Adaptable processes and systems for purifying co-precipitated or independent streams of manganese, nickel, and cobalt from lithium-ion battery waste streams

A process for recovering manganese (Mn), cobalt (Co), and nickel (Ni) from a lithium-ion battery waste stream, the process comprising:

• purifying a waste liquid stream originating from the lithium-ion battery waste stream, wherein the waste liquid stream comprises sulfuric acid (H2SO4), manganese (Mn), cobalt (Co), and nickel (Ni) to remove fluorine (F), phosphorous (P), and one or more impurity metals selected from the group consisting of:
• copper (Cu), iron (Fe), zinc (Zn), aluminum (Al), and titanium (Ti), wherein the purifying includes:
• (i) removing copper (Cu), iron (Fe), and zinc (Zn) from the waste liquid stream by a solvent extraction process;
• (ii) adding a source of calcium oxide and a first oxidant to the waste liquid stream to remove fluorine (F) by precipitating calcium fluoride (CaF2);
• and
• (iii) adjusting pH of the waste liquid stream to greater than or equal to about 3 to less than or equal to about 5 for a first duration and further adjusting pH of the waste liquid stream to greater than or equal to about 4.8 to less than or equal to about 7.2 to remove one or more impurity compounds comprising an element selected from the group consisting of:
• copper (Cu), iron (Fe), zinc (Zn), aluminum (Al), and titanium (Ti), phosphorus (P), and lead (Pb), and combinations thereof;
• processing the waste liquid stream in a system having a first metal recovery unit and a second metal recovery unit, the second metal recovery unit including a manganese (Mn) recovery unit to recover a first product comprising manganese (Mn), a nickel (Ni) recovery unit to recover a second product comprising nickel (Ni), and a cobalt (Co) recovery unit to recover a third product comprising cobalt (Co), by either recovering a co-precipitated product comprising manganese (Mn), nickel (Ni), and cobalt (Co) in the first metal recovery unit or recovering the first product comprising manganese (Mn), the second product comprising nickel (Ni), and the third product comprising (Co) in the second metal recovery unit, wherein:
• the recovering the co-precipitated product in the first metal recovery unit comprises separating the manganese (Mn), nickel (Ni), and cobalt (Co) from the waste liquid stream by conducting a co-precipitation process in a reactor by increasing pH to greater than or equal to about 10 to form a precipitated solid and separating the precipitated solid from the waste liquid stream to recover the co-precipitated product comprising manganese (Mn), nickel (Ni), and cobalt (Co);
• or
• the recovering the first product comprising manganese (Mn), the second product comprising nickel (Ni), and the third product comprising (Co) in the second metal recovery unit comprises separating manganese (Mn) from the waste liquid stream to form the first product comprising manganese (Mn) by a process comprising:
• (iv) introducing a second oxidant to the waste liquid stream to form solid manganese dioxide (MnO2);
• (v) reacting the waste liquid stream with ozone (O3) to form solid manganese dioxide (MnO2);
• or
• (vi) both (iv) and (v);
• removing the solid manganese dioxide (MnO2) from the waste liquid stream;
• and separating nickel (Ni) and cobalt (Co) from the waste liquid stream by:
• (vii) adding sulfuric acid (H2SO4) and a third oxidant to the waste liquid stream, followed by adjusting pH to greater than or equal to about 4, adding sodium hypochlorite (NaClO) to form cobalt oxyhydroxide (CoOOH), passing the waste liquid stream through a first filter to form a first retentate comprising cobalt oxyhydroxide (CoOOH) and a first filtrate comprising nickel (Ni) and liquid;
• (viii) recovering cobalt (Co) from the first retentate by purifying the cobalt oxyhydroxide (CoOOH) in the first retentate and adding sulfuric acid (H2SO4) and a fourth oxidant to the first retentate followed by adjusting pH to greater than or equal to about 4, passing the first retentate through a second filter to form a second retentate comprising cobalt oxyhydroxide (CoOOH) and a second filtrate;
• and
• (ix) recovering cobalt (Co) from the second retentate by purifying the cobalt oxyhydroxide (CoOOH) in the second retentate by adding sulfuric acid (H2SO4) and a fifth oxidant to the second retentate to form cobalt sulfate (CoSO4), followed by one or more of the following processes to form the third product comprising (Co):
• a. removing liquid from the second retentate to recover cobalt sulfate (CoSO4);
• and/or
• b. adjusting pH of the second retentate to greater than or equal to about 9 to precipitate a cobalt hydroxide product comprising one or more of cobalt hydroxide (Co(OH)2) or cobalt oxyhydroxide (CoOOH);
• (x) recovering nickel (Ni) from the second filtrate as the second product comprising nickel (Ni) by one of the following processes:
• c. removing liquid from the second filtrate to recover nickel sulfate (NiSO4);
• and/or
• d. adjusting pH of the second filtrate to greater than or equal to about 9 to precipitate nickel hydroxide (Ni(OH)2).

A system for recovering manganese (Mn), cobalt (Co), and nickel (Ni) from a lithium-ion battery waste stream, the system comprising:

• a first metal recovery unit configured to recover a co-precipitated product comprising manganese (Mn), nickel (Ni), and cobalt (Co) from a waste liquid stream originating from the lithium-ion battery waste stream comprising manganese (Mn), nickel (Ni), and cobalt (Co), the first metal recovery unit comprising:
• a co-precipitation reactor that comprises:
• a plurality of co-precipitation reactor inlets that receive the waste liquid stream, a chelating agent, and sodium hydroxide (NaOH);
• a co-precipitation reactor agitator;
• and
• at least one co-precipitation reactor outlet, wherein the co-precipitation reactor is in thermal communication with a heat source and is configured to generate a co-precipitated product comprising manganese (Mn), nickel (Ni), and cobalt (Co);
• a second metal recovery unit configured to recover a first product comprising manganese (Mn) in a manganese (Mn) recovery unit, a second product comprising nickel (Ni) in a nickel (Ni) recovery unit, and a third product comprising cobalt (Co) in a cobalt (Co) recovery unit, wherein:
• the manganese (Mn) recovery unit comprises at least one first reactor, a source of a first oxidant selected from the group consisting of:
• potassium permanganate (KMnO4), sodium permanganate (NaMnO4), and combinations thereof, a source of ozone (O3), a first filter downstream of the at least one first reactor, wherein the at least one first reactor has a plurality of first inlets receiving the first oxidant, the ozone (O3), and the waste liquid stream, a first agitator, and a first outlet through which the waste liquid stream exits to enter the first filter for separation into a first filtrate and a first retentate comprising manganese dioxide (MnO2);
• a separation unit that receives the first filtrate, the separation unit having a separation reactor, a second filter downstream of the separation reactor, a source of a first base, a source of a first acid, a source of a second oxidant, and a source of sodium hypochlorite (NaClO), wherein the separation reactor has a plurality of second inlets receiving the first base, the first acid, the second oxidant, the sodium hypochlorite (NaClO), and the first filtrate, a second agitator, and a second outlet through which the first filtrate exits to enter a second filter for separation into a second filtrate and a second retentate comprising cobalt oxyhydroxide (CoOOH);
• a cobalt (Co) recovery unit downstream of the separation unit that receives the second retentate comprising cobalt oxyhydroxide (CoOOH), the cobalt (Co) recovery unit comprising:
• a source of at least a second acid,
• a source of a third oxidant,
• at least a third reactor having a plurality of third inlets receiving the second acid, the third oxidant, and the second retentate, a third agitator, and a third outlet through which the second retentate exits,
• one or more cobalt (Co) processing units downstream from the at least a third reactor selected from:
• (i) one or more chromatographic columns for separating nickel (Ni) from cobalt (Co);
• (ii) a first evaporator or crystallizer to form cobalt sulfate (CoSO4);
• and/or
• (iii) a first precipitator to form a cobalt hydroxide product comprising one or more of cobalt hydroxide (Co(OH)2) or cobalt oxyhydroxide (CoOOH);
• and
• a nickel (Ni) recovery unit downstream of the separation unit that receives the second filtrate, the nickel (Ni) recovery unit comprising one or more of:
• a second evaporator/crystallizer to form nickel sulfate (NiSO4);
• a precipitator reactor to form nickel hydroxide (Ni(OH)2);
• and/or
• at least a fourth reactor to form nickel sulfate (NiSO4) having a plurality of fourth inlets receiving Ni(OH)2, a third acid, and a fourth oxidant, a fourth agitator, and a fourth outlet through which a stream comprising nickel sulfate (NiSO4) exits;
• a fluid conduit system for establishing fluid communication within the first metal recovery unit including the co-precipitation reactor and the second metal recovery unit including the manganese (Mn) recovery unit, the separation unit, the cobalt (Co) recovery unit, and the nickel (Ni) recovery unit;
• and at least one pump for circulating fluids within the fluid conduit system.