Method for regulating particle size of Prussian white

Patent metadata

Field	Value
Publication number	US-12195347-B2
Application number	US-202218566386-A
Country	US
Kind code	B2
Filing date	Sep 22, 2022
Priority date	Aug 15, 2022
Publication date	Jan 14, 2025
Grant date	Jan 14, 2025

Abstract

A method includes: (1) adding a food-grade manganese sulfate solution and a complexing agent solution into a sodium ferrocyanide solution for a precipitation reaction to generate Prussian white crystal nucleus; (2) replacing the food-grade manganese sulfate solution with an industrial-grade manganese sulfate solution, and keeping other conditions unchanged, so that the Prussian white crystal nucleus grow continuously to obtain a slurry; and (3) successively subjecting the slurry to an aging reaction, solid-liquid separation, washing and drying to obtain a Prussian white product with a specific particle size. The food-grade manganese sulfate solution, and the sodium ferrocyanide solution are subjected to the precipitation reaction, and then the industrial-grade manganese sulfate solution are added to continue a precipitation reaction. The particle size of the Prussian white is regulated by controlling an adding time of the two manganese sulfate solutions.

First claim

The invention claimed is:

1. A method for regulating a particle size of Prussian white, comprising the following steps of:
(1) adding a food-grade manganese sulfate solution and a complexing agent solution into a sodium ferrocyanide solution for a precipitation reaction to generate Prussian white crystal nucleus;
(2) replacing the food-grade manganese sulfate solution with an industrial-grade manganese sulfate solution, and keeping other conditions unchanged, so that the Prussian white crystal nucleus grows continuously to obtain a slurry; and
(3) successively subjecting the slurry to an aging reaction, solid-liquid separation, washing and drying to obtain a Prussian white product with a specific particle size.

2. The method according to claim 1 , wherein in the step (1), the complexing agent solution comprises any one or a combination of at least two of a citric acid solution, a maleic acid solution, a wolfberry acid solution, an ethylenediamine tetraacetic acid solution, a sodium citrate solution, or aqueous ammonia.

3. The method according to claim 1 , wherein a concentration of the sodium ferrocyanide solution in the step (1) is 0.3 mol/L to 0.6 mol/L;
a concentration of the food-grade manganese sulfate solution is 0.4 mol/L to 2 mol/L; and
a concentration of the complexing agent solution is 0.4 mol/L to 15 mol/L.

4. The method according to claim 1 , wherein a molar ratio of the food-grade manganese sulfate solution to the complexing agent solution in the step (1) is (0.1 to 20):1;
the precipitation reaction is carried out at a temperature of 50° C. to 98° C.;
nitrogen is introduced during the precipitation reaction;
stirring is carried out during the precipitation reaction, and the stirring is carried out at a rate of 200 rpm to 500 rpm; and
an adding time of the food-grade manganese sulfate solution during the precipitation reaction is 0.12 hour to 2 hours.

5. The method according to claim 1 , wherein a particle size of the Prussian white crystal nucleus in the step (1) is 0.3 μm to 0.6 μm.

6. The method according to claim 1 , wherein a concentration of the industrial-grade manganese sulfate solution in the step (2) is 0.4 mol/L to 2 mol/L.

7. The method according to claim 1 , wherein a total adding time of the food-grade manganese sulfate solution in the step (1) and the industrial-grade manganese sulfate solution in the step (2) is 8 hours; and
a molar ratio of the sodium ferrocyanide to a total amount of the food-grade manganese sulfate solution in the step (1) and the industrial-grade manganese sulfate solution in the step (2) is (1 to 1.2): 1.

8. The method according to claim 1 , wherein the aging reaction is carried out at a temperature of 30° C. to 98° C.;
the aging reaction lasts for 3 hours to 24 hours;
the washing comprises pure water washing; and
the drying is carried out at a temperature of 150° C. to 180° C.

9. The method according to claim 1 , wherein the particle size of the Prussian white product in the step (3) is 0.8 μm to 2 μm.

10. The method according to claim 1 , comprising the following steps of:
(1) adding the food-grade manganese sulfate solution with a concentration of 0.4 mol/L to 2 mol/L and the complexing agent solution with a concentration of 0.4 mol/L to 15 mol/L into the sodium ferrocyanide solution with a concentration of 0.3 mol/L to 0.6 mol/L, introducing nitrogen, and carrying out the precipitation reaction at a temperature of 50° C. to 98° C. at a stirring rate of 200 rpm to 500 rpm to generate the Prussian white crystal nucleus with a particle size of 0.3 μm to 0.6 μm;
wherein the complexing agent solution comprising any one or a combination of at least two of a citric acid solution, a maleic acid solution, a wolfberry acid solution, an ethylenediamine tetraacetic acid solution, a sodium citrate solution, or aqueous ammonia; a molar ratio of the food-grade manganese sulfate solution to the complexing agent solution is (0.1 to 20): 1; and an adding time of the food-grade manganese sulfate solution during the precipitation reaction is 0.12 hour to 2 hours;
(2) replacing the food-grade manganese sulfate solution with the industrial-grade manganese sulfate solution with a concentration of 0.4 mol/L to 2 mol/L, and keeping other conditions unchanged, so that the Prussian white crystal nucleus grows continuously to obtain a slurry;
wherein a total adding time of the food-grade manganese sulfate solution in the step (1) and the industrial-grade manganese sulfate solution in the step (2) is 8 hours; and
a molar ratio of the sodium ferrocyanide to a total amount of the food-grade manganese sulfate solution in the step (1) and the industrial-grade manganese sulfate solution in the step (2) is (1 to 1.2): 1; and
(3) successively subjecting the slurry to the aging reaction at a temperature of 30° C. to 98° C. for 3 hours to 24 hours, solid-liquid separation, pure water washing and drying at a temperature of 150° C. to 180° C. to obtain the Prussian white product with a particle size of 0.8 μm to 2 μm.

11. The method according to claim 2 , wherein a concentration of the sodium ferrocyanide solution in the step (1) is 0.3 mol/L to 0.6 mol/L;
a concentration of the food-grade manganese sulfate solution is 0.4 mol/L to 2 mol/L; and
a concentration of the complexing agent solution is 0.4 mol/L to 15 mol/L.

12. The method according to claim 2 , wherein a molar ratio of the food-grade manganese sulfate solution to the complexing agent solution in the step (1) is (0.1 to 20): 1;
the precipitation reaction is carried out at a temperature of 50° C. to 98° C.;
nitrogen is introduced during the precipitation reaction;
stirring is carried out during the precipitation reaction, and the stirring is carried out at a speed of 200 rpm to 500 rpm; and
an adding time of the food-grade manganese sulfate solution during the precipitation reaction is 0.12 hour to 2 hours.

13. The method according to claim 2 , wherein a particle size of the Prussian white crystal nucleus in the step (1) is 0.3 μm to 0.6 μm.

14. The method according to claim 2 , wherein a concentration of the industrial-grade manganese sulfate solution in the step (2) is 0.4 mol/L to 2 mol/L.

15. The method according to claim 2 , wherein a total adding time of the food-grade manganese sulfate solution in the step (1) and the industrial-grade manganese sulfate solution in the step (2) is 8 hours; and
a molar ratio of the sodium ferrocyanide to a total amount of the food-grade manganese sulfate solution in the step (1) and the industrial-grade manganese sulfate solution in the step (2) is (1 to 1.2): 1.

16. The method according to claim 2 , wherein the aging reaction is carried out at a temperature of 30° C. to 98° C.;
the aging reaction lasts for 3 hours to 24 hours;
the washing comprises pure water washing; and
the drying is carried out at a temperature of 150° C. to 180° C.

17. The method according to claim 2 , wherein the particle size of the Prussian white product in the step (3) is 0.8 μm to 2 μm.

18. The method according to claim 3 , wherein a molar ratio of the food-grade manganese sulfate solution to the complexing agent solution in the step (1) is (0.1 to 20): 1;
the precipitation reaction is carried out at a temperature of 50° C. to 98° C.;
nitrogen is introduced during the precipitation reaction;
stirring is carried out during the precipitation reaction, and the stirring is carried out at a rate of 200 rpm to 500 rpm; and
an adding time of the food-grade manganese sulfate solution during the precipitation reaction is 0.12 hour t

Assignees

• Guangdong Brunp Recycling Technology Co Ltd
• Hunan Brunp Recycling Tech Co Ltd

Inventors

• Li Yongguang
• Li Changdong
• Xu Xueliu
• Liu Genghao
• Ruan Dingshan

Classifications

• H01M4/58

  of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates · CPC title

• H01M10/054

  Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium · CPC title

• C01C3/12 Primary

  Simple or complex iron cyanides · CPC title

• C01P2006/11

  Powder tap density · CPC title

• C01P2004/61

  Micrometer sized, i.e. from 1-100 micrometer · CPC title