CN112359225A - Selective leaching process of rough cobalt hydroxide ore - Google Patents
Selective leaching process of rough cobalt hydroxide ore Download PDFInfo
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- CN112359225A CN112359225A CN202011258461.0A CN202011258461A CN112359225A CN 112359225 A CN112359225 A CN 112359225A CN 202011258461 A CN202011258461 A CN 202011258461A CN 112359225 A CN112359225 A CN 112359225A
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- China
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- ore
- slurry
- leaching
- slurrying
- acid leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a selective leaching process of rough cobalt hydroxide ore, which comprises the following steps: stirring and slurrying raw ore according to the ratio of water to water of 1:3, heating to 60-70 ℃ after slurrying, adding concentrated sulfuric acid to enable the pH of slurry to be 0.45-0.5, carrying out first-stage leaching, preferentially dissolving bivalent cobalt and trivalent iron, stirring for 5-10 min, and filtering; directly feeding the acid leaching solution into a transfer tank to remove iron, and performing secondary slurrying on acid leaching residues according to the ratio of acid leaching residues to water being 1: 2; and after secondary slurrying of the acid leaching residue, heating to 50-60 ℃, adding sodium metabisulfite for secondary reduction leaching, and maintaining the pH of the slurry to be 1.0-1.5 until the reduction potential is lower than 240 mV. Adding manganese dioxide ore into the treated slurry for pre-oxidation treatment, wherein the manganese dioxide is used for converting Fe into Fe2+Is oxidized into Fe3+When Fe is present in the slurry2+The content is lower than 0.05g/L, and the slurry is transferred into the middleIron is to be removed from the rotary tank. Compared with the traditional process, the method avoids the repeated action of the reducing agent and the oxidizing agent, and greatly saves auxiliary materials; not only improves the safety, but also shortens the reaction time and reduces the production cost.
Description
Technical Field
The invention relates to a leaching process of cobalt ore, in particular to a selective leaching process of rough cobalt hydroxide ore.
Background
Cobalt is an important strategic metal, and elemental cobalt and compounds of cobalt thereof are widely applied, and especially, the demand in the field of lithium batteries is gradually increased. The cobalt resource is poor in China and is mostly associated ore, more than 90% of the cobalt resource depends on African import and comprises hydrocobalt ore, cobalt-nickel sulfide ore, copper-cobalt alloy, crude cobalt hydroxide, cobalt carbonate and the like, wherein the cobalt content of the crude cobalt hydroxide ore is 30% -40%, and the iron content is about 3% -4%. At present, the rough cobalt hydroxide ore is mainly obtained into a cobalt-rich solution through main processes such as reduction acid leaching and the like, but because sulfur dioxide is used and sodium metabisulfite is used as a reducing agent to generate sulfur dioxide gas, the field operation environment is poor, a large amount of liquid alkali is consumed when the sulfur dioxide is fed into an absorption tower after being effectively absorbed, and an oxidant is required to be added after a large amount of Fe is reduced, so that the production cost is high.
Disclosure of Invention
The invention aims to provide a selective leaching process of crude cobalt hydroxide ore with high iron content, and aims to solve the technical problems of long reaction time, high production cost and strong pollution in the production process in the leaching process of the crude cobalt hydroxide ore with high iron content at the present stage.
A selective leaching process of crude cobalt hydroxide ore comprising the steps of:
1) primary acid leaching: stirring and slurrying raw ore according to the ratio of water to ore of 1:3, heating to 60-70 ℃ after slurrying, adding concentrated sulfuric acid to adjust the pH of slurry to 0.45-0.5, stirring for 5-10 min, and filtering; directly feeding the acid leaching solution into a transfer tank to remove iron, and performing secondary slurrying on acid leaching residues according to the ratio of acid leaching residues to water being 1: 2;
2) and (3) secondary reduction leaching: heating the acid leaching residue to 50-60 ℃ after secondary slurrying, adding sodium metabisulfite, and maintaining the pH of the slurry to be 1.0-1.5 until the reduction potential is lower than 240 mV;
3) pre-oxidation: adding the second component after the treatment of the step 2)Manganese ore oxidation of Fe2+Is oxidized into Fe3+When Fe is present in the slurry2+The content is lower than 0.05g/L, and the slurry is transferred into a transit tank to be deironized.
Further, the grade of manganese in the manganese dioxide ore is 30-50%.
Further, the iron content of the crude cobalt hydroxide ore is 3% -4%.
Compared with the traditional old process, the selective leaching process of the rough cobalt hydroxide ore with high iron content provided by the invention avoids the repeated action of the reducing agent and the oxidizing agent, and greatly saves auxiliary materials; as most of trivalent iron in the raw materials directly enters the working procedure of neutralization and deironing, the amount of reduced ferrous iron is greatly reduced, so that the oxidizing agent in the oxidation working procedure replaces sodium chlorate by natural manganese dioxide ore and has more technical and economic feasibility. Not only improves the safety of production, but also shortens the reaction time and reduces the production cost.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention.
Stirring and slurrying raw ore according to the ratio of water to water of 1:3, heating to 60-70 ℃ after slurrying, adding concentrated sulfuric acid to enable the pH of slurry to be 0.45-0.5, carrying out first-stage leaching, preferentially dissolving bivalent cobalt and trivalent iron, stirring for 5-10 min, and filtering by using a filter press; directly feeding the obtained acid leaching solution into a transfer tank for iron removal, and performing secondary slurrying on the obtained acid leaching residue according to the ratio of acid leaching residue to water being 1: 2; and after secondary slurrying of the acid leaching residue, heating to 50-60 ℃, adding sodium metabisulfite for secondary reduction leaching, and maintaining the pH of the slurry to be 1.0-1.5 until the reduction potential is lower than 240mV, so that trivalent cobalt and iron are dissolved and converted into divalent cobalt and iron. Adding manganese dioxide ore into the slurry after the treatment for pre-oxidation treatment, wherein the calculation formula of the addition amount of the manganese dioxide ore is
Wherein V is the volume of the cobalt ore leaching solution,
is Fe in the slurry2+Concentration of (A), TMnThe grade of manganese in the manganese dioxide ore. Manganese dioxide to convert Fe2+Is oxidized into Fe3+When Fe is present in the slurry2+The content is lower than 0.05g/L, and the slurry is transferred into a transit tank to be deironized.
Example 1
Stirring and slurrying crude cobalt hydroxide ore with iron content of 3% according to the ratio of ore to water being 1:3, heating to 60 ℃ after slurrying, adding concentrated sulfuric acid to adjust the pH value of slurry to be 0.5, stirring for 5min-10min, and filtering by using a filter press; and directly feeding the acid leaching solution into a transfer tank to remove iron, carrying out secondary slurrying on the acid leaching residue according to the ratio of acid leaching residue to water being 1:2, wherein after primary leaching, the leaching rate of cobalt is 70%, and the leaching rate of iron is 80%. And after slurrying the acid leaching residue, heating to 60 ℃, adding sodium metabisulfite for secondary reduction leaching, and maintaining the pH of the slurry to be 1.0 until the potential is lower than 240 mV. Adding manganese dioxide ore with the manganese grade of 42.72% into the cobalt ore leachate after the treatment for pre-oxidation treatment, wherein the adding amount of the manganese dioxide ore is detected according to the detection of Fe2+The content is calculated as Fe in the slurry2+The content is lower than 0.05g/L, and the slurry is transferred into a transit tank to be deironized.
Example 2
Stirring and slurrying crude cobalt hydroxide ore with iron content of 4% according to the ratio of ore to water being 1:3, heating to 70 ℃ after slurrying, adding concentrated sulfuric acid to adjust the pH value of slurry to be 0.45, stirring for 5min-10min, and filtering by using a filter press; directly feeding the acid leaching solution into a transfer tank to remove iron, carrying out secondary slurrying on acid leaching residues according to the ratio of acid leaching residues to water being 1:2, wherein after primary leaching, the leaching rate of cobalt is 75%, and the leaching rate of iron is 85%; heating the acid leaching residue to 50 ℃ after slurrying, adding sodium pyrosulfite to perform secondary reduction leaching, maintaining the pH of the slurry to be 1.5 until the potential is lower than 240mV, adding manganese dioxide ore with the manganese grade of 30.52% into the cobalt ore leachate after the treatment to perform pre-oxidation treatment, wherein the adding amount of the manganese dioxide ore is detected according to Fe2+The content is calculated as Fe in the slurry2+The content is lower than 0.05g/L, and the slurry is transferred into a transit tank to be deironized.
According to the selective leaching process of the crude cobalt hydroxide ore, as most of trivalent in the raw materials directly enter the neutralization and iron removal process, the amount of reduced ferrous iron is greatly reduced, and the oxidizing agent in the oxidation process replaces sodium chlorate by natural manganese dioxide ore, so that the selective leaching process has higher technical and economic feasibility. The invention can greatly save auxiliary materials and reduce the production cost.
Claims (3)
1. A selective leaching process of crude cobalt hydroxide ore, characterized by comprising the steps of:
1) primary acid leaching: stirring and slurrying raw ore according to the ratio of water to ore of 1:3, heating to 60-70 ℃ after slurrying, adding concentrated sulfuric acid to adjust the pH of slurry to 0.45-0.5, stirring for 5-10 min, and filtering; directly feeding the acid leaching solution into a transfer tank to remove iron, and performing secondary slurrying on acid leaching residues according to the ratio of acid leaching residues to water being 1: 2;
2) and (3) secondary reduction leaching: heating the acid leaching residue to 50-60 ℃ after secondary slurrying, adding sodium metabisulfite, and maintaining the pH of the slurry to be 1.0-1.5 until the reduction potential is lower than 240 mV;
3) pre-oxidation: adding manganese dioxide ore after the treatment of the step 2), and adding Fe2+Is oxidized into Fe3+When Fe is present in the slurry2+The content is lower than 0.05g/L, and the slurry is transferred into a transit tank to be deironized.
2. The selective leaching process of crude cobalt hydroxide ore according to claim 1, wherein the manganese grade in the manganese dioxide ore is 30-50%.
3. The selective leaching process of crude cobalt hydroxide ore according to claim 1, wherein the iron content of the crude cobalt hydroxide ore is 3-4%.
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| CN202011258461.0A CN112359225A (en) | 2020-11-12 | 2020-11-12 | Selective leaching process of rough cobalt hydroxide ore |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113502394A (en) * | 2021-05-26 | 2021-10-15 | 广东佳纳能源科技有限公司 | Method for recovering cobalt or nickel intermediate product |
| CN113846225A (en) * | 2021-10-28 | 2021-12-28 | 贵州中伟资源循环产业发展有限公司 | Method for combined treatment of crude cobalt hydroxide and waste ternary positive electrode |
| CN113981241A (en) * | 2021-10-22 | 2022-01-28 | 广东佳纳能源科技有限公司 | Method for treating cobalt intermediate product |
| CN115652105A (en) * | 2022-11-18 | 2023-01-31 | 金川集团股份有限公司 | Sectional leaching process for cobalt raw material |
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Patent Citations (7)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113502394A (en) * | 2021-05-26 | 2021-10-15 | 广东佳纳能源科技有限公司 | Method for recovering cobalt or nickel intermediate product |
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| CN113846225A (en) * | 2021-10-28 | 2021-12-28 | 贵州中伟资源循环产业发展有限公司 | Method for combined treatment of crude cobalt hydroxide and waste ternary positive electrode |
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| CN115652105A (en) * | 2022-11-18 | 2023-01-31 | 金川集团股份有限公司 | Sectional leaching process for cobalt raw material |
| CN115652105B (en) * | 2022-11-18 | 2023-12-19 | 金川集团股份有限公司 | Sectional leaching process for cobalt raw material |
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Application publication date: 20210212 |