CN112142080B - Method for preparing battery-grade lithium carbonate by freezing, circulating and recycling lithium precipitation concentrated mother solution - Google Patents
Method for preparing battery-grade lithium carbonate by freezing, circulating and recycling lithium precipitation concentrated mother solution Download PDFInfo
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- CN112142080B CN112142080B CN202011040364.4A CN202011040364A CN112142080B CN 112142080 B CN112142080 B CN 112142080B CN 202011040364 A CN202011040364 A CN 202011040364A CN 112142080 B CN112142080 B CN 112142080B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The invention provides a method for preparing battery-grade lithium carbonate by freezing, circulating and recycling a lithium precipitation concentrated mother solution, belonging to the field of lithium carbonate preparation and comprising the following steps of: (1) Roasting and leaching lepidolite to obtain a leaching solution, purifying, concentrating, evaporating, precipitating lithium and filtering the leaching solution to obtain lithium carbonate and a lithium precipitation mother solution; (2) Concentrating and evaporating the lithium precipitation mother liquor to obtain lithium precipitation concentrated mother liquor; (3) And (3) adding the lithium precipitation concentrated mother liquor obtained in the step (2) into the leachate to obtain a mixed liquor, purifying, concentrating and evaporating the mixed liquor, freezing to remove potassium and sodium salts, filtering, introducing ion exchange resin to remove calcium and magnesium, precipitating to obtain battery-grade lithium carbonate and lithium precipitation mother liquor, and treating the lithium precipitation mother liquor for recycling in the process. According to the invention, the lithium precipitation mother liquor is treated, then is mixed with the leachate according to a certain volume ratio, and after potassium and sodium are removed by freezing, lithium precipitation is carried out, and the obtained lithium precipitation mother liquor can be recycled in the production process, so that the cost is reduced, and the production efficiency can be improved.
Description
Technical Field
The invention relates to the field of lithium carbonate preparation, in particular to a method for preparing battery-grade lithium carbonate by freezing, recycling and reusing a lithium deposition concentrated mother solution.
Background
With the increasingly prominent energy problem, research and development and industrialization of new energy materials such as lithium ion batteries and the like are vigorously developed. China has a large amount of lepidolite mineral resources, and the extraction of metals such as lithium, rubidium, cesium and the like from the lepidolite raw material has a good development prospect. However, the content of lithium in the lepidolite raw material is about 1.7%, and the content of potassium and sodium is as high as 6.5% and 1.25%, and because potassium sodium salt has extremely high solubility in water, the impurities can reduce the quality of the lithium carbonate product on one hand, and can reduce the production efficiency on the other hand, and even can not successfully carry out the production. A lithium precipitation mother liquor obtained after lepidolite is roasted, leached, purified and precipitated with lithium contains a large amount of sodium, potassium and lithium, and CN110923452A discloses a process for recovering potassium and sodium salts from the lithium precipitation mother liquor by using ethanol, wherein only sodium and potassium are recovered, but the lithium precipitation mother liquor is not utilized. The content of sodium and potassium in the lepidolite leaching solution is high, the content of lithium is low, and no report that the lithium precipitation mother solution is circularly used in the lithium carbonate production process exists at present.
Disclosure of Invention
In order to solve the problems, the lithium precipitation mother liquor is treated and then is mixed with the leachate for use in the system, and the lithium precipitation mother liquor obtained through the steps of lithium precipitation and the like is treated and then is recycled for use in the system and mixed with the leachate for use, so that the lithium precipitation mother liquor is used for recovering lithium in the lithium precipitation mother liquor and improving the production efficiency of lithium precipitation. The invention aims to provide a method for preparing battery-grade lithium carbonate by freezing, circulating and recycling a lithium precipitation concentrated mother solution.
In order to achieve the purpose, the method for preparing the battery-grade lithium carbonate by freezing, circulating and recycling the lithium precipitation concentrated mother solution comprises the following steps of:
(1) Roasting and leaching lepidolite to obtain a leaching solution, purifying, concentrating and evaporating (MVR), precipitating lithium and filtering the leaching solution to obtain lithium carbonate and a lithium precipitation mother solution;
(2) Concentrating and evaporating the lithium precipitation mother liquor to obtain lithium precipitation concentrated mother liquor;
(3) Adding the lithium precipitation concentrated mother liquor obtained in the step (2) into the leachate obtained in the step (1) to obtain a mixed liquor, purifying, concentrating, evaporating, freezing to remove potassium and sodium salts, filtering, introducing ion exchange resin to remove calcium and magnesium, and precipitating to obtain battery-grade lithium carbonate and lithium precipitation mother liquor;
(4) And (3) mixing the lithium precipitation mother liquor treated in the step (2) with the leaching solution prepared in the step (1) for the operation of the step (3) for recycling.
Wherein, the lithium precipitation concentration mother liquor in the step (2) is a mixed solution of saturated sodium sulfate, potassium sulfate and lithium sulfate.
Wherein, the volume ratio of the lithium deposition concentration mother liquor to the leaching solution in the step (3) is 1.
Wherein the freezing temperature in the step (3) is 0-10 ℃.
The invention has the beneficial effects that:
according to the method provided by the invention, the lithium precipitation mother liquor is treated, mixed with the leachate according to a certain volume ratio, and then frozen to remove most of sodium and potassium in the mixed liquor, so that 60-75% of sodium and 20-35% of potassium in the mixing are effectively reduced, the lithium content is improved by 20-40%, lithium carbonate obtained after lithium precipitation is in a battery level, the lithium precipitation mother liquor can be recycled, and the utilization rate of lithium is improved. The content of sodium and potassium in the frozen mixed solution is greatly reduced, the adverse effect of salt deposition on the tube wall is reduced, the production efficiency is improved, and the production cost is reduced.
Detailed Description
In order to more clearly and completely describe the technical scheme of the invention, the invention is further explained in detail by the specific embodiments, and it should be understood that the specific embodiments described herein are only used for explaining the invention, and are not used for limiting the invention, and various changes can be made within the scope defined by the claims of the invention.
Example 1
(1) Roasting and leaching lepidolite to obtain a leaching solution, purifying, concentrating and evaporating (MVR), precipitating lithium and filtering the leaching solution to obtain lithium carbonate and a lithium precipitation mother solution;
(2) Concentrating and evaporating the lithium precipitation mother liquor to obtain lithium precipitation concentrated mother liquor;
(3) Adding the lithium precipitation concentrated mother liquor obtained in the step (2) into the leachate obtained in the step (1) to obtain a mixed liquor, purifying, concentrating and evaporating the mixed liquor, freezing at 5 ℃ to remove potassium and sodium salts, filtering, introducing ion exchange resin to remove calcium and magnesium, and precipitating to obtain battery-grade lithium carbonate and lithium precipitation mother liquor;
(4) And (3) mixing the lithium precipitation mother liquor treated in the step (2) with the leachate prepared in the step (1) for carrying out the operation of the step (3), and recycling.
Wherein, the lithium precipitation concentration mother liquor in the step (2) is a mixed solution of saturated sodium sulfate, potassium sulfate and lithium sulfate.
Wherein, the volume ratio of the lithium deposition concentration mother liquor to the leaching solution in the step (3) is 1.
Example 2
(1) Roasting and leaching lepidolite to obtain a leaching solution, purifying, concentrating and evaporating (MVR), precipitating lithium and filtering the leaching solution to obtain lithium carbonate and a lithium precipitation mother solution;
(2) Concentrating and evaporating the lithium precipitation mother liquor to obtain lithium precipitation concentrated mother liquor;
(3) Adding the lithium precipitation concentrated mother liquor obtained in the step (2) into the leachate obtained in the step (1) to obtain a mixed liquor, purifying, concentrating and evaporating the mixed liquor, freezing at 0 ℃ to remove potassium and sodium salts, filtering, introducing ion exchange resin to remove calcium and magnesium, and precipitating to obtain battery-grade lithium carbonate and lithium precipitation mother liquor;
(4) And (3) mixing the lithium precipitation mother liquor treated in the step (2) with the leaching solution prepared in the step (1) for the operation of the step (3) for recycling.
Wherein, the lithium precipitation concentration mother liquor in the step (2) is a mixed solution of saturated sodium sulfate, potassium sulfate and lithium sulfate.
Wherein, the volume ratio of the lithium deposition concentration mother liquor to the leaching solution in the step (3) is 1.
Example 3
(1) Roasting and leaching lepidolite to obtain a leaching solution, purifying, concentrating and evaporating (MVR), precipitating lithium and filtering the leaching solution to obtain lithium carbonate and a lithium precipitation mother solution;
(2) Concentrating and evaporating the lithium precipitation mother liquor to obtain lithium precipitation concentrated mother liquor;
(3) Adding the lithium precipitation concentrated mother liquor obtained in the step (2) into the leachate obtained in the step (1) to obtain a mixed liquor, purifying, concentrating and evaporating the mixed liquor, freezing at 10 ℃ to remove potassium and sodium salts, filtering, introducing ion exchange resin to remove calcium and magnesium, and precipitating to obtain battery-grade lithium carbonate and lithium precipitation mother liquor;
(4) And (3) mixing the lithium precipitation mother liquor treated in the step (2) with the leachate prepared in the step (1) for carrying out the operation of the step (3), and recycling.
Wherein, the lithium precipitation concentration mother liquor in the step (2) is a mixed solution of saturated sodium sulfate, potassium sulfate and lithium sulfate.
Wherein, the volume ratio of the lithium deposition concentration mother liquor to the leaching solution in the step (3) is 1.
Comparative example 1
Wherein, the volume ratio of the lithium deposition concentration mother liquor in the step (3) to the leaching solution is 1. The rest is the same as example 1.
Comparative example 2
Wherein, the volume ratio of the lithium deposition concentration mother liquor and the leaching solution in the step (3) is 1. The rest is the same as example 1.
The potassium and sodium contents in the actual production and the quality of the lithium carbonate product were measured by the methods described in the above examples and comparative examples, and the results are shown in table 1. Under otherwise identical conditions, the process described in the examples performed well, whereas the process described in the comparative example showed the deposition of potassium and sodium salts during operation, which severely affected the operation of the system.
TABLE 1
Finally, it should be emphasized that the above-described preferred embodiments of the present invention are merely examples of implementations, rather than limitations, and that many variations and modifications of the invention are possible to those skilled in the art, without departing from the spirit and scope of the invention.
Claims (2)
1. A method for preparing battery-grade lithium carbonate by freezing, circulating and recycling a lithium precipitation concentrated mother solution is characterized by comprising the following steps:
(1) Roasting and leaching lepidolite to obtain a leaching solution, purifying, concentrating, evaporating, precipitating lithium and filtering the leaching solution to obtain lithium carbonate and a lithium precipitation mother solution;
(2) Concentrating and evaporating the lithium precipitation mother liquor to obtain lithium precipitation concentrated mother liquor;
in the step (2), the lithium precipitation concentrated mother liquor is a mixed solution of saturated sodium sulfate, potassium sulfate and lithium sulfate;
(3) Adding the lithium precipitation concentrated mother liquor obtained in the step (2) into the leachate obtained in the step (1) to obtain a mixed liquor, purifying, concentrating, evaporating, freezing to remove potassium and sodium salts, filtering, introducing ion exchange resin to remove calcium and magnesium, and precipitating to obtain battery-grade lithium carbonate and lithium precipitation mother liquor;
in the step (3), the volume ratio of the lithium precipitation concentrated mother liquor to the leaching solution is 1;
(4) And (3) mixing the lithium precipitation mother liquor treated in the step (2) with the leaching solution prepared in the step (1) for the operation of the step (3) for recycling.
2. The method for preparing battery-grade lithium carbonate by refrigerating and recycling the lithium precipitation concentrated mother liquor according to claim 1, which is characterized by comprising the following steps of: the freezing temperature in the step (3) is 0-10 ℃.
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| CN112978769B (en) * | 2021-05-08 | 2023-03-28 | 雅化锂业(雅安)有限公司 | Method for removing potassium from anhydrous sodium sulfate in lithium hydroxide production |
| CN113620321A (en) * | 2021-09-10 | 2021-11-09 | 宜春银锂新能源有限责任公司 | Method for preparing industrial special-grade lithium carbonate from low-concentration lithium liquid after primary lithium precipitation |
| CN113636579A (en) * | 2021-09-10 | 2021-11-12 | 宜春银锂新能源有限责任公司 | Process for preparing lithium carbonate by novel lepidolite sulfate roasting method |
| CN117303415B (en) * | 2023-11-30 | 2024-03-12 | 常州中源工程技术有限公司 | Technology for preparing lithium carbonate from water leaching solution after lepidolite roasting |
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| CN106882822A (en) * | 2017-03-15 | 2017-06-23 | 江苏容汇通用锂业股份有限公司 | A kind of method that lithium is recycled into battery-level lithium carbonate in sinker mother liquor |
| CN108285158A (en) * | 2018-04-03 | 2018-07-17 | 山东鲁北企业集团总公司 | A kind of preparation method of battery-level lithium carbonate |
| CN109911922A (en) * | 2018-10-19 | 2019-06-21 | 辽宁旭日新能源科技有限公司 | A kind of method that lepidolite ore prepares battery-level lithium carbonate |
| CN110885090A (en) * | 2019-12-31 | 2020-03-17 | 江西南氏锂电新材料有限公司 | Method for preparing battery-grade lithium carbonate by using lepidolite as raw material through one-step method |
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