Process and production plant for recovering metal salts

Abstract

The present disclosure relates to a continuous process and a production plant for recovering metal salts from an acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations.

Description

[0001] Process and production plant for recovering metal salts

[0002] The project leading to this application has received funding from Bundesministerium fur Wirtschaft und Klimaschutz and State of Brandenburg (DE; FKZ:16BZF101A / B); the applicant bears responsibility for all disclosures herein.

[0003] Field of the invention

[0004] The present disclosure relates to a continuous process and a production plant for recovering metal salts from an acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations.

[0005] Background

[0006] Lithium ion battery materials are complex mixtures of various elements and compounds. For example, many lithium ion battery materials contain valuable metals such as lithium, aluminum, copper, nickel, cobalt, and / or manganese. It may be desirable to recover various elements and compounds from lithium ion battery materials. For example, it may be advantageous to recover lithium, aluminum, copper, nickel, cobalt, and / or manganese. Accordingly, there is a need for devices and processes for recycling lithium ion battery materials.

[0007] WO 20231054621 A1 discloses a method for recovering valuable metals from waste lithium ion batteries comprising a dissolution step for dissolving an active material powder obtained by pre-treating the waste lithium-ion batteries in a mineral acid to obtain an acid solution; and a solvent extraction step for separating manganese, cobalt, and nickel, among metals contained in the active material powder, from the acid solution through solvent extraction to obtain a first lithium salt aqueous solution as a residual liquid of the solvent extraction. WO 2020 / 124130 A1 discloses a method for the recovery of metals from a feed stream containing one or more value metals and lithium. The method comprises subjecting the feed stream to a sulfuric acid leach to form a slurry comprising a pregnant leach solution of soluble metal salts and a solid residue; separating the pregnant leach solution and the solid residue; subjecting the pregnant leach solution to one or more separate solvent extraction steps, wherein each solvent extraction step recovers one or more value metals from the pregnant leach solution, the remaining pregnant leach solution comprising lithium; and recovery of lithium from the pregnant leach solution.

[0008] JP 2017 115179 A discloses a method of recovering valuable substances, such as Co, Ni, Mn which includes: an acid leaching step to obtain a leachate by mixing a ground product of lithium ion battery wastes and / or a positive electrode material for lithium ion batteries and an acidic solution such that at least a metal component constituting the positive electrode material is dissolved in the acidic solution; and a precipitation step to generate precipitates by adjusting pH of an addition liquid, formed by adding a basic calcium compound to the leachate obtained in the acid leaching step, to be in the range of 4.6-4.9 and by adjusting the oxidation reduction potential of the addition liquid to be in the range of 200-600 mV.

[0009] It is an object of the present disclosure to provide an improved recycling plant for lithium ion battery materials and an improved recycling process for lithium ion battery materials.

[0010] Summary of the invention

[0011] The present disclosure provides a continuous process for recovering value metals from an acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations. The process involves removing impurity cations of the group consisting of Al and Fe cations and impurity anions comprising P, F, Al, and / or Si present in the solution from the solution by precipitation, precipitating and recovering a mixed metal hydroxide and / or carbonate from the aqueous solution depleted of impurity cations of the group consisting of Al and Fe cations and impurity anions comprising P, F, Al, and / or Si, precipitating and removing magnesium hydroxide from the solution, and removing lithium cations from the solution by solvent extraction.

[0012] The present disclosure also provides a production plant suitable for performing the continuous process of the present disclosure.

[0013] Brief description of the drawings

[0014] Fig. 1 is a schematic diagram of an exemplary production plant of the present disclosure.

[0015] Detailed description

[0016] The present disclosure provides a continuous process for recovering value metals from an acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations. In some embodiments, the acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations has been obtained by leaching lithium ion battery materials with sulfuric acid. Examples of suitable lithium ion battery materials for preparing the acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations include black mass, cathode active materials, and mixed metal hydroxides (MHP). The acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations may additionally contain cations of other metals like copper, iron, aluminum, magnesium, calcium, and / or titanium; as well as anions like fluoride and / or phosphate.

[0017] The continuous process of the present disclosure comprises the steps of a) optionally, adjusting the pH value of the solution to a value of from 1 .5 to 2.5 and recovering copper from the solution by solvent extraction or by precipitation of copper sulfide, followed by solid / liquid separation, b) adjusting the pH of the acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations to be in the range of from 3.0 to 4.0 by addition of sodium carbonate, and subsequently precipitating impurity cations of the group consisting of Al and Fe cations and impurity anions comprising P, F, Al, and / or Si present in the solution from the solution, c) removing solids from the mixture obtained in step b), d) adjusting the pH of the acidic aqueous solution obtained in step c) to be in the range of from 4.5 to 5.0 by addition of sodium carbonate, and subsequently precipitating impurity cations of the group consisting of Al and Fe cations and impurity anions comprising P, F, Al, and / or Si present in the solution from the solution, e) removing solids from the mixture obtained in step d), f) adjusting the pH of the aqueous solution obtained in step e) to be in the range of from 7 to 8.5, and precipitating a mixed metal hydroxide and / or carbonate from the solution, g) performing a solid / liquid separation of the mixture obtained in step f) to obtain solid mixed metal hydroxide and / or carbonate and a mother liquor, h) adding sodium hydroxide to the mother liquor obtained in step g), adjusting the pH of the mother liquor to be in the range of from 10 to 12.5, and precipitating magnesium hydroxide from the mother liquor, i) removing solids from the mixture obtained in step h), j) adjusting the pH of the aqueous solution obtained in step i) to be in the range of from 8 to 12; e.g., from 8 to 10, for instance, from 8 to 9, and subsequently removing lithium cations from the solution by solvent extraction to obtain an aqueous solution depleted of lithium cations and an organic solvent comprising lithium cations; and scrubbing and stripping the organic solvent comprising lithium cations with sulfuric acid to obtain an acidic aqueous solution comprising lithium cations.

[0018] In an optional first step a), copper is recovered by a first solvent extraction from the acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations.

[0019] Solvent extraction is a useful method for separating and purifying metal ions from an aqueous solution or leachate. This can be difficult when purifying metal ions present in a hydrated form in an aqueous solution, since it is difficult to move the ions to an organic solvent layer having a low polarity. In order to move hydrated metal ions to the organic phase, the metal ions should be in a form of an uncharged complex and the metal ions should be able to remove water molecules from the hydrated complex.

[0020] A solvent extracting agent allows the metal ions to form a non-charged complex and remove water molecules. The extraction efficiency depends on, e.g., the type of solvent extracting agent, the equilibrium pH, and the metal ions in the aqueous solution. The extraction efficiency may also be affected by, e.g., the concentration of the solvent extracting agent, the ratio of the solvent extracting agent to the aqueous solution, and the composition and concentration of the stripping solution. In some embodiments of the process, the solvent extracting agent is LIX984N, a 1 :1 mixture of 5-nonyl salicylaldoxime and 2-hydroxy-5- nonyl acetophenone.

[0021] In some embodiments, the first solvent extraction comprises

[0022] • adding an alkaline solution to the acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations to adjust the pH value of the solution to a value in the range of from 1 .5 to 2.5;

[0023] • adding a solvent extracting agent to the acidic aqueous solution,

[0024] • homogenizing the mixture of acidic aqueous solution and solvent extracting agent,

[0025] • allowing the mixture to separate into a layer of an acidic aqueous solution depleted of Cu and a layer of solvent extracting agent comprising Cu,

[0026] • separating the layer of solvent extracting agent comprising Cu from the layer of acidic aqueous solution depleted of Cu,

[0027] • mixing the separated solvent extracting agent comprising Cu with a second aqueous acidic solution,

[0028] • homogenizing the mixture,

[0029] • allowing the mixture to separate into a layer of a second aqueous solution comprising copper and a layer of solvent extracting agent, and separating the aqueous solution comprising Cu from the layer of solvent extracting agent.

[0030] In some embodiments, the first solvent extraction is a two-step process (or even a three-step process if impurities need to be scrubbed before the stripping). The optional step of scrubbing (step 2), if necessary, is carried out in-between the extraction of the target species into the organic phase (step 1 ) and the stripping (step 3).

[0031] In a first step, a solvent extracting agent (a non-polar weak acid) is dissolved in an organic liquid (diluent), such as kerosene. This mixture forms the extracting agent solution. This solution is brought into contact / mixed with the acidic aqueous solution, from which the extracting agent selectively extracts copper cations.

[0032] In a second optional step, impurities are removed from the organic phase (the extracting agent solution) by scrubbing.

[0033] Subsequently, the extracting agent solution, which now comprises copper cations, is brought into contact with an acid solution (strong acid), which causes the copper cations to be replaced by H+. In return, the copper cations transfer into the acidic aqueous solution. This solution is then called loaded stripping solution. The process of transferring the copper cations back into an aqueous phase is called stripping.

[0034] In some embodiments, copper is recovered by precipitation followed by solid / liquid separation. In some embodiments, the copper ions are removed by precipitation of copper sulfide. To precipitate copper sulfide, sulfide, hydrogen sulfide, or thiosulfate ions are added to the solution. In some embodiments, Na2SO3 is added to to the solution to precipitate copper sulfide. The precipitate is separated from the aqueous solution depleted of copper cations by solid / liquid separation, for instance, by filtration. The acidic aqueous solution depleted of Cu obtained after the first solvent extraction, or after precipitation of copper sulfide, followed by solid / liquid separation is further processed in step b).

[0035] In step b) of the process of the present disclosure, impurities are precipitated from the acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations. The precipitation involves the addition of sodium carbonate.

[0036] The impurities comprise one or more selected from iron, aluminum, magnesium, calcium, titanium, residual copper, fluoride, and phosphate. The precipitation involves the addition of a sodium carbonate solution to the acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations, thereby adjusting the pH value of the solution to a value in the range of from 3.0 to 4.0. In some embodiments of the process, air is injected into the solution to oxidize any Fe(ll) present to Fe(lll). Iron, aluminum, and titanium precipitate from the solution as hydroxides and / or oxide-hydroxides and / or carbonates, fluorides and / or phosphates, and are removed from the mother liquor in a subsequent step c) by solid-liquid separation, e.g., filtration.

[0037] The mother liquor is further processed in a second precipitation step d). The precipitation involves the addition of a sodium carbonate solution to the mother liquor obtained in step c), thereby adjusting the pH value of the solution to a value in the range of from 4.5 to 5.0. Iron, aluminum, and titanium precipitate from the solution as hydroxides and / or oxide-hydroxides and / or carbonates, fluorides and / or phosphates, and are removed from the mother liquor in a subsequent step e) by solid-liquid separation, e.g., filtration. In some embodiments of the process, some manganese also is precipitated as manganese carbonate. As the precipitate obtained in step e) may contain significant amounts of value metals, in particular, nickel, it can be recycled into a leaching step and used for generating an acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations. Using the two-stage precipitation and separation process of steps b) through e) maximizes precipitation of Al, Fe, F and thus the removal of impurities from the acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations, and it minimizes co-precipitation of value metals, and thus minimizes losses of nickel, cobalt, manganese, and lithium.

[0038] The process further comprises f) adjusting the pH of the aqueous solution depleted of manganese and impurity cations obtained in step e) to be in the range of from 7 to 8.5, and precipitating a mixed metal hydroxide and / or carbonate from the solution.

[0039] The process further comprises g) performing a solid / liquid separation of the mixture obtained in step f) to obtain solid mixed metal hydroxide and / or carbonate and a mother liquor. The mixed metal hydroxide and / or carbonate mainly comprises nickel hydroxide and / or carbonate, and also comprises cobalt hydroxide and / or carbonate and manganese hydroxide and / or carbonate. The precipitation step yields a solid with low sodium sulfate content that can be redissolved and used as feed for cathode material precursor synthesis. The mixed metal hydroxide and / or carbonate can be used without further purification for the production of cathode active materials (CAM) for lithium ion batteries. As bases like NaOH or Na2COs are used for pH adjustment in all process steps after acid leaching, Na2SO4 is formed. Due to the high concentration of Na, a NiNa(SO4)2double salt is formed upon evaporation of a recycling feed, so that recovery of Ni from the solution usually requires an additional solvent extraction step.

[0040] The process further comprises h) adding sodium hydroxide to the mother liquor obtained in step g), adjusting the pH of the mother liquor to be in the range of from 10 to 12.5, and precipitating magnesium hydroxide from the mother liquor. This step is essential for the subsequent recovery of lithium cations by solvent extraction. It has been found that magnesium cations hamper the phase separation of the organic phase from the aqueous phase in solvent extraction of lithium-containing solutions. Without prior removal of magnesium cations from the solution, solvent extraction of lithium cations does not work properly.

[0041] The process further comprises i) removing solids from the mixture obtained in step h).

[0042] The process further comprises j) adjusting the pH of the aqueous solution obtained in step i) to be in the range of from 8 to 12, e.g., from 8 to 10, for instance, from 8 to 9; and subsequently removing lithium cations from the solution by solvent extraction to obtain an aqueous solution depleted of lithium cations and an organic solvent comprising lithium cations; and scrubbing and stripping the organic solvent comprising lithium cations with sulfuric acid to obtain an acidic aqueous solution comprising lithium cations. As the aqueous solution obtained in step i) also contains high concentrations of sodium cations, recovery of lithium cations from the solution by solvent extraction offers advantages over the precipitation of lithium salts like lithium carbonate, as contamination of the acidic aqueous solution comprising lithium cations by sodium cations, and consequently, the sodium content of lithium salts recovered from the acidic aqueous solution comprising lithium cations is minimized.

[0043] In some embodiments, the process further comprises k) crystalizing lithium sulfate from the acidic aqueous solution comprising lithium cations obtained in step j).

[0044] Solvent extraction is performed in step j) using an organic solvent suitable for extracting lithium cations from an aqueous solution. Examples of suitable organic solvents include synergistic extractant mixtures comprising a betadiketone and a neutral extractant, e.g. an organic phosphate, as disclosed in J Chem Technol Biotechnol 2016; 91 : 2549-2562 (table 3); Hydrometallurgy 154 (2015) 33-39; and Hydrometallurgy 175 (2018) 35-42. Further examples of suitable organic solvents include organic solutions comprising an organic diluent, at least one phosphine oxide and at least one proton donating agent, as disclosed in WO 2013 / 065050 A1 . In some embodiments, the phosphine oxide corresponds to the general formula OPR1R2R3, wherein each of R1, R2and R3is independently selected from straight or branched C1-C10 alkyl, straight or branched C2-C10 alkenyl, straight or branched C2-C10 alkynyl, optionally substituted C5-C12 aryl, optionally substituted C4 -C12 heteroaryl; the at least one proton donating agent is selected from the group consisting of straight or branched C1-C10 alcohol, C1-C10 ketone, C1-C10 aldehyde, C3-C20 fatty acid, and any combination thereof; and the molar ratio between said phosphine oxide and an organic acid in said extracting organic solution is in the range of between about 5:1 to about 1 :5. In some embodiments, the solvent used in step f) comprises benzoyltrifluoroacetone (HBTA) and tri-n-octylphosphine oxide (TOPO). In some embodiments, the solvent used in step f) comprises thenoyltrifluoroacetone (TTA) and tri-n-octylphosphine oxide (TOPO). In some embodiments, the solvent used in step j) is a solution of 27 vol% Cyanex® 936P in dearomatized hydrocarbon fluid (Escaid™ 110).

[0045] The present disclosure also provides a production plant suitable for performing the process of the present disclosure. In some embodiments, the production plant comprises a first solvent extraction (SX) unit configured to receive an acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations. The first SX unit comprises an extraction module and a scrubbing and stripping module. In the extraction module of the SX unit, an aqueous solution is extracted with an organic solvent, an aqueous phase and an organic phase being formed in the process. The organic phase is separated from the aqueous phase and transferred to the scrubbing and stripping module, where it is extracted with an aqueous acid. After scrubbing and stripping, the organic phase is cycled back to the extraction module. Suitable solvent extraction (SX) units are known in the art.

[0046] The production plant comprises at least one first continuous stirred-tank reactor (CSTR) configured to receive an aqueous effluent of the extraction module of the first SX unit, if a first SX unit is present, or, in the alternative, to receive an acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations. If a first SX unit is present, the first CSTR is located downstream of the first SX unit. The at least one first CSTR comprises a dosing device for liquids, heating / cooling means, and gas injection means. Suitable continuous stirred- tank reactors are known in the art.

[0047] The production plant further comprises at least one first solid / liquid separation device configured to receive an effluent of the first CSTR. The at least one first solid / liquid separation device thus is located downstream of the first CSTR. In some embodiments, the first solid / liquid separation device comprises a filter press.

[0048] The production plant also comprises at least one second continuous stirred-tank reactor (CSTR) configured to receive an aqueous effluent of the at least one first solid / liquid separation device. The second CSTR thus is located downstream of the first solid / liquid separation device. The first CSTR comprises a dosing device for liquids and heating / cooling means. Suitable continuous stirred-tank reactors are known in the art.

[0049] The production plant further comprises at least one second solid / liquid separation device configured to receive an effluent of the second CSTR. The at least one second solid / liquid separation device thus is located downstream of the second CSTR. In some embodiments, the first solid / liquid separation device comprises a filter press.

[0050] The production plant also comprises at least one third continuously stirred tank reactor (CSTR) configured to receive an aqueous effluent of the at least one second solid / liquid separation device. The third CSTR thus is located downstream of the second SX unit. The third CSTR comprises a dosing device for liquids and heating / cooling means. Suitable continuously stirred tank reactors are known in the art.

[0051] The production plant further comprises at least one third solid / liquid separation device configured to receive an effluent of the third CSTR. The at least one third solid / liquid separation device thus is located downstream of the third CSTR. In some embodiments, the third solid / liquid separation device comprises a filter press.

[0052] The production plant further comprises at least one fourth continuously stirred tank reactor (CSTR) configured to receive an aqueous effluent of the third solid / liquid separation device. The fourth CSTR thus is located downstream of the third solid / liquid separation device. The fourth CSTR comprises a dosing device for liquids and heating / cooling means. Suitable continuously stirred tank reactors are known in the art.

[0053] The production plant further comprises at least one fourth solid / liquid separation device configured to receive an effluent of the fourth CSTR. The at least one fourth solid / liquid separation device thus is located downstream of the fourth CSTR. In some embodiments, the fourth solid / liquid separation device comprises a filter press.

[0054] The production plant further comprises a second solvent extraction (SX) unit configured to receive an aqueous effluent of the at least one fourth solid / liquid separation device. The second SX unit comprises an extraction module and a scrubbing and stripping module. In the extraction module of the SX unit, an aqueous solution is extracted with an organic solvent, an aqueous phase and an organic phase being formed in the process. The organic phase is separated from the aqueous phase and transferred to the scrubbing and stripping module, where it is extracted with an aqueous acid. After scrubbing and stripping, the organic phase is cycled back to the extraction module. Suitable solvent extraction (SX) units are known in the art.

[0055] The production plant further comprises a first crystallizer configured to receive an aqueous effluent of the scrubbing and stripping module of the second SX unit and to produce crystals of a first metal salt. Suitable crystallizers are known in the art. Detailed description of the drawing

[0056] A schematic diagram of an exemplary production plant of the present disclosure is shown in Fig. 1 .

[0057] The production plant comprises a first solvent extraction (SX) unit 10 which is configured to receive an acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations 1000. The first SX unit 10 comprises an extraction module 11 and a scrubbing and stripping module 12. The acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations entering the first SX unit 10 is extracted with an organic solvent in the extraction module 11 . The extracted aqueous phase leaves the extraction module 11 as an aqueous effluent 1001. The loaded organic phase is transferred to the scrubbing and stripping module 12, where it is scrubbed and stripped of metal cations with sulfuric acid to produce an acidic aqueous solution comprising the metal cations from the organic phase. The organic phase is recycled to the extraction module 11 , and the acidic aqueous solution comprising the metal cations from the organic phase leaves the scrubbing and stripping module 12 as an aqueous effluent 1002.

[0058] The production plant further comprises at least one first continuously stirred tank reactor (CSTR) 30 which is configured to receive an aqueous effluent 1001 of the extraction module 11 of the first SX unit 10. The CSTR 30 comprises a dosing device for liquids, heating / cooling means, and gas injection means. In the CSTR 30, a solution comprising sodium carbonate is added to precipitate impurities from the solution. The impurities comprise one or more selected from iron, aluminum, titanium, fluoride, and phosphate. Air is injected into the solution to oxidize any Fe(ll) present to Fe(lll). Iron, aluminum, and titanium precipitate from the solution as hydroxides and / or oxide-hydroxides and / or carbonates, fluorides and / or phosphates,

[0059] The production plant further comprises at least one first solid / liquid separation device 70 which is configured to receive an effluent 3001 of the first CSTR 30. In the at least one first solid / liquid separation device 70, the precipitated impurities 7002 are removed from the effluent of the first CSTR 30 by solid / liquid separation, e.g., filtration.

[0060] The production plant further comprises at least one second CSTR 40 which is configured to receive an aqueous effluent 7001 from the first solid / liquid separation device 70. The second CSTR 40 comprises a dosing device for liquids and heating / cooling means. In the second CSTR 40, a solution comprising sodium carbonate is added to precipitate residual impurities from the solution.

[0061] The production plant further comprises at least one second solid / liquid separation device 80 which is configured to receive an effluent 4001 of the second CSTR 40. In the at least one second solid / liquid separation device 80, solids 8002 are recovered from the effluent 4001 of the second CSTR 40 by solid / liquid separation, e.g., filtration.

[0062] The production plant further comprises at least one third continuously stirred tank reactor (CSTR) 50 which is configured to receive an aqueous effluent 8001 of the at least one second solid / liquid separation device 80. The CSTR 50 comprises a dosing device for liquids, and heating / cooling means. In the CSTR 50, a solution comprising carbonate anions is added to precipitate a mixed metal hydroxide and / or carbonate from the solution.

[0063] The production plant further comprises at least one third solid / liquid separation device 90 which is configured to receive an effluent 5001 of the third CSTR 50. In the at least one third solid / liquid separation device 90, a mixed metal hydroxide and / or carbonate 9002 is recovered from the effluent 5001 of the third CSTR 50 by solid / liquid separation, e.g., filtration.

[0064] The production plant further comprises at least one fourth CSTR 60 which is configured to receive an aqueous effluent of the third solid / liquid separation device 90. The fourth CSTR 60 comprises a dosing device for liquids and heating / cooling means. In the fourth CSTR 60, alkaline solution is added to precipitate magnesium hydroxide 10002.

[0065] The production plant further comprises at least one fourth solid / liquid separation device 100 which is configured to receive an effluent 6001 of the fourth CSTR 60. In the at least one fourth solid / liquid separation device 160, magnesium hydroxide 10002 is removed from the effluent 6001 of the fourth CSTR 60 by solid / liquid separation, e.g., filtration.

[0066] The production plant further comprises a second SX unit 20 which is configured to receive an aqueous effluent 10001 of the at least one fourth solid / liquid separation device 100. The second SX unit 20 comprises an extraction module 21 and a scrubbing and stripping module 22. The aqueous effluent 10001 of the at least one second solid / liquid separation device 100 is extracted with an organic solvent in the extraction module 21. The extracted aqueous phase leaves the extraction module 21 as an aqueous effluent 2001. The loaded organic phase is transferred to the scrubbing and stripping module 22, where it is scrubbed and stripped of metal cations with sulfuric acid to produce an acidic aqueous solution comprising the metal cations from the organic phase. The organic phase is recycled to the extraction module 21 , and the acidic aqueous solution comprising the metal cations from the organic phase leaves the scrubbing and stripping module 22 as an aqueous effluent 2002.

[0067] The production plant further comprises a first crystallizer 110 configured to receive an aqueous effluent 2002 of the scrubbing and stripping module 22 of the second SX unit 20 and to produce crystals of a first metal salt, e.g., lithium sulfate. Examples

[0068] Feeds

[0069] Example 1

[0070] 100 g of feed I containing Mn, Li, Ni, Co and Ca was heated up to 43 °C. The mixture was treated with a Na2CO3-solution until a pH of 7.2 was reached. After the reaction was complete, the precipitate was filtered off and washed, after which a dry solid residue (1) and filtrate (a) were obtained with a yield of 9.6 and 160.7 g, respectively. Constitution of fractions and yields are found in the tables below.

[0071] Example 2

[0072] 150 g of feed I containing Mn, Li, Ni, Co and Ca was heated up to 43 °C. The mixture was treated with a Na2CO3-solution until a pH of 7.4 was reached. After the reaction was complete, the precipitate was filtered off and washed, after which a dry solid residue (2) and filtrate (b) could be obtained with a yield of 16.3 and 308.0 g, respectively. Constitution of fractions and yields are found in the tables below.

[0073] Example 3

[0074] First Stage Precipitation

[0075] Feed II containing Mn, Li, Ni, Co and Ca was subjected to a continuous operation to precipitate MHP at a temperature of 60 °C. The mixture was treated with Na2CO3-solution until a final pH of 7.3 was reached. Through the addition of flocculation agents, sedimentation rate and particle size of the MHP was improved. From this operation a dry solid residue (3) and overflow (c = Feed III) was obtained. Constitution of fractions and yields are found in the tables below. Second Stage Precipitation

[0076] 200 g of feed III containing Mn, Li, Ni, Co and Ca was heated up to 40 °C. The mixture was treated with a Na2CO3-solution until a pH of 8.5 was reached. After the reaction was complete, the precipitate was filtered off and washed, after which a dry solid residue (4) and filtrate (d) could be obtained with a yield of 0.9 and 196.5 g, respectively. Constitution of fractions and yields are found in the tables below.

[0077] Example 4 (comparative example)

[0078] 1000 g of a solution I containing Mn, Li, Ni, Co and Ca was heated to 43°C. The mixture was treated with a NaOH-solution until a pH of 8 was reached, during which precipitation of a green solid occurred. After a total reaction time of 180 min, the suspension was filtered off and the solid was washed. A dry solid residue and a filtrate (e) could be obtained with a yield of 155 and 1230 g, respectively. Residual moisture and particle size distribution of the solid (5) were determined to be 58.6% and D(50) = 13.4 pm, respectively.

[0079] Table 1 Composition of the dry solids as determined by ICP-OES analysis

[0080] Solids Co Li Mn Ni Ca

[0081] 1 3.8 wt% 0.02 wt% 4.1 wt % 8.5 wt % 500 ppm

[0082] 2 10.1 wt% 0.14 wt% 11.2 wt % 23.7 wt % 0.13 wt %

[0083] 3 13.6 wt% 0.26 wt% 14.5 wt % 15.6 wt % 960 ppm

[0084] 46 6.8 wt% 1.3 wt% / 16.0 wt% /

[0085] 5 7.5 wt% 1.2 wt% 3.8 wt % 17.6 wt % 300 ppm

[0086] Table 2 composition of solutions obtained as determined by ICP-OES analysis.

[0087] Solution Co Li Mn Ni Ca a 300 ppm 0.33 wt % 300 ppm 0.11 wt % 30 ppm b 300 ppm 0.30 wt % 200 ppm 800 ppm 10 ppm c 390 ppm 0.48 wt % 290 ppm 920 ppm / d 10 ppm 0.49 wt % / 50 ppm / f 440 ppm 0.46 wt % 0.67 wt % 480 ppm 120 ppm Table 3 Final yields of selected elements in the precipitate.

[0088] Example Co Li Mn Ni Ca

[0089] 1 95.3% 0.90% 96.2% 93.3% 75%

[0090] 2 95.5% 2.40% 96.9% 93.9% 87.3%

[0091] 3 99.8% 3.08% > 94.2% 99.2% /

[0092] 4 96.8% 29.5% 50.6% 98.5% 53.6%

[0093] The following calculations were used for determining the metal yields in the solids in examples 1 , 2, and 4 wherein

[0094] E denotes a given element,

[0095] S denotes the dry solid,

[0096] EICP-S is the determined percentage-based content in the dry solid, m(Es) is the weight content of the element in the dry solid, m(EMax) is the total weight of an element found in all fractions, m(S) is the weight of the dry solid fraction, and

[0097] YEis the leaching efficiency of the respective element.

[0098] The following calculations were used for determining the metal yields in the solids in examples 3 m(E )=EICP-S* F * T ( 2 ) wherein

[0099] E denotes a given element,

[0100] S denotes the dry solid, EICP-S is the determined percentage-based content in the dry solid, m(Es) is the weight content of the element in the dry solid, m(EMax) is the total weight of an element based on the feed solution,

[0101] F is the flow rate of the continuous process, T is a time span during steady state, and YEis the leaching efficiency of the respective element.

[0102] List of reference numerals

[0103] 10 First SX unit

[0104] 11 Extraction module of first SX unit

[0105] 12 Scrubbing and stripping module of first SX unit

[0106] 20 Second SX unit

[0107] 21 Extraction module of second SX unit

[0108] 22 Scrubbing and stripping module of second SX unit

[0109] 30 Third SX unit

[0110] 31 Extraction module of third SX unit

[0111] 32 Scrubbing and stripping module of third SX unit

[0112] 40 Fourth SX unit

[0113] 41 Extraction module of fourth SX unit

[0114] 42 Scrubbing and stripping module of fourth SX unit

[0115] 50 Fifth SX unit

[0116] 51 Extraction module of fifth SX unit

[0117] 60 First CSTR

[0118] 70 Second CSTR

[0119] 80 Third CSTR

[0120] 90 Fourth CSTR

[0121] 1000 Fifth CSTR

[0122] 110 Sixth CSTR

[0123] 120 Seventh CSTR

[0124] 130 First solid / liquid separation unit

[0125] 140 Second solid / liquid separation unit

[0126] 150 Third solid / liquid separation unit

[0127] 160 Fourth solid / liquid separation unit

[0128] 170 Fifth solid / liquid separation unit

[0129] 180 Sixth solid / liquid separation unit

[0130] 190 Seventh solid / liquid separation unit

[0131] 200 First crystallizer

[0132] 210 Second crystallizer

[0133] 220 Third crystallizer 1000 Acidic aqueous solution comprising Ni, Co, Mn, and Li cations

[0134] 1001 Aqueous effluent of extraction module of first SX unit

[0135] 1002 Aqueous effluent of scrubbing and stripping module of first SX unit

[0136] 2001 Aqueous effluent of extraction module of second SX unit

[0137] 2002 Aqueous effluent of scrubbing and stripping module of second SX unit

[0138] 3001 Aqueous effluent of extraction module of third SX unit

[0139] 3002 Aqueous effluent of scrubbing and stripping module of third SX unit

[0140] 4001 Aqueous effluent of extraction module of fourth SX unit

[0141] 4002 Aqueous effluent of scrubbing and stripping module of fourth SX unit

[0142] 5001 Aqueous effluent of extraction module of fifth SX unit

[0143] 5002 Organic phase effluent of extraction module of fifth SX unit

[0144] 6001 Effluent of first CSTR

[0145] 7001 Effluent of second CSTR

[0146] 8001 Effluent of third CSTR

[0147] 9001 Effluent of fourth CSTR

[0148] 10001 Effluent of fifth CSTR

[0149] 11001 Effluent of sixth CSTR

[0150] 12001 Effluent of seventh CSTR

[0151] 13001 Aqueous effluent of first solid / liquid separation unit

[0152] 13002 Solids (First impurity precipitate)

[0153] 14001 Aqueous effluent of second solid / liquid separation unit

[0154] 14002 Solids (Second impurity precipitate)

[0155] 15001 Aqueous effluent of third solid / liquid separation unit

[0156] 15002 Solids (mixed metal hydroxide and / or carbonate precipitate)

[0157] 16001 Aqueous effluent of fourth solid / liquid separation unit

[0158] 16002 Solids (Insoluble residue)

[0159] 17001 Aqueous effluent of fifth solid / liquid separation unit

[0160] 17002 Solids (Magnesium hydroxide)

[0161] 18001 Aqueous effluent of sixth solid / liquid separation unit

[0162] 18002 Solids (Manganese hydroxide and / or carbonate)

[0163] 19001 Aqueous effluent of seventh solid / liquid separation unit

[0164] 19002 Solids (Metal hydroxides)

[0165] 21001 Mother liquor of second crystallizer

Claims

Claims1 . A continuous process for recovering metal salts from an acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations, the process comprising a) optionally, adjusting the pH of the solution to a value in the range f from 1 .5 to 2.5 and recovering copper from the solution by solvent extraction, or by precipitation of copper sulfide, followed by solid / liquid separation, b) adjusting the pH of the acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations to be in the range of from 3.0 to 4.0 by addition of sodium carbonate, and subsequently precipitating impurity cations of the group consisting of Al and Fe cations and impurity anions comprising P, F, Al, and / or Si present in the solution from the solution, c) removing solids from the mixture obtained in step b), d) adjusting the pH of the acidic aqueous solution obtained in step c) to be in the range of from 4.5 to 5.0 by addition of sodium carbonate, and subsequently precipitating impurity cations of the group consisting of Al and Fe cations and impurity anions comprising P, F, Al and / or Si present in the solution from the solution, e) removing solids from the mixture obtained in step d), f) adjusting the pH of the aqueous solution obtained in step e) to be in the range of from 7 to 8.5, and precipitating a mixed metal hydroxide and / or carbonate from the solution, g) recovering the solid mixed metal hydroxide and / or carbonate from the mixture obtained in step f), h) adding sodium hydroxide to the mother liquor obtained in step g), adjusting the pH of the mother liquor to be in the range of from 10to 12.5, and precipitating magnesium hydroxide from the mother liquor, i) removing solids from the mixture obtained in step h), j) adjusting the pH of the aqueous solution obtained in step i) to be in the range of from 8 to 12; and subsequently removing lithium cations from the solution by solvent extraction to obtain an aqueous solution depleted of lithium cations and an organic solvent comprising lithium cations; and scrubbing and stripping the organic solvent comprising lithium cations with sulfuric acid to obtain an acidic aqueous solution comprising lithium cations.

2. The process of claim 1 .further comprising k) crystalizing lithium sulfate from the acidic aqueous solution comprising cobalt cations obtained in step j).

3. The process of claim 1 or 2, wherein copper is recovered from the solution in step a) by solvent extraction and the organic solvent used is a solution of a 1 :1 mixture of 5-nonyl salicylaldoxime and 2-hydroxy-5-nonyl acetophenone.

4. The process of claim 1 or 2, wherein copper is recovered from the solution in step a) by precipitation of copper sulfide, followed by solid / liquid separation.

5. The process of claim 4, wherein sodium thiosulfate is added in step a) to precipitate copper sulfide.

6. A production plant comprising(1 ) a first solvent extraction (SX) unit (10) configured to receive an acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations (1000), the first SX unit (10) comprising i. an extraction module (11 ), ii. a scrubbing and stripping module (12),(2) at least one first continuous stirred-tank reactor (CSTR) (30) configured to receive an aqueous effluent (1001 ) of the extraction module (11 ) of the first SX unit (10), the first CSTR (30) comprising i. a dosing device for liquids, ii. heating / cooling means, iii. gas injection means,(3) at least one first solid / liquid separation device (70) configured to receive an effluent (3001) of the first CSTR (30),(4) at least one second continuous stirred-tank reactor (CSTR) (40) configured to receive an effluent (7001) of the first solid / liquid separation device (70), the second CSTR (40) comprising i. a dosing device for liquids, ii. heating / cooling means,(5) at least one second solid / liquid separation device (80) configured to receive an effluent 47001 ) of the second CSTR (40),(6) at least one third continuous stirred-tank reactor (CSTR) (50) configured to receive an aqueous effluent (8001) of the second solid / liquid separation device (80), the third CSTR (50) comprising i. a dosing device for liquids, ii. heating / cooling means,(7) at least one third solid / liquid separation device (90) configured to receive an effluent (5001) of the third CSTR (50),(8) at least one fourth continuous stirred-tank reactor (CSTR) (60) configured to receive an aqueous effluent (9001 ) of the third solid / liquid separation device (90), the fourth CSTR (60) comprising i. a dosing device for liquids, ii. heating / cooling means,(9) at least one fourth solid / liquid separation device (100) configured to receive an effluent (6001 ) of the fourth CSTR (60),(10) a second solvent extraction (SX) unit (20) configured to receive an aqueous effluent (10001 ) of the fourth solid / liquid separation device (100), the second SX unit (20) comprising i. an extraction module (21 ),ii. a scrubbing and stripping module (22),(11 ) a first crystallizer (110) configured to receive an aqueous effluent (2002) of the scrubbing and stripping module (22) of the second SX unit (20) and to produce crystals of a first metal salt.

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