Method for producing high-purity manganese sulfate monohydrate and high-purity manganese sulfate monohydrate produced by the method
View Patent ↗A method for producing high-purity manganese sulfate monohydrate from a low-grade composition includes acquiring a primary leached manganese solution by adding sulfuric acid and a reductant to a low-grade manganese-containing composition and leaching manganese therefrom; acquiring a secondary leached manganese solution from which primary impurities have been eliminated by adding calcium hydroxide to the primary leached manganese solution; acquiring a tertiary leached manganese solution from which secondary impurities have been eliminated by adding sulfides to the secondary leached manganese solution; acquiring manganese oxide from precipitating manganese by using sodium hydroxide in the tertiary leached manganese solution so as to control the pH thereof; adding sulfuric acid to the manganese oxide and redissolving; and drying the redissolved manganese oxide and acquiring high-purity manganese sulfate monohydrate. Thus the present invention allows production of high-purity manganese sulfate monohydrate from a low-grade manganese-containing composition, for use as material for a secondary battery.
1. A method for producing high-purity manganese sulfate monohydrate (MnSO 4 .H 2 O), comprising:
leaching manganese from a low-purity manganese-containing substance with sulfuric acid (H 2 SO 4 ) and a reductant to give a first manganese leachate;
obtaining a second manganese leachate by removing a first impurity from the first manganese leachate with calcium hydroxide (Ca(OH) 2 );
obtaining a third manganese leachate by removing a second impurity from the second manganese leachate with a sulfide;
precipitating manganese as a manganese oxide by adjusting pH of the third manganese leachate with sodium hydroxide (NaOH);
re-dissolving the manganese oxide with sulfuric acid;
drying the re-dissolved manganese oxide to afford high-purity manganese sulfate monohydrate (MnSO 4 .H 2 O).
2. The method of claim 1 , wherein sulfuric acid is added in an amount 0.5 to 3 times a mole content of manganese in the low-purity manganese-containing substance in the manganese leaching step.
3. The method of claim 2 , wherein the reductant of the manganese leaching step includes an oxalate (C 2 O 4 2− )-containing reagent, coke or sulfurous acid (SO 2 ) gas, and is added in an amount 0.1 to 2 times a mole content of manganese in the low-purity manganese-containing substance.
4. The method of claim 3 , wherein the oxalate-containing reagent includes oxalic acid (H 2 C 2 O 4 .2H 2 O) or sodium oxalate (Na 2 C 2 O 4 ).
5. The method of claim 4 , wherein the first impurity includes iron, and the second manganese leachate-obtaining step further comprises adding potassium and an oxidant.
6. The method of claim 5 , wherein the calcium hydroxide (Ca(OH) 2 ) is added in such an amount that the first manganese leachate has a pH of 2 to 3.
7. The method of claim 6 , further comprising heating the second manganese leachate to a temperature of 80 to 120° C. after the addition of calcium hydroxide.
8. The method of claim 7 , further comprising adjusting acidity of the first manganese leachate to a pH of 5 or higher with an additional amount of calcium hydroxide.
9. The method of claim 8 , wherein potassium is added in an amount 0.5 to 3 times a mole content of iron.
10. The method of claim 9 , wherein potassium includes potassium sulfate (K 2 SO 4 ), and the oxidant includes hydrogen peroxide (H 2 O 2 ).
11. The method of claim 10 , wherein the sulfide includes at least one selected from among sodium sulfide (Na 2 S), calcium sulfide (CaS) and hydrogen sulfide (H 2 S) and is added in an amount 2 to 5 times a total mole of the second impurity in the third manganese leachate-obtaining step.
12. The method of claim 11 , wherein the third manganese leachate-obtaining step further comprises discarding the second impurity as a sulfide slurry through solid-liquid separation.
13. The method of claim 12 , wherein the manganese precipitating step further comprises diluting the third manganese leachate in water so that the third manganese leachate has a manganese content of 50 to 100 g/L, and the acidity of the third manganese leachate is adjusted to a pH of 8 to 9 with sodium hydroxide (NaOH) to precipitate manganese in a non-oxidative atmosphere.
14. The method of claim 13 , wherein the manganese precipitating step further comprises washing the manganese oxide with water of 70 to 100° C.
15. The method of claim 14 , wherein sulfuric acid is added in an amount 0.1 to 3 times a mole content of manganese in the manganese oxide in the re-dissolving step.
16. The method of claim 15 , wherein the re-dissolving step further comprises adding the manganese oxide obtained in the manganese precipitating step to the re-dissolved manganese oxide in sulfuric acid to neutralize the re-dissolved manganese oxide to a pH of 5 to 6.
17. The method of claim 16 , wherein the re-dissolving step further comprises performing solid-liquid separation on the neutralized manganese oxide to give fourth manganese leachate.
18. The method of claim 17 , wherein the drying step is carried out by vacuum vaporization to afford manganese sulfate monohydrate as a crystal.
19. A method for producing high-purity manganese sulfate monohydrate, comprising:
leaching manganese from a low-purity manganese-containing substance with hydrochloric acid and a reductant to give a first manganese leachate;
obtaining a second manganese leachate by removing a first impurity from the first manganese leachate with potassium hydroxide;
obtaining a third manganese leachate by removing a second impurity from the second manganese leachate with a sulfide; and
adding potassium hydroxide to the third manganese leachate to precipitate manganese as a manganese oxide and adding sulfuric acid to the manganese oxide.
20. The method of claim 19 , wherein hydrochloric acid is added in an amount 2 to 4 times a mole content of manganese in the low-purity manganese-containing substance, and the reductant is added in an amount 0.5 to 2 times a mole content of manganese in the low-purity manganese-containing substance.
21. The method of claim 20 , wherein the reductant includes an oxalate (C 2 O 4 2− )-containing reagent, coke or sulfurous acid (SO 2 ) gas.
22. The method of claim 21 , wherein the first impurity includes iron and potassium hydroxide is used as a 1 M solution to adjust acidity of the first manganese leachate to a pH of 5 or higher to remove the first impurity in the second manganese leachate-obtaining step.
23. The method of claim 22 , wherein the sulfide includes sodium sulfide includes at least one selected from among sodium sulfide (Na 2 S), calcium sulfide (CaS) and hydrogen sulfide (H 2 S), and is added in an amount 10 to 50 times a total mole of the second impurity to remove the second impurity in the third manganese obtaining step.
24. The method of claim 23 , wherein potassium hydroxide is added in such an amount as to adjust acidity of the third manganese leachate to a pH of 7 to 9 to produce manganese sulfate monohydrate.
25. The method of claim 24 , further comprising adding sulfuric acid in an amount 0.5 to 1.5 times a mole content of manganese in the manganese oxide, adding an additional amount of the manganese oxide after the addition of sulfuric aid, and performing solid-liquid separation to give a fourth manganese leachate.
26. The method of claim 25 , further comprising vaporizing the fourth manganese leachate in a vacuum to afford manganese sulfate monohydrate.