CN115010152A - Lithium carbonate purification production process - Google Patents
Lithium carbonate purification production process Download PDFInfo
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- CN115010152A CN115010152A CN202210636089.5A CN202210636089A CN115010152A CN 115010152 A CN115010152 A CN 115010152A CN 202210636089 A CN202210636089 A CN 202210636089A CN 115010152 A CN115010152 A CN 115010152A
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- lithium carbonate
- lithium
- resin
- mother liquor
- hydrogenation
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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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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a lithium carbonate purification production process, which comprises the following steps: step one, size mixing; step two, hydrogenation; step three, filtering; step four, resin exchange; step five, thermal decomposition; filtering and washing, carrying out suction filtration, and leaching with pure water at 90 ℃; step seven, drying and crushing; the invention adopts normal pressure hydrogenation-resin process to purify high-impurity lithium carbonate, the chemical index of the obtained product reaches the requirement of battery-grade lithium carbonate, resin is used for adsorbing and removing calcium and magnesium, and the calcium and magnesium impurities of the obtained lithium carbonate are lower than 20x10 along with the increase of the cycle number of mother liquor ‑6 When the sulfate radical content in the mother liquor reaches 1.1 g.L ‑1 The mother liquor needs to be opened, and the total yield of the lithium carbonate is about 97.6 percent, so that the lithium loss is reduced while the purity of the lithium carbonate is improved.
Description
Technical Field
The invention relates to the technical field of lithium carbonate production, and particularly relates to a lithium carbonate purification production process.
Background
In recent years, the demand of the market for lithium batteries is increasing, and the lithium battery industry is developing rapidly. The battery-grade lithium carbonate is an important lithium source material for preparing the lithium battery cathode material, for example, the lithium iron phosphate cathode material produced by the carbothermic method is prepared by taking the battery-grade lithium carbonate as a lithium source raw material, so the demand of the battery-grade lithium carbonate is continuously increased, meanwhile, along with the gradual maturity of the lithium extraction technology from brine in China, the production cost and the price of the primary lithium carbonate are rapidly reduced, and the production of the industrial high-purity lithium carbonate basically takes the industrial lithium carbonate as the raw material, and the lithium is obtained from lithiumThe method for extracting lithium from stone or salt lake is different, the impurity content of the obtained crude lithium carbonate is also different, the purification method of the crude lithium carbonate comprises a hydrogenation decomposition method and a causticization method, the causticization method has long flow, low product yield and large slag quantity, and the most studied and applied method is the hydrogenation-complexation decomposition method, and the method is used for high-impurity raw materials, especially Ca, Mg and SO 4 2 Lithium carbonate with the content of more than 0.1 percent and even more than 0.2 percent, and in order to ensure the product purity, mother liquor needs to be frequently opened, so that the lithium loss is caused, so that a lithium carbonate purification production process is provided.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a lithium carbonate purification production process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lithium carbonate purification production process comprises the following steps:
step one, size mixing, namely mixing pure water or cooling mother liquor subjected to thermal decomposition into lithium carbonate slurry according to a solid-to-liquid ratio of 1:16-1: 28;
step two, hydrogenation;
filtering, namely filtering the hydrogenated solution in a suction filtration mode;
step four, resin exchange, namely deslagging the solution in a resin interaction mode;
step five, thermal decomposition;
filtering and washing, carrying out suction filtration, and leaching with pure water at 90 ℃;
and step seven, drying and crushing.
As further preferable in the present technical solution: in the second step, the lithium oxide slurry is put into a 600mL crystallizer, the hydrogenation temperature is room temperature, the hydrogenation time is 170min, and CO is added 2 The gas flow rate was 1L/min.
As a further preferred aspect of the present invention: in the fourth step, 80g of LSC-500 resin, an ion exchange column diameter of 1.5cm, a resin height of 20cm, an aspect ratio of 14: 1, 3L of hydrogenation solution, flow rate through column800mL·h -1 (8B.h -1 ) 1000mL of 5% hydrochloric acid, and a column flow rate of 800mL. multidot.h -1 (ii) a 1000mL of 5% sodium hydroxide and a column flow rate of 800mL -1 ；
The saturated adsorption capacity of the resin to Ca and Mg is 20Mg g -1 On the other hand, after a certain amount of hydrogenated liquid is treated by the resin, calcium and magnesium adsorption is saturated, at the moment, the resin needs to be analyzed and regenerated by hydrochloric acid, then the resin is converted into Na type by sodium hydroxide, and the hydrogenated liquid is heated and decomposed after passing through the resin.
As further preferable in the present technical solution: and in the fifth step, putting the solution after deslagging into a thermal decomposition path for thermal decomposition, wherein the temperature of thermal decomposition is 90-110 ℃, and the reaction time is 120 min.
As further preferable in the present technical solution: CO is generated in the process of decomposition and crystallization 2 The discharging and stirring speed can also have great influence, and the faster the stirring speed is, the stronger the liquid turbulence is, the more favorable the CO is 2 And continuously overflowing from the reaction system, so that the stirring is accelerated, the lithium bicarbonate solution is placed into a crystallizer, the temperature of the constant-temperature water bath is controlled to be 90 ℃, the stirring speed is 600r/min, the mass of the evaporated water is respectively 200g, then high-temperature suction filtration is carried out, and the lithium bicarbonate solution is washed by hot water at 90 ℃ for many times.
As further preferable in the present technical solution: and step seven, putting the washed product into a dryer for drying treatment, wherein the drying temperature is 450 ℃ and the drying time is 1.5 h.
As a further preferred aspect of the present invention: since lithium carbonate is a sparingly soluble substance, the solubility of lithium carbonate at 209 degrees Celsius is 1.33g (100g water) -1 Therefore, about 2.5g.L of the mother liquor after decomposition is contained -1 Directly discharging the lithium which is not precipitated to cause the loss of the lithium and influence the yield of the lithium, designing a mother liquor circulation experiment for this purpose, returning the mother liquor after the first decomposition to a hydrogenation process for the second hydrogenation, returning the mother liquor after the second decomposition to the third hydrogenation, and circulating the mother liquor for 10 times to obtain the lithium carbonate product index shown in Table 1
As can be seen from the table, the lithium carbonate obtained after the mother liquor is circulated for 10 times has high purity and completely meets the requirement of battery-grade potassium carbonate.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts normal pressure hydrogenation-resin process to purify high-impurity lithium carbonate, the chemical index of the obtained product reaches the requirement of battery-grade lithium carbonate, resin is used for adsorbing and removing calcium and magnesium, and the calcium and magnesium impurities of the obtained lithium carbonate are lower than 20x10 along with the increase of the cycle number of mother liquor -6 When the sulfate radical content in the mother liquor reaches 1.1 g.L -1 The mother liquor needs to be opened, and the total yield of the lithium carbonate is about 97.6 percent, so that the lithium loss is reduced while the purity of the lithium carbonate is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.
A lithium carbonate purification production process comprises the following steps:
step one, size mixing, namely mixing pure water or cooling mother liquor subjected to thermal decomposition into lithium carbonate slurry according to a solid-to-liquid ratio of 1:16-1: 28;
step two, hydrogenation, namely putting the lithium oxide slurry into a 600mL crystallizer, wherein the hydrogenation temperature is room temperature, the hydrogenation time is 170min, and CO is added 2 The gas flow rate is 1L/min;
filtering, namely filtering the hydrogenated solution in a suction filtration mode;
step four, resin exchange, namely deslagging the solution in a resin exchange mode, preparing 80g of LSC-500 resin, preparing an ion exchange column with the diameter of 1.5cm, the height of the resin of 20cm, and the length-diameter ratio of 14: 1, 3L of hydrogenation solution, and the flow rate of column passing through 800mL & h -1 (8B.h -1 ) 1000mL of 5% hydrochloric acid, and a column flow rate of 800mL. multidot.h -1 (ii) a 1000mL of 5% sodium hydroxide and a flow rate through the column of 800mL -1 ；
The saturated adsorption capacity of the resin to Ca and Mg is 20Mg g -1 About, after a certain amount of hydrogenated liquid is treated by the resin, calcium and magnesium adsorption reaches saturation, at the moment, the resin needs to be resolved and regenerated by hydrochloric acid, then the resin is converted into Na type by sodium hydroxide, and the hydrogenated liquid is heated and decomposed after passing through the resin;
step five, thermal decomposition, namely putting the solution after deslagging into a thermal decomposition path for thermal decomposition, wherein the temperature of thermal decomposition is 90-110 ℃, the reaction time is 120min, and CO exists in the process of decomposition and crystallization 2 The discharging and stirring speed can also have great influence, and the faster the stirring speed is, the stronger the liquid turbulence is, the more favorable the CO is 2 Continuously overflowing from the reaction system, so that the stirring is accelerated, the lithium bicarbonate solution is placed into a crystallizer, the temperature of a constant-temperature water bath is controlled to be 90 ℃, the stirring speed is 600r/min, the mass of evaporated water is respectively 200g, then high-temperature suction filtration is carried out, and the lithium bicarbonate solution is washed by hot water at 90 ℃;
filtering and washing, carrying out suction filtration, and leaching with pure water at 90 ℃;
step seven, drying and crushing, namely putting the washed product into a dryer for drying treatment, wherein the drying temperature is 450 ℃ and the drying time is 1.5 h;
since lithium carbonate is a sparingly soluble substance, the solubility of lithium carbonate at 209 degrees Celsius is 1.33g (100g water) -1 Therefore, about 2.5g.L of the mother liquor after decomposition is contained -1 Directly discharging the lithium which is not precipitated to cause the loss of the lithium and influence the yield of the lithium, designing a mother liquor circulation experiment for this purpose, returning the mother liquor after the first decomposition to a hydrogenation process for the second hydrogenation, returning the mother liquor after the second decomposition to the third hydrogenation, and circulating the mother liquor for 10 times to obtain the lithium carbonate product index shown in Table 1
As can be seen from the table, the lithium carbonate obtained after the mother liquor is circulated for 10 times has high purity and completely meets the requirement of battery-grade potassium carbonate; the invention adoptsPurifying high-impurity lithium carbonate by a pressure hydrogenation-resin process, wherein the chemical index of the obtained product meets the requirement of battery-grade lithium carbonate, removing calcium and magnesium by using resin adsorption, and the calcium and magnesium impurities of the obtained lithium carbonate are lower than 20x10 along with the increase of the cycle number of mother liquor -6， When the sulfate radical content in the mother liquor reaches 1.1 g.L -1 The mother liquor needs to be opened, and the total yield of the lithium carbonate is about 97.6 percent, so that the lithium loss is reduced while the purity of the lithium carbonate is improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. The lithium carbonate purification production process is characterized by comprising the following steps:
step one, size mixing, namely mixing pure water or cooling mother liquor subjected to thermal decomposition into lithium carbonate slurry according to a solid-to-liquid ratio of 1:16-1: 28;
step two, hydrogenation;
filtering, namely filtering the hydrogenated solution in a suction filtration mode;
step four, resin exchange, namely deslagging the solution in a resin interaction mode;
step five, thermal decomposition;
filtering and washing, carrying out suction filtration, and leaching with pure water at 90 ℃;
and step seven, drying and crushing.
2. The lithium carbonate purification production process according to claim 1, wherein in the second step, the lithium carbonate slurry is fed into a 600mL crystallizer, the hydrogenation temperature is room temperature, the hydrogenation time is 170min, and CO is used 2 The gas flow rate was 1L/min.
3. Purification of lithium carbonate according to claim 1The production process is characterized in that in the fourth step, 80g of LSC-500 resin, 1.5cm of ion exchange column diameter, 20cm of resin height, 14 of length-diameter ratio: 1, 3L of hydrogenation solution, and the flow rate of column passing through 800mL & h -1 (8B.h -1 ) 1000mL of 5% hydrochloric acid, and a column flow rate of 800mL. multidot.h -1 (ii) a 1000mL of 5% sodium hydroxide and a flow rate through the column of 800mL -1 ；
The saturated adsorption capacity of the resin to Ca and Mg is 20Mg g -1 On the other hand, after a certain amount of hydrogenated liquid is treated by the resin, calcium and magnesium adsorption is saturated, at the moment, the resin needs to be analyzed and regenerated by hydrochloric acid, then the resin is converted into Na type by sodium hydroxide, and the hydrogenated liquid is heated and decomposed after passing through the resin.
4. The lithium carbonate purification production process according to claim 1, wherein in the fifth step, the solution after deslagging is put into a thermal decomposition path for thermal decomposition, wherein the temperature of thermal decomposition is 90-110 ℃, and the reaction time is 120 min.
5. The lithium carbonate purification production process according to claim 4, wherein CO is generated in the decomposition crystallization process 2 The discharging and stirring speed can also have great influence, and the faster the stirring speed is, the stronger the liquid turbulence is, the more favorable the CO is 2 And continuously overflowing from the reaction system, so that the stirring is accelerated, the lithium bicarbonate solution is placed into a crystallizer, the temperature of the constant-temperature water bath is controlled to be 90 ℃, the stirring speed is 600r/min, the mass of the evaporated water is respectively 200g, then high-temperature suction filtration is carried out, and the lithium bicarbonate solution is washed by hot water at 90 ℃ for many times.
6. The purification production process of lithium carbonate according to claim 1, wherein in the seventh step, the washed lithium bicarbonate solution is put into a dryer for drying treatment, and the drying temperature is 450 ℃ and the drying time is 1.5 h.
7. The lithium carbonate purification production process according to claim 6, wherein,since lithium carbonate is a sparingly soluble substance, the solubility of lithium carbonate at 209 degrees Celsius is 1.33g (100g water) -1 Therefore, about 2.5g.L of the mother liquor after decomposition is contained -1 Directly discharging the lithium which is not precipitated to cause the loss of the lithium and influence the yield of the lithium, returning the mother liquor after the first decomposition to the hydrogenation process for the second hydrogenation, returning the mother liquor after the second decomposition to the third hydrogenation, and circulating the processes, wherein the indexes of the lithium carbonate product obtained after the mother liquor is circulated for 10 times are shown in Table 1
As can be seen from the table, the lithium carbonate obtained after the mother liquor is circulated for 10 times has high purity and completely meets the requirement of battery-grade potassium carbonate.
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| CN202210636089.5A CN115010152A (en) | 2022-06-07 | 2022-06-07 | Lithium carbonate purification production process |
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| CN202210636089.5A CN115010152A (en) | 2022-06-07 | 2022-06-07 | Lithium carbonate purification production process |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502720A (en) * | 2011-10-27 | 2012-06-20 | 白银扎布耶锂业有限公司 | Process for producing battery-grade lithium carbonate through processing carbonate type lithium concentrate by deep carbonation method |
| CN102531002A (en) * | 2011-12-23 | 2012-07-04 | 四川天齐锂业股份有限公司 | Method for purifying lithium carbonate |
| CN103539169A (en) * | 2013-10-24 | 2014-01-29 | 中国地质科学院郑州矿产综合利用研究所 | Method for preparing battery-grade lithium carbonate or high-purity lithium carbonate by using industrial-grade lithium carbonate |
| CN208008474U (en) * | 2018-03-12 | 2018-10-26 | 安徽科达洁能股份有限公司 | A kind of system preparing battery-level lithium carbonate |
| CN113620322A (en) * | 2021-09-17 | 2021-11-09 | 安顺远景新材料有限公司 | Method for preparing battery-grade lithium carbonate by using waste gypsum and crude lithium carbonate |
-
2022
- 2022-06-07 CN CN202210636089.5A patent/CN115010152A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502720A (en) * | 2011-10-27 | 2012-06-20 | 白银扎布耶锂业有限公司 | Process for producing battery-grade lithium carbonate through processing carbonate type lithium concentrate by deep carbonation method |
| CN102531002A (en) * | 2011-12-23 | 2012-07-04 | 四川天齐锂业股份有限公司 | Method for purifying lithium carbonate |
| CN103539169A (en) * | 2013-10-24 | 2014-01-29 | 中国地质科学院郑州矿产综合利用研究所 | Method for preparing battery-grade lithium carbonate or high-purity lithium carbonate by using industrial-grade lithium carbonate |
| CN208008474U (en) * | 2018-03-12 | 2018-10-26 | 安徽科达洁能股份有限公司 | A kind of system preparing battery-level lithium carbonate |
| CN113620322A (en) * | 2021-09-17 | 2021-11-09 | 安顺远景新材料有限公司 | Method for preparing battery-grade lithium carbonate by using waste gypsum and crude lithium carbonate |
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