthesize, and low in price.

Description

一种使用疏水性低共熔溶剂从废电池中选择性分离锂与过渡金属的协同萃取方法A synergistic extraction method for selective separation of lithium and transition metals from spent batteries using hydrophobic deep eutectic solvents 技术领域Technical field
本发明属湿法冶金技术领域，尤其涉及一种疏水性低共熔溶剂与磷酸三丁酯协同萃取剂及其对废锂电池浸出液中锂与过渡金属萃取分离的方法。The invention belongs to the technical field of hydrometallurgy, and in particular relates to a hydrophobic deep eutectic solvent and tributyl phosphate synergistic extraction agent and a method for extracting and separating lithium and transition metals in waste lithium battery leachate.
背景技术Background technique
在能源和交通系统的脱碳成为最重要的国际挑战之一的时代，锂离子电池(LIB)以其优异的储能能力被广泛应用于电子设备、电动汽车、可再生能源存储等方面，可以减少交通运输业对化石燃料的依赖。锂作为锂离子电池中的关键金属元素，因其重量轻而受到广泛关注，预计到2025年碳酸锂的需求量将超过500万吨。根据全球平均可回收含量(RC)数据，过渡金属在所有回收元素(尤其是镍和钴)中居于首位，这将导致自然资源枯竭。到2024年，仅汽车锂离子电池的总市场预计将达到2210亿美元。然而，锂离子电池产量的增加不仅导致锂、镍和钴的严重短缺，废旧的锂离子电池也将严重污染环境，而且其中有价金属的含量和纯度都高于自然界，如果不回收，将造成巨大的资源浪费，不符合清洁能源和资源化利用的理念。In an era when the decarbonization of energy and transportation systems has become one of the most important international challenges, lithium-ion batteries (LIB) are widely used in electronic equipment, electric vehicles, renewable energy storage, etc. due to their excellent energy storage capabilities. Reduce transportation’s dependence on fossil fuels. As a key metal element in lithium-ion batteries, lithium has attracted widespread attention due to its light weight. It is expected that the demand for lithium carbonate will exceed 5 million tons by 2025. According to global average recyclable content (RC) data, transition metals rank first among all recycled elements (especially nickel and cobalt), which will lead to the depletion of natural resources. The total market for automotive lithium-ion batteries alone is expected to reach $221 billion by 2024. However, the increase in the production of lithium-ion batteries has not only led to serious shortages of lithium, nickel and cobalt. Used lithium-ion batteries will also seriously pollute the environment, and the content and purity of valuable metals in them are higher than those in nature. If not recycled, it will cause It is a huge waste of resources and does not conform to the concept of clean energy and resource utilization.
目前，废锂电池的常见回收方法主要是火法冶金和湿法冶金工艺。湿法冶金工艺具有选择性高、能耗低、无有害气体等特点，比火法冶金工艺更符合绿色环保理念。在湿法冶金工艺中，电池首先经过预处理各种物理方法，然后将各种金属溶解在酸中，提纯后得到Li、Co、Ni和Mn的酸浸出液。盐酸或硫酸比其他浸出剂更经济，通常用于湿法冶金过程中锂离子电池中金属的酸还原浸出。在各种金属回收方法中，溶剂萃取因其操作简单、回收率高、可调节性好而被广泛用于金属分离。At present, the common recycling methods of waste lithium batteries are mainly pyrometallurgy and hydrometallurgy processes. The hydrometallurgical process has the characteristics of high selectivity, low energy consumption, and no harmful gases. It is more in line with the concept of green environmental protection than the pyrometallurgical process. In the hydrometallurgical process, the battery is first pretreated by various physical methods, and then various metals are dissolved in acid, and the acid leachate of Li, Co, Ni and Mn is obtained after purification. Hydrochloric acid or sulfuric acid is more economical than other leaching agents and is commonly used for acid reduction leaching of metals in lithium-ion batteries during hydrometallurgical processes. Among various metal recovery methods, solvent extraction is widely used for metal separation due to its simple operation, high recovery rate, and good adjustability.
CN112442596A公开了一种从含镍钴锰的电池中分离镍钴锰的方法，使用羧酸类萃取剂通过多级逆流萃取分步分离了镍、钴、锰。CN111850302B公开了一种使用双酮类化合物为萃取剂与有机膦化合物为协萃剂从废锂电池中分离金属的方法，经多级逆流萃取后镍钴锰的萃取率均达到99％以上。但这些萃取工艺大多需要进行多级萃取，在一定程度上加大了萃取剂的损耗，不仅使成本增加，而且造成了资源的浪费。同时，使用这些传统的萃取剂，不仅萃取效果有限，而且这些萃取剂具有易挥发、污染环境、有毒性等特点而受到限制，因此开发一种不仅萃取效率高，萃取方法简便，而且对环境友好的“绿色溶剂”就显得至关重要。CN112442596A discloses a method for separating nickel, cobalt and manganese from batteries containing nickel, cobalt and manganese. Nickel, cobalt and manganese are separated step by step through multi-stage countercurrent extraction using a carboxylic acid extractant. CN111850302B discloses a method for separating metals from waste lithium batteries using diketone compounds as extraction agents and organic phosphine compounds as co-extraction agents. After multi-stage countercurrent extraction, the extraction rate of nickel, cobalt and manganese reaches more than 99%. However, most of these extraction processes require multi-stage extraction, which increases the loss of the extraction agent to a certain extent, which not only increases the cost, but also causes a waste of resources. At the same time, the use of these traditional extraction agents not only has limited extraction effects, but also is restricted by the characteristics of volatile, environmentally polluting, and toxic extractants. Therefore, developing an extraction method that not only has high extraction efficiency, is simple, and is also environmentally friendly is needed. The "green solvent" is crucial.
发明内容 Contents of the invention
针对上述问题，本发明采用一种疏水性低共熔与磷酸三丁酯协同萃取废锂电池中的镍钴锰，将锂留在萃余液中，单级萃取能达到较高的萃取分离效果，具有对环境友好，运营成本低等特点。In response to the above problems, the present invention uses a hydrophobic eutectic and tributyl phosphate to collaboratively extract nickel, cobalt and manganese in waste lithium batteries, leaving lithium in the raffinate. Single-stage extraction can achieve higher extraction and separation effects. , which is environmentally friendly and has low operating costs.
为了达到上述目的，本发明采用以下技术方案：In order to achieve the above objects, the present invention adopts the following technical solutions:
(1)配制水相：模拟废锂电池浸出液成分，配置得到含锂、镍、钴和锰金属离子的水相；(1) Prepare the water phase: simulate the components of the waste lithium battery leachate, and prepare the water phase containing lithium, nickel, cobalt and manganese metal ions;
(2)配制疏水性低共熔溶剂：将利多卡因与正癸酸加热混合得到疏水性低共熔溶剂；(2) Prepare a hydrophobic deep eutectic solvent: heat and mix lidocaine and n-decanoic acid to obtain a hydrophobic deep eutectic solvent;
(3)配制有机相：将步骤(2)中得到的疏水性低共熔溶剂与磷酸三丁酯混合，得到有机相；(3) Prepare organic phase: mix the hydrophobic deep eutectic solvent obtained in step (2) and tributyl phosphate to obtain an organic phase;
(4)将步骤(3)中得到的有机相加入到步骤(1)得到的水相中进行混合萃取，离心分相后得到镍钴锰负载有机相和含锂萃余液；(4) Add the organic phase obtained in step (3) to the aqueous phase obtained in step (1) for mixing and extraction, and centrifuge to separate the phases to obtain a nickel-cobalt-manganese-loaded organic phase and a lithium-containing raffinate;
(5)将沉淀剂加入到步骤(4)中的含锂萃余液中得到碳酸锂沉淀；(5) Add a precipitating agent to the lithium-containing raffinate in step (4) to obtain lithium carbonate precipitation;
(6)将反萃剂加入到步骤(4)中的镍钴锰负载有机相中，得到镍钴锰反萃液和再生有机相；(6) Add the stripping agent to the nickel-cobalt-manganese-loaded organic phase in step (4) to obtain a nickel-cobalt-manganese stripping liquid and a regenerated organic phase;
进一步，步骤(1)中模拟废电池浸出液水相pH为2～6，有价金属含量分别为Li＝300～400mg/L，Ni＝1300～1500mg/L，Co＝600～700mg/L，Mn＝800～900mg/L。Further, in step (1), the pH of the aqueous phase of the simulated waste battery leachate is 2 to 6, and the valuable metal contents are Li=300~400mg/L, Ni=1300~1500mg/L, Co=600~700mg/L, and Mn. =800～900mg/L.
进一步，步骤(2)配制的疏水性低共熔溶剂中利多卡因与正癸酸通过氢键作用结合，物质的量之比为1:1。将正癸酸加热融化后加入到利多卡因中，在50℃水浴加热条件下混合得到疏水性低共熔溶剂。Further, lidocaine and n-decanoic acid in the hydrophobic deep eutectic solvent prepared in step (2) are combined through hydrogen bonding, and the ratio of the amounts of substances is 1:1. Heat and melt n-decanoic acid, add it to lidocaine, and mix under 50°C water bath heating conditions to obtain a hydrophobic deep eutectic solvent.
进一步，步骤(3)配制的有机相中包含如下结构式中的三种：
Further, the organic phase prepared in step (3) contains three of the following structural formulas:
进一步，步骤(3)配制的有机相中磷酸三丁酯与疏水性低共熔体积之比＝6:4～4:6； Further, the ratio of the volume of tributyl phosphate to the hydrophobic eutectic in the organic phase prepared in step (3) = 6:4~4:6;
进一步，步骤(4)中萃取工艺参数为加入的水相与有机相的体积之比(A/O)＝3:1～1:3，萃取温度为10～30℃，萃取级数为1级，混匀搅拌时间为20～30min，混匀搅拌转速为200～500r/min，将水相与有机相充分混匀后置于离心机中，离心转速为6000～8000r/min，离心时间为10～30min进行分相，得到镍钴锰负载有机相和含锂萃余液。Further, the extraction process parameters in step (4) are the volume ratio of the added aqueous phase and the organic phase (A/O)=3:1~1:3, the extraction temperature is 10~30°C, and the extraction level is 1. , the mixing time is 20~30min, the mixing speed is 200~500r/min, the aqueous phase and the organic phase are fully mixed and placed in a centrifuge, the centrifugation speed is 6000~8000r/min, the centrifugation time is 10 The phases are separated for ~30 minutes to obtain the nickel-cobalt-manganese-loaded organic phase and the lithium-containing raffinate.
进一步，步骤(5)中加入的沉淀剂为1.5mol/的碳酸钠溶液，加入的碳酸钠与含锂萃余液的体积的比值为2。Further, the precipitant added in step (5) is 1.5 mol/sodium carbonate solution, and the ratio of the volume of the added sodium carbonate to the lithium-containing raffinate is 2.
进一步，步骤(6)反萃取工艺使用2mol/L的HCl作为反萃剂，反萃取参数为加入的盐酸与镍钴锰负载有机相的体积的比(A/O)＝2:1，反萃取温度为24℃，反萃取级数为1级，混匀搅拌时间为30min，混匀搅拌转速为300r/min，充分混匀后置于离心机中，离心转速为8000r/min，离心时间为10min后分相得到镍钴锰反萃液和再生有机相。Further, the back-extraction process of step (6) uses 2 mol/L HCl as the back-extraction agent, and the back-extraction parameter is the volume ratio of the added hydrochloric acid to the nickel-cobalt-manganese-loaded organic phase (A/O) = 2:1. The temperature is 24°C, the back-extraction level is level 1, the mixing time is 30 minutes, the mixing speed is 300r/min, mix thoroughly and then placed in a centrifuge, the centrifugation speed is 8000r/min, the centrifugation time is 10min The phases are then separated to obtain the nickel-cobalt-manganese stripping solution and the regenerated organic phase.
附图说明Description of drawings
图1为本发明提供的废锂电池浸出液中有价金属萃取分离方法的工艺流程图。Figure 1 is a process flow chart of the extraction and separation method of valuable metals in waste lithium battery leachate provided by the present invention.
下面结合实例对本发明进一步详细说明，但下述的实例仅仅是本发明的简易例子，并不代表或限制本发明的权利保护范围，本发明的保护范围以权利要求书为准。The present invention will be further described in detail below with examples. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be determined by the claims.
具体实施方式Detailed ways
为了更好地说明本发明，便于理解本发明的技术方案，本发明的典型但非限制性的实施例如下：In order to better illustrate the present invention and facilitate understanding of the technical solution of the present invention, typical but non-limiting examples of the present invention are as follows:
实施例1Example 1
本实施例提供的一种疏水性低共熔溶剂与磷酸三丁酯协同萃取剂及其对废锂电池浸出液中锂与过渡金属萃取分离的方法流程如图1所示。This embodiment provides a synergistic extraction agent between a hydrophobic deep eutectic solvent and tributyl phosphate and its method for extracting and separating lithium and transition metals in waste lithium battery leachate, as shown in Figure 1.
本实施例的模拟废锂电池酸性浸出液中成分如下：
The components of the acid leachate of the simulated waste lithium battery in this embodiment are as follows:
本实施例所述的萃取分离方法，配制的模拟废锂电池水相pH＝2；According to the extraction and separation method described in this example, the prepared simulated waste lithium battery aqueous phase has pH=2;
本实施例所述的萃取分离方法，配制的疏水性低共熔溶剂中利多卡因与正癸酸通过氢键作用结合，物质的量之比为1:1。将正癸酸加热融化后加入到利多卡因中，在50℃水浴加热条件下混合得到疏水性低共熔溶剂；In the extraction and separation method described in this embodiment, lidocaine and n-decanoic acid in the prepared hydrophobic deep eutectic solvent are combined through hydrogen bonding, and the ratio of the amounts of substances is 1:1. Heat and melt n-decanoic acid, add it to lidocaine, and mix under 50°C water bath heating conditions to obtain a hydrophobic deep eutectic solvent;
本实施例所述的萃取分离方法，将配置好的疏水性低共熔溶剂加入到磷酸三丁酯中， 其中加入的磷酸三丁酯与疏水性低共熔的体积比为6:4，得到有机相；In the extraction and separation method described in this embodiment, the configured hydrophobic deep eutectic solvent is added to tributyl phosphate, The volume ratio of the added tributyl phosphate to the hydrophobic eutectic is 6:4 to obtain an organic phase;
本实施例所述的萃取分离方法，将配置好的有机相加入到水相中，萃取工艺参数为水相与有机相的体积比(A/O)＝2:1，萃取温度为10℃，萃取级数为1级，混匀搅拌时间20min，转速200r/min，充分混匀后置于离心机中，离心转速6000r/min，离心10min后分相得到镍钴锰负载有机相和含锂萃余液。In the extraction and separation method described in this embodiment, the configured organic phase is added to the aqueous phase. The extraction process parameters are the volume ratio of the aqueous phase to the organic phase (A/O) = 2:1, and the extraction temperature is 10°C. The extraction level is level 1. The mixing time is 20 minutes and the rotation speed is 200 r/min. After thorough mixing, place it in a centrifuge at a centrifugal speed of 6000 r/min. After centrifugation for 10 minutes, the phases are separated to obtain the nickel-cobalt-manganese-loaded organic phase and the lithium-containing extract. Remaining liquid.
本实施例所述的萃取分离方法，向含锂萃余液中加入浓度为1.5mol/L的碳酸钠溶液，加入的碳酸钠溶液与含锂萃余液的体积比为2：1，充分沉淀洗涤后得到碳酸锂溶液。In the extraction and separation method described in this embodiment, a sodium carbonate solution with a concentration of 1.5 mol/L is added to the lithium-containing raffinate. The volume ratio of the added sodium carbonate solution to the lithium-containing raffinate is 2:1, and the precipitation is sufficient. After washing, a lithium carbonate solution is obtained.
本实施例所述的萃取分离方法，反萃取工艺使用2mol/L的HCl作为反萃剂，反萃取参数为，加入的HCl与镍钴锰负载有机相的体积比(A/O)＝2:1，反萃取温度为24℃，反萃取级数为1级，混匀搅拌时间为30min，转速为300r/min，充分混匀后置于离心机中，离心转速为8000r/min，离心时间为10min后分相，得到镍钴锰反萃液和再生有机相。In the extraction and separation method described in this embodiment, the back-extraction process uses 2 mol/L HCl as the back-extraction agent. The back-extraction parameters are: the volume ratio of the added HCl to the nickel-cobalt-manganese loaded organic phase (A/O) = 2: 1. The stripping temperature is 24°C, the stripping level is 1, the mixing time is 30min, the rotation speed is 300r/min, mix thoroughly and place it in a centrifuge, the centrifugation speed is 8000r/min, the centrifugation time is After 10 minutes, the phases were separated to obtain the nickel-cobalt-manganese stripping solution and the regenerated organic phase.
实施例1的萃取实验结果如下：
The extraction experimental results of Example 1 are as follows:
在本实施例中，经单级萃取后，镍钴锰的萃取率均达到92％以上，同时萃余液中得到高纯度的锂盐溶液，实现了废锂电池中锂与过渡金属的有效分离。In this embodiment, after single-stage extraction, the extraction rate of nickel, cobalt and manganese reached more than 92%. At the same time, a high-purity lithium salt solution was obtained in the raffinate, achieving effective separation of lithium and transition metals in spent lithium batteries. .
实施例2Example 2
本实施例提供的一种疏水性低共熔溶剂与磷酸三丁酯协同萃取剂及其对废锂电池浸出液中锂与过渡金属萃取分离的方法流程如图1所示。This embodiment provides a synergistic extraction agent between a hydrophobic deep eutectic solvent and tributyl phosphate and its method for extracting and separating lithium and transition metals in waste lithium battery leachate, as shown in Figure 1.
本实施例的模拟废锂电池酸性浸出液中成分如下：
The components of the acid leachate of the simulated waste lithium battery in this embodiment are as follows:
本实施例所述的萃取分离方法，配制的模拟废锂电池水相pH＝6；According to the extraction and separation method described in this example, the prepared simulated waste lithium battery aqueous phase has pH=6;
本实施例所述的萃取分离方法，配制的疏水性低共熔溶剂中利多卡因与正癸酸通过氢键作用结合，物质的量之比为1:1。将正癸酸加热融化后加入到利多卡因中，在50℃水浴加热条件下混合得到疏水性低共熔溶剂； In the extraction and separation method described in this embodiment, lidocaine and n-decanoic acid in the prepared hydrophobic deep eutectic solvent are combined through hydrogen bonding, and the ratio of the amounts of substances is 1:1. Heat and melt n-decanoic acid, add it to lidocaine, and mix under 50°C water bath heating conditions to obtain a hydrophobic deep eutectic solvent;
本实施例所述的萃取分离方法，将配置好的疏水性低共熔溶剂加入到磷酸三丁酯中，其中加入的磷酸三丁酯与疏水性低共熔的体积比为4:6，得到有机相；In the extraction and separation method described in this embodiment, the configured hydrophobic deep eutectic solvent is added to tributyl phosphate, where the volume ratio of the added tributyl phosphate to the hydrophobic deep eutectic is 4:6, to obtain The organic phase;
本实施例所述的萃取分离方法，将配置好的有机相加入到水相中，萃取工艺参数为水相与有机相的体积比(A/O)＝2:1，萃取温度为30℃，萃取级数为1级，混匀搅拌时间30min，转速500r/min，充分混匀后置于离心机中，离心转速8000r/min，离心30min后分相，得到镍钴锰负载有机相和含锂萃余液。In the extraction and separation method described in this embodiment, the configured organic phase is added to the aqueous phase. The extraction process parameters are the volume ratio of the aqueous phase to the organic phase (A/O) = 2:1, and the extraction temperature is 30°C. The extraction level is level 1. The mixing time is 30 minutes and the rotation speed is 500 r/min. After thorough mixing, it is placed in a centrifuge at a centrifugal speed of 8000 r/min. After centrifugation for 30 minutes, the phases are separated to obtain the nickel-cobalt-manganese-loaded organic phase and lithium-containing organic phase. raffinate.
本实施例所述的萃取分离方法，向含锂萃余液中加入浓度为1.5mol/L的碳酸钠溶液，加入的碳酸钠溶液与含锂萃余液的体积比为2：1，充分沉淀洗涤后得到碳酸锂溶液。In the extraction and separation method described in this embodiment, a sodium carbonate solution with a concentration of 1.5 mol/L is added to the lithium-containing raffinate. The volume ratio of the added sodium carbonate solution to the lithium-containing raffinate is 2:1, and the precipitation is sufficient. After washing, a lithium carbonate solution is obtained.
本实施例所述的萃取分离方法，反萃取工艺使用2mol/L的HCl作为反萃剂，反萃取参数为，加入的HCl与镍钴锰负载有机相的体积比(A/O)＝2:1，反萃取温度为24℃，反萃取级数为1级，混匀搅拌时间为30min，转速为300r/min，充分混匀后置于离心机中，离心转速为8000r/min，离心时间为15min后分相，得到镍钴锰反萃液和再生有机相。In the extraction and separation method described in this embodiment, the back-extraction process uses 2 mol/L HCl as the back-extraction agent. The back-extraction parameters are: the volume ratio of the added HCl to the nickel-cobalt-manganese loaded organic phase (A/O) = 2: 1. The stripping temperature is 24°C, the stripping level is 1, the mixing time is 30min, the rotation speed is 300r/min, mix thoroughly and place it in a centrifuge, the centrifugation speed is 8000r/min, the centrifugation time is After 15 minutes, the phases were separated to obtain the nickel-cobalt-manganese stripping solution and the regenerated organic phase.
实施例2的萃取实验结果如下：
The extraction experimental results of Example 2 are as follows:
在本实施例中，经单级萃取后，镍钴锰的萃取率均达到98％，同时萃余液中得到高纯度的锂盐溶液，实现了废锂电池中锂与过渡金属的有效分离。In this embodiment, after single-stage extraction, the extraction rate of nickel, cobalt and manganese reaches 98%. At the same time, a high-purity lithium salt solution is obtained in the raffinate, achieving effective separation of lithium and transition metals in spent lithium batteries.
实施例3Example 3
本实施例提供的一种疏水性低共熔溶剂与磷酸三丁酯协同萃取剂及其对废锂电池浸出液中锂与过渡金属萃取分离的方法流程如图1所示。This embodiment provides a synergistic extraction agent between a hydrophobic deep eutectic solvent and tributyl phosphate and its method for extracting and separating lithium and transition metals in waste lithium battery leachate, as shown in Figure 1.
本实施例的模拟废锂电池酸性浸出液中成分如下：
The components of the acid leachate of the simulated waste lithium battery in this embodiment are as follows:
本实施例所述的萃取分离方法，配制的模拟废锂电池水相pH＝3；According to the extraction and separation method described in this example, the prepared simulated waste lithium battery aqueous phase has pH=3;
本实施例所述的萃取分离方法，配制的疏水性低共熔溶剂中利多卡因与正癸酸通过氢键作用结合，物质的量之比为1:1。将正癸酸加热融化后加入到利多卡因中，在50℃水浴 加热条件下混合得到疏水性低共熔溶剂；In the extraction and separation method described in this embodiment, lidocaine and n-decanoic acid in the prepared hydrophobic deep eutectic solvent are combined through hydrogen bonding, and the ratio of the amounts of substances is 1:1. Heat and melt n-decanoic acid, add it to lidocaine, and heat it in a 50°C water bath. Mix under heating conditions to obtain a hydrophobic deep eutectic solvent;
本实施例所述的萃取分离方法，将配置好的疏水性低共熔溶剂加入到磷酸三丁酯中，其中加入的磷酸三丁酯与疏水性低共熔的体积比为4:6，得到有机相；In the extraction and separation method described in this embodiment, the configured hydrophobic deep eutectic solvent is added to tributyl phosphate, where the volume ratio of the added tributyl phosphate to the hydrophobic deep eutectic is 4:6, to obtain The organic phase;
本实施例所述的萃取分离方法，将配置好的有机相加入到水相中，萃取工艺参数为水相与有机相的体积比(A/O)＝3:1，萃取温度为24℃，萃取级数为1级，混匀搅拌时间30min，转速300r/min，充分混匀后置于离心机中，离心转速8000r/min，离心10min后分相。得到镍钴锰负载有机相和含锂萃余液。In the extraction and separation method described in this embodiment, the configured organic phase is added to the aqueous phase. The extraction process parameters are the volume ratio of the aqueous phase to the organic phase (A/O) = 3:1, and the extraction temperature is 24°C. The extraction level is level 1. The mixing time is 30 minutes and the rotation speed is 300 r/min. Mix thoroughly and place it in a centrifuge. The centrifugation speed is 8000 r/min. Centrifuge for 10 minutes and then separate the phases. The nickel-cobalt-manganese-loaded organic phase and lithium-containing raffinate are obtained.
本实施例所述的萃取分离方法，向含锂萃余液中加入浓度为1.5mol/L的碳酸钠溶液，加入的碳酸钠溶液与含锂萃余液的体积比为2：1，充分沉淀洗涤后得到碳酸锂溶液。In the extraction and separation method described in this embodiment, a sodium carbonate solution with a concentration of 1.5 mol/L is added to the lithium-containing raffinate. The volume ratio of the added sodium carbonate solution to the lithium-containing raffinate is 2:1, and the precipitation is sufficient. After washing, a lithium carbonate solution is obtained.
本实施例所述的萃取分离方法，反萃取工艺使用2mol/L的HCl作为反萃剂，反萃取参数为，加入的HCl与镍钴锰负载有机相的体积比(A/O)＝2:1，反萃取温度为24℃，反萃取级数为1级，混匀搅拌时间为30min，转速为300r/min，充分混匀后置于离心机中，离心转速为8000r/min，离心时间为10min后分相，得到镍钴锰反萃液和再生有机相。In the extraction and separation method described in this embodiment, the back-extraction process uses 2 mol/L HCl as the back-extraction agent. The back-extraction parameters are: the volume ratio of the added HCl to the nickel-cobalt-manganese loaded organic phase (A/O) = 2: 1. The stripping temperature is 24°C, the stripping level is 1, the mixing time is 30min, the rotation speed is 300r/min, mix thoroughly and place it in a centrifuge, the centrifugation speed is 8000r/min, the centrifugation time is After 10 minutes, the phases were separated to obtain the nickel-cobalt-manganese stripping solution and the regenerated organic phase.
实施例3的萃取实验结果如下：
The extraction experimental results of Example 3 are as follows:
在本实施例中，经单级萃取后，镍钴锰的萃取率均达到93％，同时萃余液中得到高纯度的锂盐溶液，实现了废锂电池中锂与过渡金属的有效分离。In this embodiment, after single-stage extraction, the extraction rate of nickel, cobalt and manganese reaches 93%. At the same time, a high-purity lithium salt solution is obtained in the raffinate, achieving effective separation of lithium and transition metals in spent lithium batteries.
实施例4Example 4
本实施例提供的一种疏水性低共熔溶剂与磷酸三丁酯协同萃取剂及其对废锂电池浸出液中锂与过渡金属萃取分离的方法流程如图1所示。This embodiment provides a synergistic extraction agent between a hydrophobic deep eutectic solvent and tributyl phosphate and its method for extracting and separating lithium and transition metals in waste lithium battery leachate, as shown in Figure 1.
本实施例的模拟废锂电池酸性浸出液中成分如下：
The components of the acid leachate of the simulated waste lithium battery in this embodiment are as follows:
本实施例所述的萃取分离方法，配制的模拟废锂电池水相pH＝3；According to the extraction and separation method described in this example, the prepared simulated waste lithium battery aqueous phase has pH=3;
本实施例所述的萃取分离方法，配制的疏水性低共熔溶剂中利多卡因与正癸酸通过氢 键作用结合，物质的量之比为1:1。将正癸酸加热融化后加入到利多卡因中，在50℃水浴加热条件下混合得到疏水性低共熔溶剂；In the extraction and separation method described in this example, lidocaine and n-decanoic acid in the prepared hydrophobic deep eutectic solvent are passed through hydrogen The bonding effect combines, and the ratio of the amounts of substances is 1:1. Heat and melt n-decanoic acid, add it to lidocaine, and mix under 50°C water bath heating conditions to obtain a hydrophobic deep eutectic solvent;
本实施例所述的萃取分离方法，将配置好的疏水性低共熔溶剂加入到磷酸三丁酯中，其中加入的磷酸三丁酯与疏水性低共熔的体积比为4:6，得到有机相；In the extraction and separation method described in this embodiment, the configured hydrophobic deep eutectic solvent is added to tributyl phosphate, where the volume ratio of the added tributyl phosphate to the hydrophobic deep eutectic is 4:6, to obtain The organic phase;
本实施例所述的萃取分离方法，将配置好的有机相加入到水相中，萃取工艺参数为水相与有机相的体积比(A/O)＝1:3，萃取温度为24℃，萃取级数为1级，混匀搅拌时间30min，转速300r/min，充分混匀后置于离心机中，离心转速8000r/min，离心10min后分相，得到镍钴锰负载有机相和含锂萃余液。In the extraction and separation method described in this embodiment, the configured organic phase is added to the aqueous phase. The extraction process parameters are the volume ratio of the aqueous phase to the organic phase (A/O) = 1:3, and the extraction temperature is 24°C. The extraction level is level 1. The mixing time is 30 minutes and the rotation speed is 300 r/min. After thorough mixing, it is placed in a centrifuge at a centrifugal speed of 8000 r/min. After centrifugation for 10 minutes, the phases are separated to obtain the nickel-cobalt-manganese-loaded organic phase and lithium-containing organic phase. raffinate.
本实施例所述的萃取分离方法，向含锂萃余液中加入浓度为1.5mol/L的碳酸钠溶液，加入的碳酸钠溶液与含锂萃余液的体积比为2：1，充分沉淀洗涤后得到碳酸锂溶液。In the extraction and separation method described in this embodiment, a sodium carbonate solution with a concentration of 1.5 mol/L is added to the lithium-containing raffinate. The volume ratio of the added sodium carbonate solution to the lithium-containing raffinate is 2:1, and the precipitation is sufficient. After washing, a lithium carbonate solution is obtained.
本实施例所述的萃取分离方法，反萃取工艺使用2mol/L的HCl作为反萃剂，反萃取参数为，加入的HCl与镍钴锰负载有机相的体积比(A/O)＝2:1，反萃取温度为24℃，反萃取级数为1级，混匀搅拌时间为30min，转速为300r/min，充分混匀后置于离心机中，离心转速为8000r/min，离心时间为10min后分相，得到镍钴锰反萃液与再生有机相。In the extraction and separation method described in this embodiment, the back-extraction process uses 2 mol/L HCl as the back-extraction agent. The back-extraction parameters are: the volume ratio of the added HCl to the nickel-cobalt-manganese loaded organic phase (A/O) = 2: 1. The stripping temperature is 24°C, the stripping level is 1, the mixing time is 30min, the rotation speed is 300r/min, mix thoroughly and place it in a centrifuge, the centrifugation speed is 8000r/min, the centrifugation time is After 10 minutes, the phases were separated to obtain the nickel-cobalt-manganese stripping solution and the regenerated organic phase.
实施例4的萃取实验结果如下：
The extraction experimental results of Example 4 are as follows:
在本实施例中，经单级萃取后，镍钴锰的萃取率均达到99％，同时萃余液中得到高纯度的锂盐溶液，实现了废锂电池中锂与过渡金属的有效分离。In this embodiment, after single-stage extraction, the extraction rate of nickel, cobalt and manganese reaches 99%. At the same time, a high-purity lithium salt solution is obtained in the raffinate, achieving effective separation of lithium and transition metals in spent lithium batteries.
实施例5Example 5
本实施例提供的一种疏水性低共熔溶剂与磷酸三丁酯协同萃取剂及其对废锂电池浸出液中锂与过渡金属萃取分离的方法流程如图1所示。This embodiment provides a synergistic extraction agent between a hydrophobic deep eutectic solvent and tributyl phosphate and its method for extracting and separating lithium and transition metals in waste lithium battery leachate, as shown in Figure 1.
本实施例的模拟废锂电池酸性浸出液中成分如下：
The components of the acid leachate of the simulated waste lithium battery in this embodiment are as follows:
本实施例所述的萃取分离方法，配制的模拟废锂电池水相pH＝3； According to the extraction and separation method described in this example, the prepared simulated waste lithium battery aqueous phase has pH=3;
本实施例所述的萃取分离方法，配制的疏水性低共熔溶剂中利多卡因与正癸酸通过氢键作用结合，物质的量之比为1:1。将正癸酸加热融化后加入到利多卡因中，在50℃水浴加热条件下混合得到疏水性低共熔溶剂；In the extraction and separation method described in this embodiment, lidocaine and n-decanoic acid in the prepared hydrophobic deep eutectic solvent are combined through hydrogen bonding, and the ratio of the amounts of substances is 1:1. Heat and melt n-decanoic acid, add it to lidocaine, and mix under 50°C water bath heating conditions to obtain a hydrophobic deep eutectic solvent;
本实施例所述的萃取分离方法，将配置好的疏水性低共熔溶剂加入到磷酸三丁酯中，其中加入的磷酸三丁酯与疏水性低共熔的体积比为4:6，得到有机相；In the extraction and separation method described in this embodiment, the configured hydrophobic deep eutectic solvent is added to tributyl phosphate, where the volume ratio of the added tributyl phosphate to the hydrophobic deep eutectic is 4:6, to obtain The organic phase;
本实施例所述的萃取分离方法，将配置好的有机相加入到水相中，萃取工艺参数为水相与有机相的体积比(A/O)＝1:2，萃取温度为24℃，萃取级数为1级，混匀搅拌时间30min，转速300r/min，充分混匀后置于离心机中，离心转速8000r/min，离心10min后分相，得到镍钴锰负载有机相和含锂萃余液。In the extraction and separation method described in this embodiment, the configured organic phase is added to the aqueous phase. The extraction process parameters are the volume ratio of the aqueous phase to the organic phase (A/O) = 1:2, and the extraction temperature is 24°C. The extraction level is level 1. The mixing time is 30 minutes and the rotation speed is 300 r/min. After thorough mixing, it is placed in a centrifuge at a centrifugal speed of 8000 r/min. After centrifugation for 10 minutes, the phases are separated to obtain the nickel-cobalt-manganese-loaded organic phase and lithium-containing organic phase. raffinate.
本实施例所述的萃取分离方法，向含锂萃余液中加入浓度为1.5mol/L的碳酸钠溶液，加入的碳酸钠溶液与含锂萃余液的体积比为2：1，充分沉淀洗涤后得到碳酸锂溶液。In the extraction and separation method described in this embodiment, a sodium carbonate solution with a concentration of 1.5 mol/L is added to the lithium-containing raffinate. The volume ratio of the added sodium carbonate solution to the lithium-containing raffinate is 2:1, and the precipitation is sufficient. After washing, a lithium carbonate solution is obtained.
本实施例所述的萃取分离方法，反萃取工艺使用2mol/L的HCl作为反萃剂，反萃取参数为，加入的HCl与镍钴锰负载有机相的体积比(A/O)＝2:1，反萃取温度为24℃，反萃取级数为1级，混匀搅拌时间为30min，转速为300r/min，充分混匀后置于离心机中，离心转速为8000r/min，离心时间为10min后分相，得到镍钴锰反萃液和再生有机相。In the extraction and separation method described in this embodiment, the back-extraction process uses 2 mol/L HCl as the back-extraction agent. The back-extraction parameters are: the volume ratio of the added HCl to the nickel-cobalt-manganese loaded organic phase (A/O) = 2: 1. The back-extraction temperature is 24°C, the back-extraction level is level 1, the mixing time is 30 minutes, the rotation speed is 300 r/min, mix thoroughly and then place it in a centrifuge, the centrifugation speed is 8000 r/min, and the centrifugation time is After 10 minutes, the phases were separated to obtain the nickel-cobalt-manganese stripping solution and the regenerated organic phase.
实施例5的萃取实验结果如下：
The extraction experimental results of Example 5 are as follows:
在本实施例中，经单级萃取后，镍钴锰的萃取率均达到98％，同时萃余液中得到高纯度的锂盐溶液，实现了废锂电池中锂与过渡金属的有效分离。 In this embodiment, after single-stage extraction, the extraction rate of nickel, cobalt and manganese reaches 98%. At the same time, a high-purity lithium salt solution is obtained in the raffinate, achieving effective separation of lithium and transition metals in spent lithium batteries.

Claims (5)

  1. 一种使用疏水性低共熔溶剂从废电池中选择性分离锂与过渡金属的协同萃取方法，其特征在于，包括如下步骤：A collaborative extraction method for selectively separating lithium and transition metals from waste batteries using a hydrophobic deep eutectic solvent, which is characterized by including the following steps:
    (1)配制水相：模拟废锂电池浸出液成分，配置得到含锂、镍、钴和锰金属离子的水相；其中水相pH值为2～6，有价金属含量分别为Li＝300～400mg/L，Ni＝1300～1500mg/L，Co＝600～700mg/L，Mn＝800～900mg/L；(1) Prepare the water phase: simulate the components of the waste lithium battery leachate, and prepare a water phase containing lithium, nickel, cobalt and manganese metal ions; the pH value of the water phase is 2 to 6, and the valuable metal content is Li=300~ 400mg/L, Ni=1300~1500mg/L, Co=600~700mg/L, Mn=800~900mg/L;
    (2)配制疏水性低共熔溶剂：利多卡因与正癸酸通过氢键作用结合，物质的量之比为1:1；将正癸酸加热融化后加入到利多卡因中，在50℃水浴加热条件下混合，得到疏水性低共熔溶剂；(2) Prepare a hydrophobic deep eutectic solvent: lidocaine and n-decanoic acid are combined through hydrogen bonding, and the ratio of the amounts of substances is 1:1; heat and melt n-decanoic acid and add it to lidocaine at 50 Mix under heating conditions in a water bath at ℃ to obtain a hydrophobic deep eutectic solvent;
    (3)配制有机相：将步骤(2)中得到的疏水性低共熔溶剂与磷酸三丁酯混合，得到有机相；有机相中磷酸三丁酯与疏水性低共熔体积之比＝6:4～4:6；(3) Prepare the organic phase: Mix the hydrophobic deep eutectic solvent obtained in step (2) and tributyl phosphate to obtain an organic phase; the ratio of the volume of tributyl phosphate to the hydrophobic deep eutectic in the organic phase = 6 :4～4:6;
    (4)将步骤(3)中得到的有机相加入到步骤(1)得到的水相中进行混合萃取，离心分相后得到镍钴锰负载有机相和含锂萃余液；(4) Add the organic phase obtained in step (3) to the aqueous phase obtained in step (1) for mixing and extraction, and centrifuge to separate the phases to obtain a nickel-cobalt-manganese-loaded organic phase and a lithium-containing raffinate;
    (5)将沉淀剂加入到步骤(4)中的含锂萃余液中得到碳酸锂沉淀；(5) Add a precipitating agent to the lithium-containing raffinate in step (4) to obtain lithium carbonate precipitation;
    (6)将反萃剂加入到步骤(4)中的镍钴锰负载有机相中，得到镍钴锰反萃液和再生有机相；(6) Add the stripping agent to the nickel-cobalt-manganese-loaded organic phase in step (4) to obtain a nickel-cobalt-manganese stripping liquid and a regenerated organic phase;
  2. 根据权利要求1所述的萃取方法，其特征在于，步骤(3)配制的有机相中包含如下结构式：
    The extraction method according to claim 1, characterized in that the organic phase prepared in step (3) contains the following structural formula:
  3. 根据权利要求1所述的萃取方法，其特征在于，步骤(4)中萃取工艺参数为加入的水相与有机相的体积之比即A/O＝3:1～1:3，萃取温度为10～30℃，萃取级数为1级，混匀搅拌时间为20～30min，混匀搅拌转速为200～500r/min，将水相与有机相充分混匀后置于离心机中，离心转速为6000～8000r/min，离心时间为10～30min进行分相，得到镍钴锰负载有机相与含锂萃余液。The extraction method according to claim 1, wherein the extraction process parameter in step (4) is the volume ratio of the added aqueous phase and the organic phase, that is, A/O=3:1~1:3, and the extraction temperature is 10~30℃, the extraction level is level 1, the mixing time is 20~30min, the mixing speed is 200~500r/min, the water phase and the organic phase are fully mixed and placed in a centrifuge, the centrifuge speed The centrifugation time is 6000 to 8000 r/min, and the centrifugation time is 10 to 30 minutes for phase separation to obtain a nickel-cobalt-manganese-loaded organic phase and a lithium-containing raffinate.
  4. 根据权利要求1所述的萃取方法，其特征在于，步骤(5)中加入的沉淀剂为1.5mol/的碳酸钠溶液，加入的碳酸钠与含锂萃余液的体积的比值为2。The extraction method according to claim 1, characterized in that the precipitant added in step (5) is 1.5 mol/sodium carbonate solution, and the ratio of the volume of the added sodium carbonate to the lithium-containing raffinate is 2.
  5. 根据权利要求1所述的萃取方法，其特征在于，步骤(6)反萃取工艺使用2mol/L的HCl作为反萃剂，反萃取参数为加入的盐酸与镍钴锰负载有机相的体积比即A/O＝2:1，反萃取温度为24℃，反萃取级数为1级，混匀搅拌时间为30min，混匀搅拌转速为300r/min，充分混匀后置于离心机中，离心转速为8000r/min，离心时间为10min后分相，得到镍钴锰反萃液与再生有机相。 The extraction method according to claim 1, characterized in that the stripping process of step (6) uses 2 mol/L HCl as the stripping agent, and the stripping parameter is the volume ratio of the added hydrochloric acid and the nickel-cobalt-manganese loaded organic phase, that is, A/O=2:1, back-extraction temperature is 24℃, back-extraction level is 1, mixing and stirring time is 30min, mixing and stirring speed is 300r/min, mix thoroughly and place in centrifuge, centrifuge The rotation speed is 8000r/min, the centrifugation time is 10 minutes, and then the phases are separated to obtain the nickel-cobalt-manganese stripping solution and the regenerated organic phase.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115074551B (en) * 2022-06-29 2023-10-17 北京工业大学 Synergistic extraction method for selectively separating lithium and transition metal from waste battery by using hydrophobic eutectic solvent
CN115505757B (en) * 2022-10-21 2023-05-23 中国地质科学院郑州矿产综合利用研究所 Method for recycling lithium and manganese of waste lithium manganate lithium battery positive electrode material by eutectic solvent

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170077564A1 (en) * 2012-04-04 2017-03-16 Worcester Polytechnic Institute Method and apparatus for recycling lithium-ion batteries
CN111187911A (en) * 2020-01-15 2020-05-22 中国科学院过程工程研究所 Method for selectively extracting lithium in waste ternary batteries by using functionalized ionic liquid
CN111270073A (en) * 2020-02-03 2020-06-12 广东省稀有金属研究所 Method for recovering valuable metals from leachate of waste lithium ion battery electrode material
US20200399737A1 (en) * 2019-06-24 2020-12-24 William Marsh Rice University Recycling li-ion batteries using green chemicals and processes
CN112226632A (en) * 2020-09-11 2021-01-15 江苏大学 Method for selectively extracting and precipitating lithium in lithium mother liquor by using hydrophobic eutectic solvent
CN114438343A (en) * 2022-01-24 2022-05-06 中国科学院过程工程研究所 Difunctional hydrophobic eutectic solvent for selectively extracting lithium and preparation method and application method thereof
CN115074551A (en) * 2022-06-29 2022-09-20 北京工业大学 Synergistic extraction method for selectively separating lithium and transition metal from waste battery by using hydrophobic eutectic solvent

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9957459B2 (en) * 2014-11-03 2018-05-01 Exxonmobil Research And Engineering Company Low transition temperature mixtures or deep eutectic solvents and processes for preparation thereof
CN106319228B (en) * 2016-08-26 2018-06-19 荆门市格林美新材料有限公司 A kind of method of synchronous recycling nickel cobalt manganese in manganese waste slag from nickel and cobalt containing
US11932557B2 (en) * 2020-06-30 2024-03-19 University Of Kentucky Research Foundation Detection and extraction of plastic contaminants within water using hydrophobic deep eutectic solvents
CN111850302B (en) * 2020-07-16 2021-11-09 中国科学院青海盐湖研究所 Method for extracting metal ions from lithium battery
CN112522517A (en) * 2020-11-30 2021-03-19 北京博萃循环科技有限公司 Method for recycling nickel, cobalt, manganese and lithium
CN112662877B (en) * 2020-12-02 2023-12-12 广西科技师范学院 Method for preparing high-purity nickel sulfate from electrolytic manganese sulfide slag

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170077564A1 (en) * 2012-04-04 2017-03-16 Worcester Polytechnic Institute Method and apparatus for recycling lithium-ion batteries
US20200399737A1 (en) * 2019-06-24 2020-12-24 William Marsh Rice University Recycling li-ion batteries using green chemicals and processes
CN111187911A (en) * 2020-01-15 2020-05-22 中国科学院过程工程研究所 Method for selectively extracting lithium in waste ternary batteries by using functionalized ionic liquid
CN111270073A (en) * 2020-02-03 2020-06-12 广东省稀有金属研究所 Method for recovering valuable metals from leachate of waste lithium ion battery electrode material
CN112226632A (en) * 2020-09-11 2021-01-15 江苏大学 Method for selectively extracting and precipitating lithium in lithium mother liquor by using hydrophobic eutectic solvent
CN114438343A (en) * 2022-01-24 2022-05-06 中国科学院过程工程研究所 Difunctional hydrophobic eutectic solvent for selectively extracting lithium and preparation method and application method thereof
CN115074551A (en) * 2022-06-29 2022-09-20 北京工业大学 Synergistic extraction method for selectively separating lithium and transition metal from waste battery by using hydrophobic eutectic solvent

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHANG HEPENG; CHEN JINQING: "Research Progress of Hydrophobic Eutectic Solvent Extraction of Metal Ions", YOUSE JINSHU KEXUE YU GONGCHENG - NONFERROUS METALS SCIENCE AND ENGINEERING, YOUSE JINSHU KEXUE YU GONGCHENG BIANJIBU, vol. 12, no. 4, 31 August 2021 (2021-08-31), pages 9 - 18, XP009551937, ISSN: 1674-9669, DOI: 10.13264/j.cnki.ysjskx.2021.04.002 *

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