CN113174485A - Method for deeply removing calcium and manganese in cobalt sulfate solution - Google Patents
Method for deeply removing calcium and manganese in cobalt sulfate solution Download PDFInfo
- Publication number
- CN113174485A CN113174485A CN202110475475.6A CN202110475475A CN113174485A CN 113174485 A CN113174485 A CN 113174485A CN 202110475475 A CN202110475475 A CN 202110475475A CN 113174485 A CN113174485 A CN 113174485A
- Authority
- CN
- China
- Prior art keywords
- manganese
- cobalt sulfate
- calcium
- sulfate solution
- organic phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Abstract
The invention provides a method for deeply removing calcium and manganese in a cobalt sulfate solution, which is to mix P204 and sulfonated kerosene to prepare an organic phase; heating a calcium and manganese-containing cobalt sulfate solution to 50-60 ℃, adding the prepared organic phase for extraction, controlling the flow ratio of the organic phase to the water phase to be O/A =1: 1-6: 1 in the extraction process, extracting calcium and manganese into the organic phase, and retaining cobalt in a raffinate; the cobalt sulfate crystal with the pH value of more than 3.0 is obtained by clarifying, deoiling, evaporating and crystallizing the raffinate, spraying hot water on the obtained crystal and drying the obtained crystal, and the obtained cobalt sulfate crystal has the advantages of high quality, simple process, wider control range, improved quality of the cobalt sulfate product and higher economic benefit.
Description
Technical Field
The invention belongs to the technical field of nickel-cobalt hydrometallurgy, and particularly relates to a method for deeply removing calcium and manganese in a cobalt sulfate solution.
Background
In the hydrometallurgical production, when nickel hydroxide cobalt is used as a raw material to produce nickel sulfate and cobalt sulfate, the obtained cobalt sulfate product is often high in manganese and calcium due to unstable selectivity and process control of an extracting agent, so that the quality of the cobalt sulfate product is reduced, and the benefit is reduced.
In the production process of industrial cobalt sulfate, cobalt nickel hydroxide solid materials are leached and then subjected to the procedures of P204 impurity removal, C272 cobalt magnesium separation and the like to obtain a cobalt sulfate solution, and the solution has high calcium and manganese contents, so that the calcium and manganese contents of the product are high when the solution is directly used for producing a cobalt sulfate product, and impurity calcium and magnesium enrichment can be formed in mother liquor, so that the quality of the cobalt sulfate product is seriously influenced.
Disclosure of Invention
The invention aims to provide a method for deeply removing calcium and manganese in a cobalt sulfate solution, which is characterized in that after a nickel hydroxide cobalt solid material is leached, a calcium and manganese containing cobalt sulfate solution is obtained through the procedures of P204 impurity removal, C272 cobalt-magnesium separation and the like, P204 without saponification is adopted for deeply removing calcium and manganese, and crystallized crystals are sprayed by hot water, so that the pH value of the product is improved, and a high-quality cobalt sulfate product is obtained.
(1) P204 and sulfonated kerosene are mixed and diluted, wherein the volume fraction of the P204 is 10-30%, an organic phase is prepared, the P204 does not need to be saponified, and the regenerated P204 can be directly used.
(2) Heating a calcium and manganese-containing cobalt sulfate solution to 50-60 ℃ (the extraction efficiency is reduced due to the fact that the temperature is too low, the solution is too high, and the organic extractant is seriously volatilized), adding the prepared organic phase to perform extraction, controlling the flow ratio of the organic phase to the water phase to be O/A =1: 1-6: 1 in the extraction process, controlling the extraction stages to be 2-8 stages, extracting calcium and manganese into the organic phase, retaining cobalt in raffinate, enabling the pH of the raffinate to be more than or equal to 4.5, enabling the pH of the raffinate to be more than or equal to 1.5, replacing the organic extractant after circulating for 12 hours, and directly using the replaced loaded organic through regeneration.
(3) Clarifying the separated raffinate (the oil content is separated, the oil content of the clarified raffinate is less than 1%), deoiling (the oil content of the deoiled solution is less than 20 ppm), evaporating and crystallizing to obtain crystals, spraying the crystals with hot water at 40-50 ℃, and drying to obtain cobalt sulfate crystals with the pH value of more than 3.0, wherein Ca in the cobalt sulfate crystals is less than 0.0005%, and Mn in the cobalt sulfate crystals is less than 0.006%.
In summary, the calcium and manganese contained cobalt sulfate solution obtained by the processes of P204 impurity removal, C272 cobalt magnesium separation and the like after leaching the nickel hydroxide cobalt solid material is deeply subjected to calcium and manganese removal, the calcium and manganese contained cobalt sulfate solution is heated to 50-60 ℃, then calcium and manganese are extracted by unsaponifiable P204, the raffinate is clarified, subjected to oil removal, evaporation and crystallization, and the crystallized crystals are sprayed by hot water, so that the pH value of the product is increased, and the high-quality cobalt sulfate product is obtained. The invention has simple process and wider control range, improves the quality of the cobalt sulfate product and has higher economic benefit.
Detailed Description
The method for deeply removing calcium and manganese in the cobalt sulfate solution of the invention is described in detail with reference to the specific embodiments.
Example 1
A method for deeply removing calcium and manganese in a cobalt sulfate solution comprises the following steps:
(1) p204 is mixed with sulfonated kerosene, wherein the volume fraction of P204 is 15%, the mixture is configured into an organic phase, the P204 does not need to be saponified, and the P204 can be directly used after regeneration.
(2) Heating a calcium and manganese-containing cobalt sulfate solution to 55 ℃ (the extraction efficiency is reduced due to the fact that the temperature is too low, the solution with too high temperature and an organic extractant are seriously volatilized), adding the prepared organic phase for extraction, controlling the flow ratio of the organic phase to the water phase to be O/A =3:1 in the extraction process, controlling the extraction stage number to be 5, extracting calcium and manganese into the organic phase, retaining cobalt in raffinate, enabling the pH of the raffinate to be more than or equal to 4.5, enabling the pH of the raffinate to be more than or equal to 1.5, circulating the organic extractant for 12h, then replacing, and directly using the replaced loaded organic through regeneration (the regeneration section is 4).
(3) And (3) carrying out 1-stage clarification on the separated raffinate (the oil content is separated, the oil content of the clarified raffinate is less than 1%), deoiling (the oil content of the deoiled solution is less than 20 ppm), evaporating, cooling to 38 ℃, carrying out heat preservation and crystallization for 12 hours, filtering to obtain crystals, spraying with hot water at 48 ℃, carrying out suction filtration by using vacuum, and drying to obtain the cobalt sulfate crystals with the pH value of more than 3.0.
The calcium and manganese containing cobalt sulfate solution and the raffinate composition after extraction are as follows (g/L):
the cobalt sulfate crystal composition after deep calcium and manganese removal is as follows (%):
example 2
The method for deeply removing calcium and manganese in the cobalt sulfate solution is the same as that of the embodiment 1;
the calcium and manganese containing cobalt sulfate solution and the raffinate composition after extraction are as follows (g/L):
the cobalt sulfate crystal composition after deep calcium and manganese removal is as follows (%):
Claims (4)
1. a method for deeply removing calcium and manganese in a cobalt sulfate solution comprises the following steps:
(1) mixing and diluting P204 and sulfonated kerosene, wherein the volume fraction of P204 is 10-30%, and preparing an organic phase;
(2) heating a calcium and manganese-containing cobalt sulfate solution to 50-60 ℃, adding the prepared organic phase for extraction, controlling the flow ratio of the organic phase to the water phase to be O/A =1: 1-6: 1 in the extraction process, extracting calcium and manganese into the organic phase, and retaining cobalt in a raffinate;
(3) and clarifying, deoiling, evaporating and crystallizing the raffinate to obtain crystals, spraying hot water on the crystals, and drying to obtain the cobalt sulfate crystals with the pH value of more than 3.0.
2. The method for deeply removing calcium and manganese in the cobalt sulfate solution as claimed in claim 1, wherein: in the step (2), the number of extraction stages is 2-8.
3. The method for deeply removing calcium and manganese in the cobalt sulfate solution as claimed in claim 1, wherein: in the step (3), the oil content after oil removal is less than 20 ppm.
4. The method for deeply removing calcium and manganese in the cobalt sulfate solution as claimed in claim 1, wherein: in the step (4), the temperature of the hot water is 40-50 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110475475.6A CN113174485A (en) | 2021-04-29 | 2021-04-29 | Method for deeply removing calcium and manganese in cobalt sulfate solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110475475.6A CN113174485A (en) | 2021-04-29 | 2021-04-29 | Method for deeply removing calcium and manganese in cobalt sulfate solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113174485A true CN113174485A (en) | 2021-07-27 |
Family
ID=76925457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110475475.6A Pending CN113174485A (en) | 2021-04-29 | 2021-04-29 | Method for deeply removing calcium and manganese in cobalt sulfate solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113174485A (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1112460A (en) * | 1977-02-28 | 1981-11-17 | Franklin F. Clark | Solvent extraction process |
| GB2104053A (en) * | 1981-08-17 | 1983-03-02 | Inco Ltd | Production of nickel and cobalt sulphates and chlorides |
| US20040175618A1 (en) * | 2003-03-04 | 2004-09-09 | Canon Kabushiki Kaisha | Lithium metal composite oxide particles, process of producing lithium metal composite oxide particles, electrode structure containing lithium metal composite oxide particles, process of producing electrode structure, and lithium secondary battery having electrode structure |
| CN106222411A (en) * | 2016-08-26 | 2016-12-14 | 德清县立荣金属粉末有限公司 | Three sections of extraction copper removals, manganese, ferrum, calcium, methods of magnesium are used from cobalt salt solution |
| CN106756013A (en) * | 2016-11-25 | 2017-05-31 | 桂林理工大学 | A kind of method of the direct nickel cobalt saponification of P204, P507 |
| JP2017226568A (en) * | 2016-06-21 | 2017-12-28 | 住友金属鉱山株式会社 | Method for producing high purity cobalt sulfate aqueous solution |
| CN108441633A (en) * | 2018-05-21 | 2018-08-24 | 兰州金川新材料科技股份有限公司 | A kind of production method of electronic-grade sulfuric acid cobalt liquor |
| CN108517403A (en) * | 2018-06-30 | 2018-09-11 | 贵州中伟资源循环产业发展有限公司 | A kind of method of metallic cobalt battery grade cobalt sulfate |
| CN108677009A (en) * | 2018-05-21 | 2018-10-19 | 兰州金川新材料科技股份有限公司 | A kind of depth abstraction impurity removal method of cobalt chloride solution |
| CN110616322A (en) * | 2019-09-20 | 2019-12-27 | 华中科技大学 | Non-saponification extraction method for extracting and separating cobalt, nickel and manganese by using acidic extracting agent |
| CN111056576A (en) * | 2018-10-16 | 2020-04-24 | 四川省九维新材料科技有限公司 | Method for preparing battery-grade cobalt sulfate from low-grade cobalt-sulfur tailings |
| CN112708779A (en) * | 2020-12-08 | 2021-04-27 | 金川集团镍盐有限公司 | Preparation method of cobalt sulfate solution |
-
2021
- 2021-04-29 CN CN202110475475.6A patent/CN113174485A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1112460A (en) * | 1977-02-28 | 1981-11-17 | Franklin F. Clark | Solvent extraction process |
| GB2104053A (en) * | 1981-08-17 | 1983-03-02 | Inco Ltd | Production of nickel and cobalt sulphates and chlorides |
| US20040175618A1 (en) * | 2003-03-04 | 2004-09-09 | Canon Kabushiki Kaisha | Lithium metal composite oxide particles, process of producing lithium metal composite oxide particles, electrode structure containing lithium metal composite oxide particles, process of producing electrode structure, and lithium secondary battery having electrode structure |
| JP2017226568A (en) * | 2016-06-21 | 2017-12-28 | 住友金属鉱山株式会社 | Method for producing high purity cobalt sulfate aqueous solution |
| CN106222411A (en) * | 2016-08-26 | 2016-12-14 | 德清县立荣金属粉末有限公司 | Three sections of extraction copper removals, manganese, ferrum, calcium, methods of magnesium are used from cobalt salt solution |
| CN106756013A (en) * | 2016-11-25 | 2017-05-31 | 桂林理工大学 | A kind of method of the direct nickel cobalt saponification of P204, P507 |
| CN108441633A (en) * | 2018-05-21 | 2018-08-24 | 兰州金川新材料科技股份有限公司 | A kind of production method of electronic-grade sulfuric acid cobalt liquor |
| CN108677009A (en) * | 2018-05-21 | 2018-10-19 | 兰州金川新材料科技股份有限公司 | A kind of depth abstraction impurity removal method of cobalt chloride solution |
| CN108517403A (en) * | 2018-06-30 | 2018-09-11 | 贵州中伟资源循环产业发展有限公司 | A kind of method of metallic cobalt battery grade cobalt sulfate |
| CN111056576A (en) * | 2018-10-16 | 2020-04-24 | 四川省九维新材料科技有限公司 | Method for preparing battery-grade cobalt sulfate from low-grade cobalt-sulfur tailings |
| CN110616322A (en) * | 2019-09-20 | 2019-12-27 | 华中科技大学 | Non-saponification extraction method for extracting and separating cobalt, nickel and manganese by using acidic extracting agent |
| CN112708779A (en) * | 2020-12-08 | 2021-04-27 | 金川集团镍盐有限公司 | Preparation method of cobalt sulfate solution |
Non-Patent Citations (1)
| Title |
|---|
| 苏华: "溶剂萃取法制备锂离子电池用硫酸钴工艺研究", 《稀有金属与硬质合金》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107447110B (en) | A kind of preparation method of LITHIUM BATTERY manganese sulfate | |
| CN108117105B (en) | A kind of refining methd of Copper making by-product crude nickle sulphate | |
| CN111057848A (en) | Method for extracting lithium from lithium-containing solution by solvent extraction | |
| CN102329224A (en) | Method for purifying dodecanedioic acid | |
| CN112142081A (en) | Method for preparing battery-grade lithium carbonate by using lepidolite | |
| JP2024514986A (en) | Method and apparatus for extracting lithium carbonate for batteries from P507 raffinate | |
| CN108622938B (en) | Method for preparing ammonium dimolybdate from molybdenum-containing solution | |
| CN105366722B (en) | The method of normal temperature extraction production high purity vanadic anhydride | |
| CN112777641A (en) | Method for simultaneously preparing battery-grade manganese sulfate and feed-grade manganese sulfate | |
| CN113120941A (en) | Method for extracting high-purity scandium oxide from scandium-containing nickel cobalt hydroxide in short process | |
| CN108910938B (en) | Method for jointly producing zinc sulfate monohydrate and zinc sulfate heptahydrate | |
| CN113174485A (en) | Method for deeply removing calcium and manganese in cobalt sulfate solution | |
| CN102010007A (en) | Method for producing industrial-grade ammonium dimolybdate by combination method | |
| CN102126756B (en) | Method for producing industrial grade ammonium paramolybdate | |
| CN102633293B (en) | Method for refining multistage circulation evaporation-free copper sulfate | |
| CN101274777A (en) | Method for extracting vanadic anhydride from vanadium-containing liquid | |
| CN111018939A (en) | Rapid refining method of tea saponin | |
| CN103172122A (en) | Method for purifying high purity ammonium rhenate from liquid containing ammonium rhenate | |
| CN106350419B (en) | Utilize the method for the wine brewing yellow water production compound Wine blending liquid of lactic acid | |
| KR20190074416A (en) | Method for manufacturing high purity metal salt | |
| CN114959302A (en) | Method for preparing nickel sulfate/cobalt from laterite-nickel ore | |
| CN106380022A (en) | Treatment process of H acid industrial wastewater, device and special adsorbent resin material | |
| CN107805405B (en) | A method of improving capsanthin smell | |
| CN101205085A (en) | Method for producing secondary ammonium molybdate by molybdenum recovery material | |
| CN112921174B (en) | Method for hydrometallurgical preparation of cobalt intermediate product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210727 |