# US 12,006,227 B2 · Nickel-iron wet treatment method and application thereof

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- Number: US 12,006,227 B2
- Document ID: US12006227B2
- Status: Granted
- Kind: B2
- Application number: 18/260,241
- Filed: 2022-06-06
- Published: 2024-02-01
- Granted: 2024-06-11
- Earliest claimed: 2021-07-20
- Assignees: Guangdong Brunp Recycling Technology Co., Ltd.; Hunan Brunp Recycling Technology Co., Ltd.; Hunan Brunp Ev Recycling Co., Ltd.
- Applicants: Guangdong Brunp Recycling Technology Co., Ltd.; Hunan Brunp Recycling Technology Co., Ltd.; Hunan Brunp Ev Recycling Co., Ltd.
- Inventors: Haijun Yu; Yinghao Xie; Aixia Li; Xuemei Zhang; Changdong Li
- Web page: https://patentgrep.com/patent/US12006227B2

## CPC

- C01G 49/06: Ferric oxide [Fe2O3]
- C22B 23/043: {Sulfurated acids or salts thereof}
- C01G 49/02: Oxides; Hydroxides {(C01G49/0018 takes precedence)}
- C01G 53/01: Preparation or separation involving a liquid-liquid extraction, an adsorption or an ion-exchange
- C01G 53/10: Sulfates
- C22B 1/24: Binding; Briquetting {; Granulating}
- C22B 3/08: Sulfuric acid {, other sulfurated acids or salts thereof}
- C22B 3/22: by physical processes, e.g. by filtration, by magnetic means {, or by thermal decomposition} (treatment or purification of solutions by liquid-liquid extraction C22B3/26)
- C22B 3/3842: {Phosphinic acid, e.g. H2P(O)(OH)}
- C22B 3/3844: {Phosphonic acid, e.g. H2P(O)(OH)2}
- C22B 3/408: {using a mixture of phosphorus-based acid derivatives of different types}
- C22B 3/44: by chemical processes (treatment or purification of solutions by liquid-liquid extraction C22B3/26, by ion-exchange extraction C22B3/42)
- C22B 7/005: {Separation by a physical processing technique only, e.g. by mechanical breaking}
- C22B 7/007: {by acid leaching}
- C22B 23/0461: {by chemical methods}
- Y02P 10/20: Recycling
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C22B: PRODUCTION AND REFINING OF METALS (electrolytic C25); PRETREATMENT OF RAW MATERIALS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Disclosed are a nickel-iron wet treatment method and an application thereof. The treatment method comprises: in a high-pressure oxygen environment, mixing a crushed nickel-iron material, sulphuric acid and a corrosion aid, performing an acid leaching reaction, then performing solid-liquid separation on slurry subjected to acid leaching, adding an oxidant into the obtained filtrate, performing heating, removing the corrosion aid, adding a precipitating agent into the filtrate, controlling the pH value of the filtrate, and performing solid-liquid separation to obtain a ferric hydroxide precipitate and a nickel-containing filtrate; and performing extraction and back extraction on the nickel-containing filtrate to prepare battery-grade nickel sulphate. According to the present invention, the nickel-iron is subjected to oxidation acid dissolution in cooperation with the corrosion aid under the high-pressure oxygen and acidic conditions; the nickel-iron is extremely prone to oxidation in the high-pressure oxygen environment; and a strong oxidant is added into the filtrate subsequently, so that ferrous ions in the filtrate are completely converted into ferric ions, and the corrosion aid can be oxidized to generate pollution-free carbon dioxide and water, thereby avoiding the impact of the corrosion aid on the subsequent extraction process.

## Claims

### Claim 1

A wet treatment method for ferronickel, comprising the following steps:
(1) pretreating a raw material: ferronickel having a nickel content of 22.35% is pulverized to powders or particles;
(2) performing first high-pressure acid leaching: in a high-pressure oxygen atmosphere at 6.5 MPa and 90° C., the pulverized ferronickel obtained in step (1) is subjected to acid leaching with sulfuric acid having a concentration of 3 mol/L, and performing acid leaching reaction; acetic acid is added in to obtain a slurry mixture; a solid-liquid ratio of the slurry mixture is 1:100 g/mL, and the acid leaching reaction is performed for 3 h;
(3) filtrating: after completing the reaction in step (2), filtration is performed to obtain a filtrate and a residue; the pulverized ferronickel obtained in step (1) is added in the filtrate and subjected to a second leaching to displace the small number of copper ions; filtration is performed again to obtain a ferronickel reside and a copper-removed filtrate; the ferronickel residue is reused in the first high-pressure acid leaching in step (2); after a plurality of cycles, when the ferronickel residue is tested to reach a predetermined copper content, the ferronickel residue is subjected to leaching at normal pressure to obtain a leaching solution and a leaching residue; the leaching solution is reused in the first high-pressure acid leaching, and the leaching residue is conveyed to a copper factory for further treatment;
(4) precipitating: ammonium chlorate is added in the copper-removed filtrate in step (3) to oxidize ferrous ions in the copper-removed filtrate, and heated at a temperature between 60° C. to 70° C. to remove the acetic acid, so as to prevent the acetic acid from affecting the subsequent extracting process;
(5) precipitating under control: ammonium hydroxide is added in the filtrate obtained in step (4), and pH of the filtrate is controlled in a range of 3 to 3.5, and filtration is performed again to obtain a ferric hydroxide precipitate and a nickel-containing filtrate; the ferric hydroxide precipitate is washed and heated to obtain ferric oxide red.

### Claim 2

A wet treatment method for ferronickel, comprising the following steps:
(1) pretreating a raw material: ferronickel having a nickel content of 25.85% is pulverized to powders or particles;
(2) performing high-pressure acid leaching: in a high-pressure oxygen atmosphere at 3.0 MPa and 50° C., the pulverized raw material obtained in step (1) is subjected to acid leaching with sulfuric acid having a concentration of 8 mol/L, and acetylacetone is added in to obtain a slurry mixture; a solid-liquid ratio of the slurry mixture is 1:200 g/mL, and the acid leaching reaction is performed for 1.5 h;
(3) filtrating: after completing the reaction in step (2), filtration is performed to obtain a filtrate and a residue; the pulverized ferronickel obtained in step (1) is added in the filtrate and subjected to a second leaching to displace the small number of copper ions; filtration is performed again to obtain a ferronickel reside and a copper-removed filtrate; the ferronickel residue is reused in the first high-pressure acid leaching in step (2); after a plurality of cycles, when the ferronickel residue is tested to reach a predetermined copper content, the ferronickel residue is subjected to leaching at normal pressure to obtain a leaching solution and a leaching residue; the leaching solution is reused in the first high-pressure acid leaching, and the leaching residue is conveyed to a copper factory for further treatment;
(4) precipitating process: ammonium nitrate is added in the copper-removed filtrate in step (3) to oxidize ferrous ions in the copper-removed filtrate, and heated at a temperature between 75° C. to 85° C. to remove the acetylacetone, so as to prevent the acetylacetone from affecting the subsequent extracting process;
(5) precipitating under control: ammonium hydroxide is added in the filtrate obtained in step (4), and pH of the filtrate is controlled in a range of 3 to 3.5, and filtration is performed again to obtain a ferric hydroxide precipitate and a nickel-containing filtrate; the ferric hydroxide precipitate is washed and heated to obtain ferric oxide red.

### Claim 3

A wet treatment method for ferronickel, comprising the following steps:
(1) pretreating a raw material: ferronickel having a nickel content of 55.35% is pulverized to powders or particles;
(2) performing high-pressure acid leaching: in a high-pressure oxygen atmosphere at 5.0 MPa and 70° C., the pulverized raw material obtained in step (1) is subjected to acid leaching with sulfuric acid having a concentration of 5 mol/L, and oxalic acid is added in to obtain a slurry mixture; a solid-liquid ratio of the slurry mixture is 1:300 g/mL, and the acid leaching reaction is performed for 3 hours;
(3) filtrating: after completing the reaction in step (2), filtration is performed to obtain a filtrate and a residue; the pulverized ferronickel obtained in step (1) is added in the filtrate and subjected to a second leaching to displace the small number of copper ions; filtration is performed again to obtain a ferronickel residue and a copper-removed filtrate; the ferronickel residue is reused in the first high-pressure acid leaching in step (2); after a plurality of cycles, when the ferronickel residue is tested to reach a predetermined copper content, the ferronickel residue is subjected to leaching at normal pressure to obtain a leaching solution and a leaching residue; the leaching solution is reused in the first high-pressure acid leaching, and the leaching residue is conveyed to a copper factory for further treatment;
(4) precipitating: ammonium nitrate is added in the copper-removed filtrate in step (3) to oxidize ferrous ions in the copper-removed filtrate, and heated at a temperature between 80° C. to 95° C. to remove the oxalic acid, so as to prevent the oxalic acid from affecting the subsequent extracting process;
(5) precipitating under control: ammonium hydroxide is added in the filtrate obtained in step (4), and pH of the filtrate is controlled in a range of 3 to 3.5, and filtration is performed again to obtain a ferric hydroxide precipitate and a nickel-containing filtrate; the ferric hydroxide precipitate is washed and heated to obtain ferric oxide red.