WO2020220559A1 - Procédé de récupération de métaux de valeur présents dans des batteries usagées au lithium ternaire de nickel-cobalt-manganèse - Google Patents

Procédé de récupération de métaux de valeur présents dans des batteries usagées au lithium ternaire de nickel-cobalt-manganèse Download PDF

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WO2020220559A1
WO2020220559A1 PCT/CN2019/105497 CN2019105497W WO2020220559A1 WO 2020220559 A1 WO2020220559 A1 WO 2020220559A1 CN 2019105497 W CN2019105497 W CN 2019105497W WO 2020220559 A1 WO2020220559 A1 WO 2020220559A1
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Prior art keywords
cobalt
extraction
nickel
raffinate
sulfuric acid
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PCT/CN2019/105497
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English (en)
Chinese (zh)
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詹稳
甄爱钢
余心亮
张景伟
李斌
陈健
赵海敏
陈红娟
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浙江天能新材料有限公司
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Publication of WO2020220559A1 publication Critical patent/WO2020220559A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/10—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/10—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/10—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/005—Preliminary treatment of scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • 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
    • 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
    • C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
    • 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
    • C22B7/007—Wet processes by acid leaching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the invention relates to the technical field of waste lithium ion battery recovery, in particular to a method for recovering valuable metals in waste nickel cobalt manganese ternary lithium batteries.
  • the Chinese invention patent with publication number CN105591171A discloses a method for recovering the cathode material of a waste nickel-cobalt-manganese ternary lithium-ion battery.
  • the method dissolves the cathode material with an alkali, and separates the dissolved solution I and the insoluble matter; Acid hydrolyze the substance to obtain dissolving liquid II, adjust the pH value to alkaline to form a precipitate, obtain filtrate I and precipitate I; acid hydrolyze the precipitate I to obtain dissolving liquid III, add ammonia water to it for complexation, adjust the pH value After it is alkaline, add soluble carbonate and filter to obtain filtrate II and precipitate II; add soluble carbonate to filtrate II and heat to obtain precipitate III; after acidolysis, adjust the pH to 3.0 ⁇ 3.5, add hypochlorite to adjust the pH to 2.0-3.0, filter to obtain filtrate III and precipitate IV.
  • the Chinese invention patent with publication number CN109449523A discloses a comprehensive recovery method for waste lithium ion batteries, including: first leaching ternary waste lithium battery cell powder with sulfuric acid and potassium permanganate to obtain the first leaching solution and The first leaching residue; the first leaching solution is immersed with sodium carbonate to obtain lithium carbonate; the first leaching residue is selectively reduced and leached with hydrogen peroxide and sulfuric acid to obtain the second leaching solution and the second leaching residue; adjusting the pH of the second leaching solution to 4.2 -4.5, extract the second leachate with P204 to obtain P204 raffinate and P204 loaded organic phase; back-extract P204 loaded organic phase with sulfuric acid, evaporate and crystallize to obtain manganese sulfate; adjust the pH value of P204 raffinate to 4.5- 5.
  • the pH value is 5-5.5.
  • the C272 extract is extracted with P507 to obtain the P507-supported organic phase.
  • the P507-supported organic phase is back-extracted with sulfuric acid to obtain a nickel sulfate solution, which is evaporated and crystallized to obtain nickel sulfate.
  • the present invention provides a method for recovering valuable metals in waste nickel-cobalt-manganese ternary lithium batteries
  • a method for recovering valuable metals in waste nickel-cobalt-manganese ternary lithium batteries including the following steps:
  • step (4) The raffinate obtained in step (4) is used to extract cobalt with P507.
  • the ratio of oil to water is controlled to be 0.8 ⁇ 0.9:1, lye is used for saponification, and the saponification rate is controlled to be 55% ⁇ 60%;
  • step (5) The raffinate obtained in step (5) is extracted by using C272 to remove impurities, to obtain a C272 raffinate after removing Mg 2+ ;
  • step (7) The raffinate obtained in step (7) is reacted with sodium carbonate to collect lithium carbonate.
  • lithium batteries need to be discharged before being broken to discharge the remaining power to avoid explosion or combustion during the broken process.
  • the discharge can be immersed in a salt solution. After crushing, the crushed material is carbonized at a high temperature to consume the organic matter, and the remaining is mainly some metal elements. Carbonization is generally carried out in a carbonization furnace, and natural gas can be used for heating. After carbonization, it can be crushed again if necessary to make the electrode material into a powder form. Of course, it is also possible to crush the remaining larger particles again after air selection.
  • the air-selected powders are mainly electrode materials for the next processing, while the steel shell of the lithium battery becomes granular, which can be directly recycled after being separated from the powders.
  • step (2) when sulfuric acid is used for leaching, concentrated sulfuric acid is generally used, and concentrated sulfuric acid with a concentration of 98% is preferably used.
  • the step (2) is divided into two steps when the powder is leached with sulfuric acid:
  • the leaching solution I and the leaching solution II are mixed to obtain the leaching solution.
  • the mass of the reducing agent is 0.2 to 0.5 times that of the powder; the mass of hydrogen peroxide is 0.1 to 0.4 times that of the filter residue I.
  • the powder or filter residue I Before leaching with sulfuric acid, the powder or filter residue I needs to be slurried with water to facilitate subsequent leaching.
  • the liquid to solid ratio of the powder or filter residue I to water can be 4 to 5:1.
  • the main control parameter of the added sulfuric acid is the pH of the reaction, and there is no special requirement for the concentration of sulfuric acid used.
  • Leaching through a two-step method can ensure the leaching rate.
  • the reaction time of the two-step leaching reaction can be 1 hour. Of course, the longer the reaction time, the higher the leaching rate.
  • the concentration of the corresponding metal elements in the leaching solution or filter residue can be tested after the reaction, such as Ni, Co, Mn, Li, etc. Concentration to calculate the leaching rate.
  • the step (3) of removing Fe 2+ , Al 3+ , Ca 2+ and Mg 2+ in the leachate includes:
  • the amount of the oxidant added is 0.2-0.5 times the mass of Fe 2+ ; the neutralizer is sodium carbonate, and the pH is adjusted to 4.5-5.0.
  • the fluoride is sodium fluoride, and the added amount is 4-7 times the total mass of Ca 2+ and Mg 2+ .
  • the removal operation of some non-principal impurities in the leachate is beneficial to the preparation of higher-purity products during subsequent extraction and the reduction of impurities therein.
  • the filter residue produced in steps (2) and (3) also contains a small amount of Ni, Co and other components, and the residue washing operation can be selected to improve the overall recovery rate.
  • the residue washing operation can be terminated.
  • the obtained filtrate is used as the water for the slurry powder and filter residue I in the leaching process or as the leaching solution and step (2)
  • the obtained leachate is mixed and enters the next process.
  • step (4) uses a sulfuric acid solution with a concentration of 100-120 g/L for back extraction
  • step (5) uses a sulfuric acid solution with a concentration of 150-220 g/L for back extraction
  • step (7) uses a concentration of 100-220 g/L for back extraction.
  • Different extraction agents have different isotherms for different metal ions.
  • Different extraction agents are used to extract various metal ions successively, and then different concentrations of sulfuric acid solutions are used (in the case of close amounts, different pH can be achieved)
  • the metal ions extracted by the extractant are stripped out to obtain the corresponding sulfate, which can be further processed to obtain the sulfate product, and the extractant after the stripping can be reused.
  • P507 is used for extraction in two steps, and the extraction of cobalt and nickel is determined according to the isotherm of the P507 extractant for metal ion extraction at different pHs, so that the separation of cobalt and nickel can be achieved.
  • step (8) before using sodium carbonate reaction to collect lithium carbonate, the raffinate obtained in step (7) is adjusted to pH 9-10 to remove impurities, and the filter residue is concentrated to remove sodium salt to obtain a lithium-containing mother liquor.
  • the concentration of Li + in the raffinate is generally 1 ⁇ 3g/L.
  • the residue After removing impurities by adjusting pH 9 ⁇ 10 with sodium hydroxide solution, the residue is filtered and then concentrated. During the concentration process, the sodium salt is saturated and then precipitated.
  • the sodium salt is mainly The composition is sodium sulfate, and the precipitated sodium salt is separated and dried and packaged and stored for sale.
  • the concentration of Li + in the lithium-containing mother liquor is 12-15 g/L. During the concentration process, periodically check the concentration of Li + and stop the concentration after reaching the standard.
  • step (b) The lithium carbonate precipitate obtained in step (a) is reconstituted by adding sulfuric acid, and the pH is adjusted to 10-13 to remove impurities. After filtering the residue, sodium carbonate is added for reaction. The reaction temperature is 95°C ⁇ 98°C. The lithium carbonate precipitate is obtained by the reaction and washed. , Drying to obtain lithium carbonate.
  • the reaction temperature is selected from 95°C ⁇ 98 for the second purification of lithium carbonate. At this temperature, it can be ensured that the product obtained by the reaction has a good crystal form, and it is not easy to coat the sodium salt, and the sodium salt adhering to the surface can be washed away with water, so that the product lithium carbonate has a better purity.
  • the method for recovering valuable metals in the waste nickel-cobalt-manganese ternary lithium battery of the present invention through the Fe 2+ , Al 3+ , Ca 2+ and Mg 2+ de-impurity treatment before extraction, so that the subsequent recovery of valuable metals
  • the product purity is relatively high.
  • the ratio of oil to water is controlled to be 0.8-0.9:1, and the saponification rate is controlled to be 55% to 60%.
  • the saponification rate is reduced and the ratio of oil to water is appropriately reduced. The remaining cobalt remains in the water phase to ensure that magnesium will not be extracted, thereby ensuring that the magnesium impurity in the cobalt sulfate product meets the standard.
  • a step of magnesium extraction is added after cobalt extraction and before nickel extraction to remove residual magnesium as much as possible and increase the purity of the nickel sulfate product obtained from nickel extraction.
  • C272 extractant is used for extracting magnesium, using its characteristic of separating the isotherm curves of cobalt-magnesium and nickel, and controlling only extracting magnesium and cobalt without extracting nickel, so as to achieve the separation of magnesium and nickel.
  • the scraps are carbonized at a high temperature in a carbonization furnace to consume organic matter, and the remaining are mainly some metal elements.
  • the powder selected by the winnowing is mainly the electrode material (hereinafter referred to as the ternary black powder), which is used in the next step.
  • the steel shell, etc. becomes granular and can be recycled directly after being separated from the powder.
  • the secondary leaching residue is cleaned with clean water and 98% sulfuric acid to adjust the pH to about 3.0. After filtering, the washing water is used as the pre-leaching solution.
  • the two leaching solutions were mixed to obtain 1100 mL leaching solution, and the content of some major metal elements was tested. The test results are shown in Table 4.
  • P204 impurity removal mix 2L of 25% P204 organic phase, add 32% liquid caustic soda (sodium hydroxide solution) to saponify, the saponification rate is 70%, and the organic phase is compared with the pre-extraction liquid at a ratio of 2:1
  • the test results of raffinate and back extraction liquid are shown in Table 7.
  • manganese sulfate crystals are MnSO 4 ⁇ H 2 O, each molecule contains 1 crystal water, and manganese sulfate crystals are obtained.
  • the amount is 76g, the purity is 99.6%, and the recovery rate is 98.54%.
  • the cobalt sulfate solution is evaporated and crystallized into cobalt sulfate crystals (the cobalt sulfate crystals are CoSO 4 ⁇ 7H 2 O, and each molecule contains 7 crystal water) to obtain 108 g of cobalt sulfate crystals with a purity of 99.3% and a recovery rate of 98.57%.
  • the stripping liquid After the stripping liquid is back-leached and added sodium fluoride to remove magnesium, it then enters the P204 pre-extraction liquid.
  • P507 nickel extraction mix 2L of 25% P507 organic phase, add 32% liquid caustic soda for saponification, and the saponification rate is 70%.
  • Back extraction shake for 5 minutes and then clarify for 10 minutes, release the lower back extraction liquid, raffinate liquid 1800mL and back extraction liquid 300mL, the test results of raffinate and back extraction liquid are shown in Table 10.
  • the nickel sulfate solution is evaporated and crystallized into nickel sulfate crystals (the nickel sulfate crystals are NiSO 4 ⁇ 6H 2 O, and each molecule contains 6 crystal water) to obtain 182 g of nickel sulfate crystals with a purity of 99.35% and a recovery rate of 98%.
  • the obtained lithium carbonate has high purity and low sodium salt content.
  • the scraps are carbonized at a high temperature in a carbonization furnace to consume organic matter, and the remaining are mainly some metal elements.
  • the powder selected by the winnowing is mainly the electrode material (hereinafter referred to as the ternary black powder), which is used in the next step.
  • the steel shell, etc. becomes granular and can be recycled directly after being separated from the powder.
  • the secondary leaching residue is cleaned with clean water and 98% sulfuric acid to adjust the pH to about 3.0. After filtering, the washing water is used as the pre-leaching solution.
  • the two leaching solutions were mixed to obtain 1170 mL leaching solution, and the content of some major metal elements was tested. The test results are shown in Table 15.
  • P204 impurity removal mix 3L of 25% P204 organic phase, add 32% sodium hydroxide solution to saponify, the saponification rate is 70%, the organic phase and the pre-extraction liquid are added to the separatory funnel in a ratio of 2:1 for extraction Shake for 5 minutes and then clarify for 10 minutes, then add 200mL 15g/L sulfuric acid solution to wash the organic phase, shake for 5 minutes and then clarify for 10 minutes, release the lower raffinate 1600mL, and then add 200mL 100g/L sulfuric acid to the separatory funnel The solution was subjected to back extraction, shaken for 5 minutes and then clarified for 10 minutes, and the lower back extraction liquid was discharged. The test results of the raffinate and the back extraction liquid are shown in Table 18.
  • manganese sulfate solution is added with alkali sulfide to remove impurities
  • P204 extractant is used to remove Ca, and then evaporated and crystallized into manganese sulfate crystals (manganese sulfate crystals are MnSO 4 ⁇ H 2 O, each molecule contains 1 crystal water) to obtain manganese sulfate crystals 68.93g, purity 99.5%, recovery rate 98.76%.
  • the cobalt sulfate solution is evaporated and crystallized into cobalt sulfate crystals (the cobalt sulfate crystals are CoSO 4 ⁇ 7H 2 O, and each molecule contains 7 crystal water) to obtain 92 g of cobalt sulfate crystals with a purity of 99.3% and a recovery rate of 98.74%.
  • Extraction of magnesium from C272 mix 500 mL of 10% C272 organic phase, add 32% liquid caustic soda for saponification, and the saponification rate is 20%. Add the organic phase and the pre-extraction liquid to a separatory funnel at a ratio of 0.3:1 for extraction. Shake for 5 minutes and then clarify for 10 minutes, then add 100mL 15g/L sulfuric acid solution to wash the organic phase, shake for 5 minutes and then clarify for 10 minutes, release the lower raffinate 1950mL, and then add 50mL 200g/L sulfuric acid solution to the separatory funnel Perform back extraction, shake for 5 minutes and then clarify for 10 minutes, release the lower back extraction liquid, 1950 mL of raffinate and 50 mL of back extraction. The test results of raffinate and back extraction are shown in Table 20.
  • the stripping liquid After the stripping liquid is back-leached and added sodium fluoride to remove magnesium, it then enters the P204 pre-extraction liquid.
  • P507 nickel extraction mix 2L of 25% P507 organic phase, add 32% liquid caustic soda for saponification, and the saponification rate is 70%.
  • Back extraction shake for 5 minutes and then clarify for 10 minutes, release the lower back extraction liquid, raffinate 2250mL and back extraction liquid 300mL, the test results of raffinate and back extraction liquid are shown in Table 21.
  • the nickel sulfate solution is evaporated and crystallized into nickel sulfate crystals (the nickel sulfate crystals are NiSO 4 ⁇ 6H 2 O, and each molecule contains 6 crystal water) to obtain 140 g of nickel sulfate crystals with a purity of 99.6% and a recovery rate of 98.2%.
  • the obtained lithium carbonate has high purity and low sodium salt content.
  • Example 1 Take the same batch of ternary black powder in Example 1 for testing.
  • the leaching operation is the same as that in Example 1.
  • the extraction method is different.
  • the saponification rate is controlled to 65%, and the oil-water ratio (organic The ratio of phase and pre-extraction liquid) is 1:1, and finally cobalt is extracted to obtain cobalt sulfate crystals (cobalt sulfate crystals are CoSO 4 ⁇ 7H 2 O, each molecule contains 7 crystal water) 93.5g, purity 98.21%, and Co content It is 19.9%, and the Mg content is 0.0078%.
  • nickel sulfate crystals are NiSO 4 ⁇ 6H 2 O, each molecule contains 6 crystal water) 135g, purity 98.32%, of which The Ni content is 20.65%, and the Mg content is 0.0069%.
  • Example 2 The P507 nickel extraction residue after leaching and extraction in the same way as in Example 2 was subjected to lithium carbonate precipitation. Only the temperature was used for the precipitation of lithium carbonate at 80°C, and the other steps were the same. The purity of the finally obtained lithium carbonate product was tested and the purity was 98.52% , The Na content is 0.25%. Compared with Examples 1 and 2, Comparative Example 2 has more sodium salt impurities. It shows that at lower temperature, it is easy to coat sodium salt when lithium carbonate precipitates.
  • the percentages are all mass percentages.

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Abstract

L'invention concerne un procédé de récupération de métaux de valeur présents dans des batteries usagées au lithium ternaire de nickel-cobalt-manganèse, le procédé comprenant : l'élimination d'impuretés à base de Fe2+, Al3+, Ca2+ et Mg2+ avant l'extraction de sorte que la pureté de produits métalliques de valeur récupérés par la suite est élevée. Pendant l'extraction de cobalt, le rapport huile-eau est réglé pour être de 0,8 à 0,9:1 et le taux de saponification est réglé pour être de 55 % à 60 % ; grâce à la diminution du taux de saponification et à la diminution de manière appropriée du rapport huile-eau, le cobalt présent dans une phase aqueuse est réglé pour ne pas être complètement extrait, une petite quantité de cobalt étant laissée dans la phase aqueuse, ce qui garantit ainsi que du magnésium n'est pas extrait et que les impuretés à base de magnésium présentes dans des produits de type sulfate de cobalt satisfont à une norme. Une étape d'une opération d'extraction de magnésium est ajoutée après l'extraction de cobalt et avant l'extraction de nickel, du magnésium résiduel est éliminé autant que possible et la pureté des produits de type sulfate de nickel obtenus après extraction de nickel est augmentée. Un agent d'extraction C272 est utilisé pour l'extraction de magnésium, la caractéristique de celui-ci selon laquelle les courbes isothermes d'extraction de cobalt, de magnésium et de nickel sont largement séparées est utilisée et l'extraction uniquement de magnésium et de cobalt tandis que le nickel n'est pas extrait est maîtrisée, d'où il résulte que le magnésium et le nickel sont séparés.
PCT/CN2019/105497 2019-04-28 2019-09-12 Procédé de récupération de métaux de valeur présents dans des batteries usagées au lithium ternaire de nickel-cobalt-manganèse WO2020220559A1 (fr)

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WO2023026931A1 (fr) * 2021-08-26 2023-03-02 Ｊｆｅスチール株式会社 Procédé d'élimination de manganèse et procédé de production d'oxyde ferrique
CN115893497A (zh) * 2022-11-14 2023-04-04 广东邦普循环科技有限公司 一种从含钙铜铬硅的锰溶液中制备高纯硫酸锰的方法
US11876196B2 (en) 2020-08-24 2024-01-16 Green Li-Ion Pte. Ltd. Process for removing impurities in the recycling of lithium-ion batteries
WO2024042115A1 (fr) 2022-08-24 2024-02-29 Umicore Procédé de préparation d'une solution de sulfate de nickel de haute pureté

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