Method for the hydrometallurgical recovery of lithium from the lithium manganese oxide-containing fraction of used galvanic cells
First Claim
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1. A method for hydrometallurgical recovery of lithium from a fraction of used galvanic cells containing lithium manganese oxide, the method comprising the steps of:
- adding the fraction of used galvanic cells containing lithium manganese oxide with a particle size up to 500 μ
m to a hyper-stoichiometric amount of oxalic acid based on the manganese content in the lithium manganese oxide, wherein a 0.1 to 1.0 molar excess of oxalic acid is used, and is solubilized in a solid/liquid ratio in the range of 10 g/l to 250 g/l at a temperature in the range of 30°
C. to 70°
C. to form a lithium-containing solution;
separating the lithium-containing solution from a remaining residue; and
washing the remaining residue at least twice to form a washing solution containing lithium;
wherein the separated lithium-containing solution and the washing solution containing lithium are combined, a dissolved manganese residue content is reduced by precipitation as hydroxide, separated and washed, and a remaining lithium-containing solution is further purified by conversion into a carbonate, chloride or sulfate.
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Abstract
The invention relates to a method for the hydrometallurgical recovery of lithium from the lithium manganese oxide-containing fraction of used galvanic cells.
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17 Claims
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1. A method for hydrometallurgical recovery of lithium from a fraction of used galvanic cells containing lithium manganese oxide, the method comprising the steps of:
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adding the fraction of used galvanic cells containing lithium manganese oxide with a particle size up to 500 μ
m to a hyper-stoichiometric amount of oxalic acid based on the manganese content in the lithium manganese oxide, wherein a 0.1 to 1.0 molar excess of oxalic acid is used, and is solubilized in a solid/liquid ratio in the range of 10 g/l to 250 g/l at a temperature in the range of 30°
C. to 70°
C. to form a lithium-containing solution;separating the lithium-containing solution from a remaining residue; and washing the remaining residue at least twice to form a washing solution containing lithium; wherein the separated lithium-containing solution and the washing solution containing lithium are combined, a dissolved manganese residue content is reduced by precipitation as hydroxide, separated and washed, and a remaining lithium-containing solution is further purified by conversion into a carbonate, chloride or sulfate. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16)
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15. A method comprising the steps of:
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(A) contacting a fraction of used galvanic cells containing lithium manganese oxide with oxalic acid, wherein the fraction containing lithium manganese oxide has a particle size up to 500 μ
m and a mole ratio of lithium manganese oxide to oxalic acid is in the range of from 1;
4 to 1;
4.5;(B) solubilizing the lithium contained in the fraction containing lithium manganese oxide at a solid/liquid ratio in the range of 10 g/l to 250 g/l at a temperature in the range of 30°
C. to 70°
C. to form a lithium-containing solution;(C) separating the lithium-containing solution from a remaining residue; (D) washing the remaining residue at least twice to form a washing solution containing lithium; (E) combining the lithium-containing solution from step (C) and the washing solution containing lithium from step (D) to form a combined solution containing lithium; (F) reducing a dissolved manganese residue content in the combined solution containing lithium by precipitation of manganese hydroxide; (G) separating the precipitated manganese hydroxide from the combined solution containing lithium to form a remaining lithium-containing solution; and (H) purifying the remaining lithium-containing solution by conversion into lithium carbonate, lithium chloride or lithium sulfate; wherein heat is supplied by reaction heat in step (B), without an additional heat source, and the temperature is controlled by regulating the mole ratio of lithium manganese oxide to oxalic acid. - View Dependent Claims (17)
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Specification