CN115074551A - Synergistic extraction method for selectively separating lithium and transition metal from waste battery by using hydrophobic eutectic solvent - Google Patents
Synergistic extraction method for selectively separating lithium and transition metal from waste battery by using hydrophobic eutectic solvent Download PDFInfo
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- 238000000605 extraction Methods 0.000 title claims abstract description 106
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 86
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 230000005496 eutectics Effects 0.000 title claims abstract description 44
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 43
- 239000002904 solvent Substances 0.000 title claims abstract description 42
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 23
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 22
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 12
- 239000010926 waste battery Substances 0.000 title claims abstract description 5
- 239000012074 organic phase Substances 0.000 claims abstract description 57
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002699 waste material Substances 0.000 claims abstract description 39
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011572 manganese Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 16
- 239000010941 cobalt Substances 0.000 claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000012071 phase Substances 0.000 claims abstract description 9
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 29
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- 238000005119 centrifugation Methods 0.000 claims description 28
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000008346 aqueous phase Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000005191 phase separation Methods 0.000 claims description 16
- NNJVILVZKWQKPM-UHFFFAOYSA-N Lidocaine Chemical compound CCN(CC)CC(=O)NC1=C(C)C=CC=C1C NNJVILVZKWQKPM-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229960004194 lidocaine Drugs 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 38
- 238000000034 method Methods 0.000 abstract description 28
- 229910052748 manganese Inorganic materials 0.000 abstract description 12
- 238000002386 leaching Methods 0.000 abstract description 9
- 238000009854 hydrometallurgy Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- -1 nickel-cobalt-manganese transition metal Chemical class 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910017709 Ni Co Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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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
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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
- 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
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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
- C22B47/00—Obtaining manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- 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
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
A synergistic extraction method for selectively separating lithium and transition metal from waste batteries by using a hydrophobic eutectic solvent belongs to the technical field of hydrometallurgy, provides a synergistic extraction method with good separation and extraction effects, and particularly discloses a hydrophobic eutectic and tributyl phosphate (TBP) synergistic extraction agent and a method for separating lithium and transition metal from leachate of waste lithium batteries. The method comprises the following steps: (1) preparing a hydrophobic eutectic solvent; (2) preparing an extraction organic phase; (3) co-extracting nickel, cobalt and manganese; (4) back extraction of nickel, cobalt and manganese; (5) and (4) lithium precipitation. The method has good extraction effect on the nickel-cobalt-manganese transition metal, high purity of lithium in the residual water phase, realizes high-efficiency recovery of valuable metal in the leaching solution of the anode material of the waste lithium battery, and is a novel green solvent with small pollution, simple and convenient synthesis and low price of the used eutectic solvent.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy, and particularly relates to a hydrophobic eutectic solvent and tributyl phosphate synergistic extraction agent and a method for extracting and separating lithium and transition metal from a waste lithium battery leaching solution.
Background
In an era when decarburization of energy and a traffic system becomes one of the most important international challenges, a Lithium Ion Battery (LIB) is widely applied to electronic devices, electric automobiles, renewable energy storage and the like with excellent energy storage capacity, and dependence of the transportation industry on fossil fuels can be reduced. Lithium is a key metal element in lithium ion batteries and is receiving wide attention due to its light weight, and it is expected that the demand for lithium carbonate will exceed 500 million tons by 2025. According to the global average Recoverable Content (RC) data, transition metals are the first of all recovered elements (especially nickel and cobalt), which leads to natural resource depletion. By 2024, the total market for automotive lithium ion batteries alone is expected to reach $ 2210 billion. However, the increase of the output of the lithium ion battery not only causes serious shortage of lithium, nickel and cobalt, but also causes serious environmental pollution of the waste lithium ion battery, and the content and purity of valuable metals in the waste lithium ion battery are higher than those in the nature, and if the waste lithium ion battery is not recycled, huge resource waste is caused, and the concept of clean energy and resource utilization is not met.
At present, the common recovery method of the waste lithium battery mainly comprises pyrometallurgical and hydrometallurgical processes. The hydrometallurgical process has the characteristics of high selectivity, low energy consumption, no harmful gas and the like, and is more in line with the green environmental protection concept than the pyrometallurgical process. In the hydrometallurgical process, the battery is pretreated by various physical methods, various metals are dissolved in acid, and 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 in hydrometallurgical processes. Among various metal recovery methods, solvent extraction is widely used for metal separation because of its simple operation, high recovery rate, and good adjustability.
CN112442596A discloses a method for separating nickel, cobalt and manganese from a battery containing nickel, cobalt and manganese, wherein nickel, cobalt and manganese are separated step by multistage countercurrent extraction using carboxylic acid extractant. CN111850302B discloses a method for separating metals from waste lithium batteries by using a diketone compound as an extracting agent and an organic phosphine compound as a co-extracting agent, wherein the extraction rates of nickel, cobalt and manganese after multi-stage countercurrent extraction are all more than 99%. However, most of these extraction processes require multi-stage extraction, which increases the loss of the extractant to a certain extent, not only increases the cost, but also causes waste of resources. Meanwhile, the traditional extracting agents are limited in extracting effect, and have the characteristics of volatility, environmental pollution, toxicity and the like, so that the development of a green solvent which is high in extracting efficiency, simple and convenient in extracting method and environment-friendly is very important.
Disclosure of Invention
Aiming at the problems, the method adopts the hydrophobic eutectic and tributyl phosphate to cooperatively extract nickel, cobalt and manganese in the waste lithium battery, leaves lithium in the raffinate, can achieve higher extraction and separation effects through single-stage extraction, and has the characteristics of environmental friendliness, low operation cost and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
(1) preparing a water phase: simulating the components of the leachate of the waste lithium battery, and preparing a water phase containing lithium, nickel, cobalt and manganese metal ions;
(2) preparing a hydrophobic eutectic solvent: heating and mixing lidocaine and n-decanoic acid to obtain a hydrophobic eutectic solvent;
(3) preparing an organic phase: mixing the hydrophobic eutectic solvent obtained in the step (2) with tributyl phosphate to obtain an organic phase;
(4) adding the organic phase obtained in the step (3) into the aqueous phase obtained in the step (1) for mixed extraction, and performing centrifugal phase separation to obtain a nickel-cobalt-manganese loaded organic phase and a lithium-containing raffinate;
(5) adding a precipitator into the lithium-containing raffinate obtained in the step (4) to obtain lithium carbonate precipitate;
(6) adding a stripping agent into the nickel-cobalt-manganese loaded organic phase in the step (4) to obtain a nickel-cobalt-manganese stripping solution and a regenerated organic phase;
furthermore, the pH value of the water phase of the leachate of the waste battery simulated in the step (1) is 2-6, the content of valuable metals is 300-400 mg/L, 1300-1500 mg/L, 600-700 mg/L and 800-900 mg/L respectively.
Further, the lidocaine and the n-decanoic acid in the hydrophobic eutectic solvent prepared in the step (2) are combined through hydrogen bonding, and the ratio of the amount of the substances is 1: 1. Heating and melting n-capric acid, adding into lidocaine, and mixing under heating in water bath at 50 deg.C to obtain hydrophobic eutectic solvent.
Further, the organic phase prepared in the step (3) comprises the following structural formula:
further, the ratio of tributyl phosphate to the hydrophobic eutectic volume in the organic phase prepared in the step (3) is 6:4 to 4: 6;
further, the extraction process parameters in the step (4) are that the volume ratio (A/O) of the added water phase to the organic phase is 3: 1-1: 3, the extraction temperature is 10-30 ℃, the extraction stage number is 1, the mixing and stirring time is 20-30 min, the mixing and stirring speed is 200-500 r/min, the water phase and the organic phase are fully mixed and then placed in a centrifuge, the centrifugation speed is 6000-8000 r/min, and the centrifugation time is 10-30 min for phase separation, so that the nickel-cobalt-manganese loaded organic phase and the lithium-containing raffinate are obtained.
Further, the precipitant added in step (5) is a 1.5 mol/volume sodium carbonate solution, and the ratio of the added sodium carbonate to the volume of the lithium-containing raffinate is 2.
Further, in the step (6), 2mol/L HCl is used as a stripping agent in the stripping process, the stripping parameters are that the volume ratio (A/O) of the added hydrochloric acid to the nickel-cobalt-manganese loaded organic phase is 2:1, the stripping temperature is 24 ℃, the stripping stage number is 1, the mixing and stirring time is 30min, the mixing and stirring speed is 300r/min, the nickel-cobalt-manganese stripping solution and the regenerated organic phase are obtained by phase separation after fully mixing and placing in a centrifuge, the centrifugation speed is 8000r/min and the centrifugation time is 10 min.
Drawings
Fig. 1 is a process flow chart of the method for extracting and separating valuable metals from the leachate of the waste lithium battery provided by the invention.
The present invention is further described in detail with reference to the following examples, which are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
Detailed Description
In order to better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The flow of the method for extracting and separating lithium and transition metal from leachate of waste lithium batteries by using the synergistic extraction agent of the hydrophobic eutectic solvent and tributyl phosphate and the method for extracting and separating lithium and transition metal from leachate of waste lithium batteries provided in this embodiment are shown in fig. 1.
The components in the acid leaching solution for simulating the waste lithium battery in the embodiment are as follows:
| element(s) | Li | Ni | Co | Mn |
| Content (mg/L) | 377.9 | 1502 | 601.9 | 885.3 |
In the extraction separation method described in this example, the pH of the aqueous phase of the prepared simulated waste lithium battery is 2;
in the extraction separation method described in this example, lidocaine and n-decanoic acid in the prepared hydrophobic eutectic solvent are bonded by hydrogen bonding, and the ratio of the amounts of the substances is 1: 1. Heating and melting n-capric acid, adding into lidocaine, and mixing under heating in water bath at 50 deg.C to obtain hydrophobic eutectic solvent;
in the extraction separation method described in this embodiment, a prepared hydrophobic eutectic solvent is added to tributyl phosphate, wherein the volume ratio of the added tributyl phosphate to the hydrophobic eutectic solvent is 6:4, and an organic phase is obtained;
in the extraction separation method described in this embodiment, a prepared organic phase is added into an aqueous phase, and the extraction process parameters are that the volume ratio (a/O) of the aqueous phase to the organic phase is 2:1, the extraction temperature is 10 ℃, the number of extraction stages is 1 stage, the mixing and stirring time is 20min, the rotation speed is 200r/min, the mixture is placed in a centrifuge after being fully mixed, the centrifugation rotation speed is 6000r/min, and after 10min of centrifugation, phase separation is performed to obtain a nickel-cobalt-manganese loaded organic phase and a lithium-containing raffinate.
In the extraction separation method described in this example, a sodium carbonate solution with a concentration of 1.5mol/L is added to a lithium-containing raffinate, and the volume ratio of the added sodium carbonate solution to the lithium-containing raffinate is 2: and 1, fully precipitating and washing to obtain a lithium carbonate solution.
In the extraction separation method described in this embodiment, 2mol/L HCl is used as a stripping agent in the stripping process, the stripping parameters are that the volume ratio (a/O) of the added HCl to the nickel-cobalt-manganese loaded organic phase is 2:1, the stripping temperature is 24 ℃, the number of stripping stages is 1, the mixing and stirring time is 30min, the rotation speed is 300r/min, the mixture is placed in a centrifuge after being fully mixed, the centrifugation rotation speed is 8000r/min, and the phase separation is performed after the centrifugation time is 10min, so as to obtain the nickel-cobalt-manganese stripping solution and the regenerated organic phase.
The results of the extraction experiment of example 1 are as follows:
| element(s) | Initial solution concentration (mg/L) | Concentration of raffinate (mg/L) | Extraction rate |
| Li | 377.9 | 348.8 | 7.70％ |
| Ni | 1502 | 12.8 | 99.15％ |
| Co | 601.9 | 13 | 97.84％ |
| Mn | 885.3 | 67.8 | 92.34％ |
In this embodiment, after single-stage extraction, the extraction rates of nickel, cobalt and manganese all reach more than 92%, and meanwhile, a high-purity lithium salt solution is obtained from the raffinate, so that effective separation of lithium and transition metal in the waste lithium battery is realized.
Example 2
The flow of the method for extracting and separating lithium and transition metal from leachate of waste lithium batteries by using the synergistic extraction agent of the hydrophobic eutectic solvent and tributyl phosphate and the method for extracting and separating lithium and transition metal from leachate of waste lithium batteries provided in this embodiment are shown in fig. 1.
The components in the acid leaching solution for simulating the waste lithium battery in the embodiment are as follows:
| element(s) | Li | Ni | Co | Mn |
| Content (mg/L) | 377.9 | 1502 | 601.9 | 885.3 |
In the extraction separation method described in this example, the pH of the aqueous phase of the prepared simulated waste lithium battery is 6;
in the extraction separation method described in this example, lidocaine and n-decanoic acid in the prepared hydrophobic eutectic solvent are bonded by hydrogen bonding, and the ratio of the amounts of the substances is 1: 1. Heating and melting n-decanoic acid, adding the melted n-decanoic acid into lidocaine, and mixing under the water bath heating condition of 50 ℃ to obtain a hydrophobic eutectic solvent;
in the extraction separation method described in this embodiment, a prepared hydrophobic eutectic solvent is added to tributyl phosphate, wherein the volume ratio of the added tributyl phosphate to the hydrophobic eutectic solvent is 4:6, and an organic phase is obtained;
in the extraction separation method described in this embodiment, a prepared organic phase is added into an aqueous phase, and the extraction process parameters are that the volume ratio (a/O) of the aqueous phase to the organic phase is 2:1, the extraction temperature is 30 ℃, the number of extraction stages is 1 stage, the mixing and stirring time is 30min, the rotation speed is 500r/min, the mixture is placed in a centrifuge after being fully mixed, the centrifugation rotation speed is 8000r/min, and the phase separation is performed after the centrifugation is 30min, so that a nickel-cobalt-manganese loaded organic phase and a lithium-containing raffinate are obtained.
In the extraction separation method described in this example, a sodium carbonate solution with a concentration of 1.5mol/L is added to a lithium-containing raffinate, and the volume ratio of the added sodium carbonate solution to the lithium-containing raffinate is 2: and 1, fully precipitating and washing to obtain a lithium carbonate solution.
In the extraction separation method described in this embodiment, 2mol/L HCl is used as a stripping agent in the stripping process, the stripping parameters are that the volume ratio (a/O) of the added HCl to the nickel-cobalt-manganese loaded organic phase is 2:1, the stripping temperature is 24 ℃, the number of stripping stages is 1, the mixing and stirring time is 30min, the rotation speed is 300r/min, the mixture is placed in a centrifuge after being fully mixed, the centrifugation rotation speed is 8000r/min, and the phase separation is performed after the centrifugation time is 15min, so as to obtain the nickel-cobalt-manganese stripping solution and the regenerated organic phase.
The results of the extraction experiment of example 2 are as follows:
| element(s) | Initial solution concentration (mg/L) | Concentration of raffinate (mg/L) | Extraction rate |
| Li | 377.9 | 323.7 | 14.34％ |
| Ni | 1502 | 2.2 | 99.85％ |
| Co | 601.9 | 1.9 | 99.68％ |
| Mn | 885.3 | 16.6 | 98.12％ |
In this embodiment, after single-stage extraction, the extraction rates of nickel, cobalt and manganese all reach 98%, and meanwhile, a high-purity lithium salt solution is obtained from the raffinate, so that effective separation of lithium and transition metal in the waste lithium battery is realized.
Example 3
The flow of the method for extracting and separating lithium and transition metal from leachate of waste lithium batteries by using the synergistic extraction agent of the hydrophobic eutectic solvent and tributyl phosphate and the method for extracting and separating lithium and transition metal from leachate of waste lithium batteries provided in this embodiment are shown in fig. 1.
The components in the acid leaching solution for simulating the waste lithium battery in the embodiment are as follows:
| element(s) | Li | Ni | Co | Mn |
| Content (mg/L) | 360.9 | 1453 | 587.1 | 862.8 |
In the extraction separation method described in this example, the pH of the aqueous phase of the prepared simulated waste lithium battery is 3;
in the extraction separation method described in this example, lidocaine and n-decanoic acid in the prepared hydrophobic eutectic solvent are bonded by hydrogen bonding, and the ratio of the amounts of the substances is 1: 1. Heating and melting n-capric acid, adding into lidocaine, and mixing under heating in water bath at 50 deg.C to obtain hydrophobic eutectic solvent;
in the extraction separation method described in this embodiment, a prepared hydrophobic eutectic solvent is added to tributyl phosphate, wherein the volume ratio of the added tributyl phosphate to the hydrophobic eutectic solvent is 4:6, and an organic phase is obtained;
in the extraction separation method described in this embodiment, a prepared organic phase is added into an aqueous phase, and the extraction process parameters are that the volume ratio (a/O) of the aqueous phase to the organic phase is 3:1, the extraction temperature is 24 ℃, the number of extraction stages is 1 stage, the mixing and stirring time is 30min, the rotation speed is 300r/min, the mixture is placed in a centrifuge after being fully mixed, the centrifugation rotation speed is 8000r/min, and the phase separation is performed after centrifugation for 10 min. Obtaining a nickel-cobalt-manganese loaded organic phase and lithium-containing raffinate.
In the extraction separation method described in this example, a sodium carbonate solution with a concentration of 1.5mol/L is added to a lithium-containing raffinate, and the volume ratio of the added sodium carbonate solution to the lithium-containing raffinate is 2: and 1, fully precipitating and washing to obtain a lithium carbonate solution.
In the extraction separation method described in this embodiment, 2mol/L HCl is used as a stripping agent in the stripping process, the stripping parameters are that the volume ratio (a/O) of the added HCl to the nickel-cobalt-manganese loaded organic phase is 2:1, the stripping temperature is 24 ℃, the number of stripping stages is 1, the mixing and stirring time is 30min, the rotation speed is 300r/min, the mixture is placed in a centrifuge after being fully mixed, the centrifugation rotation speed is 8000r/min, and the phase separation is performed after the centrifugation time is 10min, so as to obtain the nickel-cobalt-manganese stripping solution and the regenerated organic phase.
The results of the extraction experiment of example 3 are as follows:
| element(s) | Initial solution concentration (mg/L) | Concentration of raffinate (mg/L) | Extraction rate |
| Li | 360.1 | 306.9 | 14.96％ |
| Ni | 1453 | 18.7 | 98.71％ |
| Co | 587.1 | 13.9 | 97.63％ |
| Mn | 862.8 | 51.9 | 93.98％ |
In this embodiment, after single-stage extraction, the extraction rates of nickel, cobalt and manganese all reach 93%, and meanwhile, a high-purity lithium salt solution is obtained from the raffinate, so that effective separation of lithium and transition metal in the waste lithium battery is realized.
Example 4
The flow of the method for extracting and separating lithium and transition metal from leachate of waste lithium batteries by using the synergistic extraction agent of the hydrophobic eutectic solvent and tributyl phosphate and the method for extracting and separating lithium and transition metal from leachate of waste lithium batteries provided in this embodiment are shown in fig. 1.
The components in the acid leaching solution for simulating the waste lithium battery in the embodiment are as follows:
| element(s) | Li | Ni | Co | Mn |
| Content (mg/L) | 360.9 | 1453 | 587.1 | 862.8 |
In the extraction separation method described in this example, the pH of the aqueous phase of the prepared simulated waste lithium battery is 3;
in the extraction separation method described in this example, lidocaine and n-decanoic acid in the prepared hydrophobic eutectic solvent are bonded by hydrogen bonding, and the ratio of the amounts of the substances is 1: 1. Heating and melting n-capric acid, adding into lidocaine, and mixing under heating in water bath at 50 deg.C to obtain hydrophobic eutectic solvent;
in the extraction separation method described in this embodiment, a prepared hydrophobic eutectic solvent is added to tributyl phosphate, wherein the volume ratio of the added tributyl phosphate to the hydrophobic eutectic solvent is 4:6, and an organic phase is obtained;
in the extraction separation method described in this embodiment, a prepared organic phase is added into an aqueous phase, and the extraction process parameters are that the volume ratio (a/O) of the aqueous phase to the organic phase is 1:3, the extraction temperature is 24 ℃, the number of extraction stages is 1 stage, the mixing and stirring time is 30min, the rotation speed is 300r/min, the mixture is placed in a centrifuge after being fully mixed, the centrifugation rotation speed is 8000r/min, and the phase separation is performed after the centrifugation is 10min, so that a nickel-cobalt-manganese loaded organic phase and a lithium-containing raffinate are obtained.
In the extraction separation method described in this example, a sodium carbonate solution with a concentration of 1.5mol/L is added to a lithium-containing raffinate, and the volume ratio of the added sodium carbonate solution to the lithium-containing raffinate is 2: and 1, fully precipitating and washing to obtain a lithium carbonate solution.
In the extraction separation method described in this embodiment, 2mol/L HCl is used as a stripping agent in the stripping process, the stripping parameters are that the volume ratio (a/O) of the added HCl to the nickel-cobalt-manganese loaded organic phase is 2:1, the stripping temperature is 24 ℃, the number of stripping stages is 1, the mixing and stirring time is 30min, the rotation speed is 300r/min, the mixture is placed in a centrifuge after being fully mixed, the centrifugation rotation speed is 8000r/min, and the phase separation is performed after the centrifugation time is 10min, so as to obtain the nickel-cobalt-manganese stripping solution and the regenerated organic phase.
The results of the extraction experiment of example 4 are as follows:
| element(s) | Initial solution concentration (mg/L) | Concentration of raffinate (mg/L) | Extraction rate |
| Li | 360.1 | 299.9 | 16.90％ |
| Ni | 1453 | 0.8 | 99.94％ |
| Co | 587.1 | 1.2 | 99.80％ |
| Mn | 862.8 | 6.5 | 99.25％ |
In this embodiment, after single-stage extraction, the extraction rates of nickel, cobalt and manganese all reach 99%, and meanwhile, a high-purity lithium salt solution is obtained from the raffinate, so that effective separation of lithium and transition metal in the waste lithium battery is realized.
Example 5
The flow of the method for extracting and separating lithium and transition metal from leachate of waste lithium batteries by using the synergistic extraction agent of the hydrophobic eutectic solvent and tributyl phosphate and the method for extracting and separating lithium and transition metal from leachate of waste lithium batteries provided in this embodiment are shown in fig. 1.
The components in the acid leaching solution for simulating the waste lithium battery in the embodiment are as follows:
in the extraction separation method described in this example, the pH of the aqueous phase of the prepared simulated waste lithium battery is 3;
in the extraction separation method described in this embodiment, lidocaine and n-decanoic acid in the prepared hydrophobic eutectic solvent are combined through hydrogen bonding, and the ratio of the amounts of the substances is 1: 1. Heating and melting n-capric acid, adding into lidocaine, and mixing under heating in water bath at 50 deg.C to obtain hydrophobic eutectic solvent;
in the extraction separation method described in this embodiment, a prepared hydrophobic eutectic solvent is added to tributyl phosphate, wherein the volume ratio of the added tributyl phosphate to the hydrophobic eutectic solvent is 4:6, and an organic phase is obtained;
in the extraction separation method described in this embodiment, a prepared organic phase is added into an aqueous phase, and the extraction process parameters are that the volume ratio (a/O) of the aqueous phase to the organic phase is 1:2, the extraction temperature is 24 ℃, the number of extraction stages is 1 stage, the mixing and stirring time is 30min, the rotation speed is 300r/min, the mixture is placed in a centrifuge after being fully mixed, the centrifugation rotation speed is 8000r/min, and the phase separation is performed after the centrifugation is 10min, so that a nickel-cobalt-manganese loaded organic phase and a lithium-containing raffinate are obtained.
In the extraction separation method described in this example, a sodium carbonate solution with a concentration of 1.5mol/L is added to a lithium-containing raffinate, and the volume ratio of the added sodium carbonate solution to the lithium-containing raffinate is 2: and 1, fully precipitating and washing to obtain a lithium carbonate solution.
In the extraction separation method described in this embodiment, 2mol/L HCl is used as a stripping agent in the stripping process, the stripping parameters are that the volume ratio (a/O) of the added HCl to the nickel-cobalt-manganese loaded organic phase is 2:1, the stripping temperature is 24 ℃, the number of stripping stages is 1, the mixing and stirring time is 30min, the rotation speed is 300r/min, the mixture is placed in a centrifuge after being fully mixed, the centrifugation rotation speed is 8000r/min, and the phase separation is performed after the centrifugation time is 10min, so as to obtain the nickel-cobalt-manganese stripping solution and the regenerated organic phase.
The results of the extraction experiment of example 5 are as follows:
| element(s) | Initial solution concentration (mg/L) | Concentration of raffinate (mg/L) | Extraction rate |
| Li | 377.9 | 307.3 | 18.68％ |
| Ni | 1502 | 0.6 | 99.96％ |
| Co | 601.9 | 1.3 | 99.78％ |
| Mn | 885.3 | 9.2 | 98.96％ |
In this embodiment, after single-stage extraction, the extraction rates of nickel, cobalt and manganese all reach 98%, and meanwhile, a high-purity lithium salt solution is obtained from the raffinate, so that effective separation of lithium and transition metal in the waste lithium battery is realized.
Claims (5)
1. A synergic extraction method for selectively separating lithium and transition metals from waste batteries using a hydrophobic eutectic solvent, characterized by comprising the steps of:
(1) preparing a water phase: simulating the components of the leachate of the waste lithium battery, and preparing a water phase containing lithium, nickel, cobalt and manganese metal ions; wherein the pH value of the water phase is 2-6, the content of valuable metals is respectively 300-400 mg/L of Li, 1300-1500 mg/L of Ni, 600-700 mg/L of Co and 800-900 mg/L of Mn;
(2) preparing a hydrophobic eutectic solvent: the lidocaine and the n-decanoic acid are combined through hydrogen bond action, and the ratio of the amount of the substances is 1: 1; heating and melting n-capric acid, adding into lidocaine, and mixing under heating in water bath at 50 deg.C to obtain hydrophobic eutectic solvent;
(3) preparing an organic phase: mixing the hydrophobic eutectic solvent obtained in the step (2) with tributyl phosphate to obtain an organic phase; the volume ratio of tributyl phosphate to the hydrophobic eutectic in the organic phase is 6: 4-4: 6;
(4) adding the organic phase obtained in the step (3) into the aqueous phase obtained in the step (1) for mixed extraction, and performing centrifugal phase separation to obtain a nickel-cobalt-manganese loaded organic phase and a lithium-containing raffinate;
(5) adding a precipitator into the lithium-containing raffinate obtained in the step (4) to obtain lithium carbonate precipitate;
(6) and (5) adding a stripping agent into the nickel-cobalt-manganese loaded organic phase obtained in the step (4) to obtain a nickel-cobalt-manganese stripping solution and a regenerated organic phase.
2. The extraction process of claim 1, wherein the organic phase formulated in step (3) comprises the formula:
3. the extraction method of claim 1, wherein the extraction process parameters in the step (4) are that the volume ratio of the added aqueous phase to the organic phase, i.e. A/O, is 3:1 to 1:3, the extraction temperature is 10 to 30 ℃, the number of extraction stages is 1, the mixing and stirring time is 20 to 30min, the mixing and stirring speed is 200 to 500r/min, the aqueous phase and the organic phase are fully mixed and then placed in a centrifuge, the centrifugation speed is 6000 to 8000r/min, and the centrifugation time is 10 to 30min for phase separation, so as to obtain the nickel-cobalt-manganese loaded organic phase and the lithium-containing raffinate.
4. The extraction process according to claim 1, wherein the precipitant added in step (5) is 1.5mol/l sodium carbonate solution, and the ratio of the volume of the added sodium carbonate to the volume of the lithium-containing raffinate is 2.
5. The extraction method according to claim 1, wherein the back-extraction process in the step (6) uses 2mol/L HCl as a back-extraction agent, the back-extraction parameters are that the volume ratio of the added hydrochloric acid to the nickel-cobalt-manganese loaded organic phase is A/O2: 1, the back-extraction temperature is 24 ℃, the number of back-extraction stages is 1, the mixing and stirring time is 30min, the mixing and stirring speed is 300r/min, the mixture is placed in a centrifuge after being fully mixed, the centrifugation speed is 8000r/min, and the phase separation is performed after the centrifugation time is 10min, so that the nickel-cobalt-manganese back-extraction solution and the regenerated organic phase are obtained.
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| JP2023573586A JP7548642B2 (en) | 2022-06-29 | 2023-06-09 | Synergistic extraction method for selective separation of lithium and transition metals from waste batteries using hydrophobic deep eutectic solvents |
| PCT/CN2023/099256 WO2024001716A1 (en) | 2022-06-29 | 2023-06-09 | Synergistic extraction method for selectively separating lithium and transition metals from waste batteries by using hydrophobic deep eutectic solvent |
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|---|---|---|---|---|
| CN115505757A (en) * | 2022-10-21 | 2022-12-23 | 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 anode materials of waste lithium manganate lithium batteries through eutectic solvent |
| WO2024001716A1 (en) * | 2022-06-29 | 2024-01-04 | 北京工业大学 | Synergistic extraction method for selectively separating lithium and transition metals from waste batteries by using hydrophobic deep eutectic solvent |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319228A (en) * | 2016-08-26 | 2017-01-11 | 荆门市格林美新材料有限公司 | Method for recycling nickel, cobalt and manganese synchronously from waste residues containing nickel, cobalt and manganese |
| US20180223211A1 (en) * | 2014-11-03 | 2018-08-09 | Exxonmobil Research And Engineering Company | Low transition temperature mixtures or deep eutectic solvents and processes for preparation thereof |
| CN111850302A (en) * | 2020-07-16 | 2020-10-30 | 中国科学院青海盐湖研究所 | Method for extracting metal ions from lithium battery |
| 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 |
| 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 |
| CN112662877A (en) * | 2020-12-02 | 2021-04-16 | 广西科技师范学院 | Method for preparing high-purity nickel sulfate from electrolytic manganese sulfide slag |
| US20210403346A1 (en) * | 2020-06-30 | 2021-12-30 | University Of Kentucky Research Foundation | Detection and extraction of plastic contaminants within water using hydrophobic deep eutectic solvents |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10522884B2 (en) * | 2012-04-04 | 2019-12-31 | Worcester Polytechnic Institute | Method and apparatus for recycling lithium-ion batteries |
| CN108179286A (en) | 2018-01-10 | 2018-06-19 | 北京工业大学 | A kind of method that nickel cobalt is detached from solution |
| US11591670B2 (en) * | 2019-06-24 | 2023-02-28 | William Marsh Rice University | Recycling Li-ion batteries using green chemicals and processes |
| CN111180819B (en) | 2019-12-30 | 2021-07-27 | 荆门市格林美新材料有限公司 | Preparation method of battery-grade Ni-Co-Mn mixed solution and battery-grade Mn solution |
| 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 |
| CN112553481A (en) | 2020-12-11 | 2021-03-26 | 中南大学 | Production method of electrolytic manganese |
| JP2023022934A (en) | 2021-08-04 | 2023-02-16 | 国立大学法人九州大学 | Recovery apparatus of metal, and recovery method of metal |
| CN114438343B (en) * | 2022-01-24 | 2023-03-17 | 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 |
| CN115029556A (en) | 2022-06-14 | 2022-09-09 | 桐乡市思远环保科技有限公司 | Method for recycling waste lithium ion battery cathode material |
| 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 |
-
2022
- 2022-06-29 CN CN202210750305.9A patent/CN115074551B/en active Active
-
2023
- 2023-06-09 JP JP2023573586A patent/JP7548642B2/en active Active
- 2023-06-09 WO PCT/CN2023/099256 patent/WO2024001716A1/en unknown
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180223211A1 (en) * | 2014-11-03 | 2018-08-09 | Exxonmobil Research And Engineering Company | Low transition temperature mixtures or deep eutectic solvents and processes for preparation thereof |
| CN106319228A (en) * | 2016-08-26 | 2017-01-11 | 荆门市格林美新材料有限公司 | Method for recycling nickel, cobalt and manganese synchronously from waste residues containing nickel, cobalt and manganese |
| US20210403346A1 (en) * | 2020-06-30 | 2021-12-30 | University Of Kentucky Research Foundation | Detection and extraction of plastic contaminants within water using hydrophobic deep eutectic solvents |
| CN111850302A (en) * | 2020-07-16 | 2020-10-30 | 中国科学院青海盐湖研究所 | Method for extracting metal ions from lithium battery |
| 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 |
| 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 |
| CN112662877A (en) * | 2020-12-02 | 2021-04-16 | 广西科技师范学院 | Method for preparing high-purity nickel sulfate from electrolytic manganese sulfide slag |
Non-Patent Citations (1)
| Title |
|---|
| GUILLAUME ZANTE: "Solvent extraction fractionation of manganese, cobalt, nickel and lithium using ionic liquids and deep eutectic solvents", 《MINERALS ENGINEERING》, pages 1 - 10 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024001716A1 (en) * | 2022-06-29 | 2024-01-04 | 北京工业大学 | Synergistic extraction method for selectively separating lithium and transition metals from waste batteries by using hydrophobic deep eutectic solvent |
| CN115505757A (en) * | 2022-10-21 | 2022-12-23 | 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 anode materials of waste lithium manganate lithium batteries through eutectic solvent |
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