CA2820112C - Method for preparing high-purity lithium carbonate - Google Patents
Method for preparing high-purity lithium carbonate Download PDFInfo
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Abstract
The invention relates to a method for preparing high-purity lithium carbonate, and belongs to the technical field of preparation of high-purity lithium carbonate. The technical solution of the invention is as follows: Battery-grade lithium hydroxide monohydrate is prepared a solution with 50 - 90g/L Li2O; then introducing CO2 gas at a flow rate of 3 - 5L/s into the lithium hydroxide solution, lowering the flow rate of CO2 to 2 - 3L/s when the Li2O concentration of the solution decreases to 40g/L,the flow rate of CO2 is lowered down to 0.8 - 1.2L/s when the Li2O concentration of the solution decreases to 20g/L; when massive solid appears in the solution, stopping introducing the gas to obtain a lithium carbonate slurry; separating the lithium carbonate slurry, washing the solid, and drying to a moisture content of lower than 0.1% to obtain high-purity lithium carbonate with a purity of 99.99%.
Description
:A 02820112 2013-08-05 Method for Preparing High-purity Lithium Carbonate Field of the Invention The invention relates to a method for preparing high-purity lithium carbonate, and belongs to the technical field of preparation of high-purity lithium carbonate.
Technical background Li2CO3 is widely applied to such fields as ceramics, glass, atomic energy, aerospace, lithium battery, lithium alloy and pharmaceutical, and also used as a raw material for preparing various lithium compounds. For different purposes, the requirements for purity and particle size of lithium carbonate are different. 99.9% high-purity lithium carbonate is used for cathode material of lithium ion batteries, 99.99% high-purity lithium carbonate is used for electrolyte of lithium ion batteries, and 99.999% high-purity lithium carbonate is used for pharmaceutical or elastic surface wave elements. With the continuous expansion of application scope of lithium products in the high-tech field, demands for lithium salts at home and abroad are increasingly growing, and requirements for purity of products are higher. Therefore, it is imperative to develop high value-added high-purity lithium salt products.
Existing methods for preparing high-purity lithium carbonate mainly include:
1) Zintl Harder Dauth method, which introduces more reagents. It is obviously difficult to enable products to reach the impurity as required by customers currently.
Technical background Li2CO3 is widely applied to such fields as ceramics, glass, atomic energy, aerospace, lithium battery, lithium alloy and pharmaceutical, and also used as a raw material for preparing various lithium compounds. For different purposes, the requirements for purity and particle size of lithium carbonate are different. 99.9% high-purity lithium carbonate is used for cathode material of lithium ion batteries, 99.99% high-purity lithium carbonate is used for electrolyte of lithium ion batteries, and 99.999% high-purity lithium carbonate is used for pharmaceutical or elastic surface wave elements. With the continuous expansion of application scope of lithium products in the high-tech field, demands for lithium salts at home and abroad are increasingly growing, and requirements for purity of products are higher. Therefore, it is imperative to develop high value-added high-purity lithium salt products.
Existing methods for preparing high-purity lithium carbonate mainly include:
1) Zintl Harder Dauth method, which introduces more reagents. It is obviously difficult to enable products to reach the impurity as required by customers currently.
2) LiOH ammonium bicarbonate precipitation method. It is expected that products with a purity higher than 99.5% can be obtained after purification of LiOH and by use of usual recrystallization methods. "Research on Preparation Process of High-purity Lithium Carbonate" in Petrochemical Industry Application (2008) introduces a method for synthetizing high-purity lithium carbonate using technical grade lithium hydroxide and analytically pure ammonium carbonate as raw materials by a double decomposition method.
The products produced with such method exceed requirements of national standard GB10576_89, with main components up to 99.9% and above. The method has disadvantages of ammonia gas release, non-environmental friendly, high lithium content of mother solution and low lithium yield coefficient.
The products produced with such method exceed requirements of national standard GB10576_89, with main components up to 99.9% and above. The method has disadvantages of ammonia gas release, non-environmental friendly, high lithium content of mother solution and low lithium yield coefficient.
3) Technical lithium carbonate, by using such methods as electrolytic method, Li2CO3 recrystallization, hydrogen carbonate decomposition, carbonate hydrogenation precipitation, :A 02820112 2013-08-05 =
sodium carbonate chemical precipitation, may used for producing high-purity lithium carbonate. Impurity content of Li2CO3 prepared by the methods is still higher and the process is complex. For example, in Chinese invention patent 200710019052.3 "A
Process Method for Preparing High-purity Lithium Carbonate Using Salt Lake Lithium Resources", lithium carbonate with a purity of 99.9% is obtained by using crude lithium carbonate extracted from salt lake brine as a raw material, introducing CO2 for hydrogenation, performing various impurity removal processes, decomposing lithium bicarbonate in negative pressure conditions and then washing repeatedly.
With regard to LiOH solution CO2 precipitation method, as mentioned in Wang Yunqi 's (Xinjiang Haoxin Lithium Salts Development Co., Ltd.)Discussion on Methods for Preparation of High-purity Lithium Carbonate that it can be seen from LiOH
ammonium bicarbonate precipitation method that Li2CO3 can be obtained only by introducing carbonate in LiOH, and CO2 is a widely used gas. Therefore, a reaction system is free from large quantity of impurities in the following reaction.
2LiOH + CO2 ¨>Li2CO3 + H2O
Washed CO2 gas can reach a fairly pure standard, that is, the purity of products depends exclusively on LiOH, the method is the immediate and widely used method for preparing high-purity lithium carbonate, and technical LiOH is generally used to react with lithium carbonate directly to obtain 99% products. However, 99.99% lithium carbonate can not be directly obtained by the method.
Summary of the Invention The technical problem to be solved in the invention is to provide a method using lithium hydroxide to directly prepare 99.99% lithium carbonate via a simple production process.
The technical solution of the invention is as follows:
a. Battery-grade lithium hydroxide monohydrate is prepared into a solution with 50 -90g/L Li2O;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Li2O
concentration of the solution decreases to 40g/L; the flow rate of CO2 is lowered down to 0.8 - 1.2L/s when the Li20 concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry.
This has not only saved the consumption of CO2 gas, also ensured the precipitated Li2CO3 won't be hydrogenated into LiHCO3 that will affect the primary yield of lithium, while avoided the inclusion of lithium carbonate; and c. Separating High-purity lithium carbonate can be gained by separating, washing and drying the lithium carbonate slurry obtained in step b to a moisture content of lower than 0.1%.
According to another aspect of the present invention, there is provided a method for preparing lithium carbonate having a purity of 99.99% or greater, comprising the steps of: (a) preparing a lithium hydroxide solution with an equivalent Li20 concentration of 50-90 g/L from a battery-grade lithium hydroxide monohydrate; (b) introducing CO2 gas into the lithium hydroxide solution described in step (a) at a flow rate of 3-5 L/s to precipitate lithium carbonate and obtain a lithium carbonate slurry, the flow rate of CO2 being lowered down to 2-3 L/s when the equivalent Li20 concentration of the solution decreases to 40 g/L;
and the flow rate of CO2 being lowered down to 0.8-1.2 L/s when the equivalent Li20 concentration of the solution decreases to 20 g/L; (c) washing and drying the lithium carbonate slurry obtained in step (b) to a moisture content of lower than 0.1%
by weight.
In order to further reduce Ca2+ and Mg2+ contents in products, conventional methods are used to remove Ca2+ and Mg2+ contents from the lithium hydroxide solution in step a to allow Ca2+ concentration of products to be lower than 3ppm and Mg2+
concentration of products to be lower than lppm by usually adding lithium phosphate, lithium dihydrogen phosphate, oxalic acid or EDTA to reach this goal, and the insoluble impurities in the solutions is filtered out by filter pressing.
The stirring rate in step b is kept at 60 - 80rpm during gas introduction. The Li2CO3 obtained has large particle size and is less likely to generate secondary aggregation by controlling the stirring rate. Too slow rotation speed is unfavorable for=
collision between ions, affecting reaction speed, and too fast rotation speed easily causes generated lithium carbonate particles to be smashed, affecting product quality.
Reaction temperature reported in existing technical documents is 50 C in step b, and reaction is carried out at 10 - 30 C in the invention. No additional energy is needed in the invention, and too high temperature will result in low utilization rate of CO2 gas, and too low temperature will result in reduced reaction speed and severe caking.
In step b, the temperature is risen to 80 - 120 C after the gas stops introducing, and the temperature is held for 20 - 50min for crystal grain growth.
In addition, in order to completely wash and remove water-soluble impurities in step c, water washing is important. Water is added at a solid-to-liquid ratio (weight ratio) of 1:2 - 4, stir washing temperature is controlled at 90 - 98 C for centrifugal separation, solid is a wet lithium carbonate product, and sodium, potassium, sulfate radicals and other foreign ions are dissolved in the stir washing water to be separated with lithium carbonate.
One embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared into a solution with 50 -90g/L Li20;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 3L/s when the Li20 concentration of the solution decreases to 40g,/L; the flow rate of CO2 is lowered down to 3a :A 02820112 2013-08-05 0.8 - 1.2L/s when the Li20 concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry.
This has not only saved the consumption of CO2 gas, also ensured the precipitated Li2CO3 won't be hydrogenated into LiHCO3 that will affect the primary yield of lithium, while avoided the inclusion of lithium carbonate; and c. Separating. High-purity lithium carbonate can be gained by separating, washing and drying (at 105V) the lithium carbonate slurry obtained in step b to a moisture content of lower than 0.1%.
Another embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared into a solution with 50 -90g/L Li20, Ca2+ and Mg2+ contents of which are removed by conventional methods, usually adding lithium phosphate, lithium dihydrogen phosphate, oxalic acid or EDTA to reach this goal, and the insoluble impurities in the solutions is filtered out by filter pressing;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Li20 concentration of the solution decreases to 40g/L; the flow rate of CO2 is lowered down to 0.8 - 1.2L/s when the Li20 concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry.
This has not only saved the consumption of CO2 gas, also ensured the precipitated Li2CO3 won't be hydrogenated into LiHCO3 that will affect the primary yield of lithium, while avoided the inclusion of lithium carbonate; and c. Separating. High-purity lithium carbonate can be gained by separating, washing and drying the lithium carbonate slurry obtained in step b to a moisture content of lower than 0.1%.
Another embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared a solution with 50 -90g/L Li20, Ca2+ and Mg2+ contents of which are removed by conventional methods, usually adding lithium phosphate, lithium dihydrogen phosphate, oxalic acid or EDTA to reach this goal, and the insoluble impurities in the solutions is filtered out by filter pressing;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Li2O
concentration of the solution decreases to 40g/L; the flow rate of CO2 is lowered down to
sodium carbonate chemical precipitation, may used for producing high-purity lithium carbonate. Impurity content of Li2CO3 prepared by the methods is still higher and the process is complex. For example, in Chinese invention patent 200710019052.3 "A
Process Method for Preparing High-purity Lithium Carbonate Using Salt Lake Lithium Resources", lithium carbonate with a purity of 99.9% is obtained by using crude lithium carbonate extracted from salt lake brine as a raw material, introducing CO2 for hydrogenation, performing various impurity removal processes, decomposing lithium bicarbonate in negative pressure conditions and then washing repeatedly.
With regard to LiOH solution CO2 precipitation method, as mentioned in Wang Yunqi 's (Xinjiang Haoxin Lithium Salts Development Co., Ltd.)Discussion on Methods for Preparation of High-purity Lithium Carbonate that it can be seen from LiOH
ammonium bicarbonate precipitation method that Li2CO3 can be obtained only by introducing carbonate in LiOH, and CO2 is a widely used gas. Therefore, a reaction system is free from large quantity of impurities in the following reaction.
2LiOH + CO2 ¨>Li2CO3 + H2O
Washed CO2 gas can reach a fairly pure standard, that is, the purity of products depends exclusively on LiOH, the method is the immediate and widely used method for preparing high-purity lithium carbonate, and technical LiOH is generally used to react with lithium carbonate directly to obtain 99% products. However, 99.99% lithium carbonate can not be directly obtained by the method.
Summary of the Invention The technical problem to be solved in the invention is to provide a method using lithium hydroxide to directly prepare 99.99% lithium carbonate via a simple production process.
The technical solution of the invention is as follows:
a. Battery-grade lithium hydroxide monohydrate is prepared into a solution with 50 -90g/L Li2O;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Li2O
concentration of the solution decreases to 40g/L; the flow rate of CO2 is lowered down to 0.8 - 1.2L/s when the Li20 concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry.
This has not only saved the consumption of CO2 gas, also ensured the precipitated Li2CO3 won't be hydrogenated into LiHCO3 that will affect the primary yield of lithium, while avoided the inclusion of lithium carbonate; and c. Separating High-purity lithium carbonate can be gained by separating, washing and drying the lithium carbonate slurry obtained in step b to a moisture content of lower than 0.1%.
According to another aspect of the present invention, there is provided a method for preparing lithium carbonate having a purity of 99.99% or greater, comprising the steps of: (a) preparing a lithium hydroxide solution with an equivalent Li20 concentration of 50-90 g/L from a battery-grade lithium hydroxide monohydrate; (b) introducing CO2 gas into the lithium hydroxide solution described in step (a) at a flow rate of 3-5 L/s to precipitate lithium carbonate and obtain a lithium carbonate slurry, the flow rate of CO2 being lowered down to 2-3 L/s when the equivalent Li20 concentration of the solution decreases to 40 g/L;
and the flow rate of CO2 being lowered down to 0.8-1.2 L/s when the equivalent Li20 concentration of the solution decreases to 20 g/L; (c) washing and drying the lithium carbonate slurry obtained in step (b) to a moisture content of lower than 0.1%
by weight.
In order to further reduce Ca2+ and Mg2+ contents in products, conventional methods are used to remove Ca2+ and Mg2+ contents from the lithium hydroxide solution in step a to allow Ca2+ concentration of products to be lower than 3ppm and Mg2+
concentration of products to be lower than lppm by usually adding lithium phosphate, lithium dihydrogen phosphate, oxalic acid or EDTA to reach this goal, and the insoluble impurities in the solutions is filtered out by filter pressing.
The stirring rate in step b is kept at 60 - 80rpm during gas introduction. The Li2CO3 obtained has large particle size and is less likely to generate secondary aggregation by controlling the stirring rate. Too slow rotation speed is unfavorable for=
collision between ions, affecting reaction speed, and too fast rotation speed easily causes generated lithium carbonate particles to be smashed, affecting product quality.
Reaction temperature reported in existing technical documents is 50 C in step b, and reaction is carried out at 10 - 30 C in the invention. No additional energy is needed in the invention, and too high temperature will result in low utilization rate of CO2 gas, and too low temperature will result in reduced reaction speed and severe caking.
In step b, the temperature is risen to 80 - 120 C after the gas stops introducing, and the temperature is held for 20 - 50min for crystal grain growth.
In addition, in order to completely wash and remove water-soluble impurities in step c, water washing is important. Water is added at a solid-to-liquid ratio (weight ratio) of 1:2 - 4, stir washing temperature is controlled at 90 - 98 C for centrifugal separation, solid is a wet lithium carbonate product, and sodium, potassium, sulfate radicals and other foreign ions are dissolved in the stir washing water to be separated with lithium carbonate.
One embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared into a solution with 50 -90g/L Li20;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 3L/s when the Li20 concentration of the solution decreases to 40g,/L; the flow rate of CO2 is lowered down to 3a :A 02820112 2013-08-05 0.8 - 1.2L/s when the Li20 concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry.
This has not only saved the consumption of CO2 gas, also ensured the precipitated Li2CO3 won't be hydrogenated into LiHCO3 that will affect the primary yield of lithium, while avoided the inclusion of lithium carbonate; and c. Separating. High-purity lithium carbonate can be gained by separating, washing and drying (at 105V) the lithium carbonate slurry obtained in step b to a moisture content of lower than 0.1%.
Another embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared into a solution with 50 -90g/L Li20, Ca2+ and Mg2+ contents of which are removed by conventional methods, usually adding lithium phosphate, lithium dihydrogen phosphate, oxalic acid or EDTA to reach this goal, and the insoluble impurities in the solutions is filtered out by filter pressing;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Li20 concentration of the solution decreases to 40g/L; the flow rate of CO2 is lowered down to 0.8 - 1.2L/s when the Li20 concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry.
This has not only saved the consumption of CO2 gas, also ensured the precipitated Li2CO3 won't be hydrogenated into LiHCO3 that will affect the primary yield of lithium, while avoided the inclusion of lithium carbonate; and c. Separating. High-purity lithium carbonate can be gained by separating, washing and drying the lithium carbonate slurry obtained in step b to a moisture content of lower than 0.1%.
Another embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared a solution with 50 -90g/L Li20, Ca2+ and Mg2+ contents of which are removed by conventional methods, usually adding lithium phosphate, lithium dihydrogen phosphate, oxalic acid or EDTA to reach this goal, and the insoluble impurities in the solutions is filtered out by filter pressing;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Li2O
concentration of the solution decreases to 40g/L; the flow rate of CO2 is lowered down to
4 =
:A 02820112 2013-08-05 0.8 - 1.2L/s when the Li20 concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry.
The stirring rate is kept at 60 - 80rpm during gas introduction. The Li2CO3 obtained has large particle size and is less likely to generate secondary aggregation by controlling the stirring rate. Too slow rotation speed is unfavorable for collision between ions, affecting reaction speed, and too fast rotation speed easily causes generated lithium carbonate particles to be smashed, affecting product quality.
c. Separating. High-purity lithium carbonate can be gained by separating, washing and drying the lithium carbonate slurry obtained in step b to a moisture content of lower than 0.1%.
Another embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared a solution with 50 -90g/L Li2O, Ca2+ and Mg2+ contents of which are removed by conventional methods, usually adding lithium phosphate, lithium dihydrogen phosphate, oxalic acid or EDTA to reach this goal, and the insoluble impurities in the solutions is filtered out by filter pressing;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Li20 concentration of the solution decreases to 40g/L; the flow rate of CO2 is lowered down to 0.8 - 1.2L/s when the Li20 concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry; The stirring rate is kept at 60 - 80rpm during gas introduction. The temperature is risen to 80 - 120 C after the gas stops introducing, and the temperature is held for 20 -50min for crystal grain growth; and c. Separating. High-purity lithium carbonate can be gained by separating, washing and drying the lithium carbonate slurry obtained in step b to a moisture content of lower than 0.1%.
Another embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared into a solution with 50 -90g/L Li20, Ca2+ and Mg2+ contents of which are removed by conventional methods, usually adding lithium phosphate, lithium dihydrogen phosphate, oxalic acid or EDTA to reach this goal, and the insoluble impurities in the solutions is filtered out by filter pressing;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Li20
:A 02820112 2013-08-05 0.8 - 1.2L/s when the Li20 concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry.
The stirring rate is kept at 60 - 80rpm during gas introduction. The Li2CO3 obtained has large particle size and is less likely to generate secondary aggregation by controlling the stirring rate. Too slow rotation speed is unfavorable for collision between ions, affecting reaction speed, and too fast rotation speed easily causes generated lithium carbonate particles to be smashed, affecting product quality.
c. Separating. High-purity lithium carbonate can be gained by separating, washing and drying the lithium carbonate slurry obtained in step b to a moisture content of lower than 0.1%.
Another embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared a solution with 50 -90g/L Li2O, Ca2+ and Mg2+ contents of which are removed by conventional methods, usually adding lithium phosphate, lithium dihydrogen phosphate, oxalic acid or EDTA to reach this goal, and the insoluble impurities in the solutions is filtered out by filter pressing;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Li20 concentration of the solution decreases to 40g/L; the flow rate of CO2 is lowered down to 0.8 - 1.2L/s when the Li20 concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry; The stirring rate is kept at 60 - 80rpm during gas introduction. The temperature is risen to 80 - 120 C after the gas stops introducing, and the temperature is held for 20 -50min for crystal grain growth; and c. Separating. High-purity lithium carbonate can be gained by separating, washing and drying the lithium carbonate slurry obtained in step b to a moisture content of lower than 0.1%.
Another embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared into a solution with 50 -90g/L Li20, Ca2+ and Mg2+ contents of which are removed by conventional methods, usually adding lithium phosphate, lithium dihydrogen phosphate, oxalic acid or EDTA to reach this goal, and the insoluble impurities in the solutions is filtered out by filter pressing;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Li20
5 :A 02820112 2013-08-05 concentration of the solution decreases to 40g/L; the flow rate of CO2 is lowered down to 0.8 - 1.2L/s when the Li20 concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry; The stirring rate is kept at 60 - 80rpm during gas introduction. The temperature is risen to 80 - 120C after the gas stops introducing, and the temperature is held for 20 -50min for crystal grain growth; and c. Separating. After the lithium carbonate slurry obtained in step b is separated, water is added into the solid according to the solid-to-liquid ratio (weight ratio) of 1:2 ¨ 4. The lithium carbonate product can be obtained after stirring and washing at 90 -98 C , centrifugal separating, and drying to a moisture content of lower than 0.1%.
Mother solutions obtained by centrifugal separation in step c of all embodiments of the invention can be reused for preparing LiOH solution in step a.
The beneficial effects of the invention are as follows: battery-grade lithium hydroxide monohydrate can be used as a raw material to simply and conveniently prepare high-purity lithium carbonate with a purity of 99.99% by the method of the invention without further purification.
Brief Description of the Drawing Figure 1 is the process flow chart of a method for preparing high-purity lithium carbonate of the invention.
Description of the Preferred Embodiment One embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared a solution with 50 -90g/L Li20;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Li20 concentration of the solution decreases to 40g/L; the flow rate of CO2 is lowered down to 0.8 - 1.2L/s when the Li2O concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry.
This has not only saved the consumption of CO2 gas, also ensured the precipitated Li2CO3 won't be hydrogenated into LiHCO3 that will affect the primary yield of lithium, while avoided the inclusion of lithium carbonate; and
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry; The stirring rate is kept at 60 - 80rpm during gas introduction. The temperature is risen to 80 - 120C after the gas stops introducing, and the temperature is held for 20 -50min for crystal grain growth; and c. Separating. After the lithium carbonate slurry obtained in step b is separated, water is added into the solid according to the solid-to-liquid ratio (weight ratio) of 1:2 ¨ 4. The lithium carbonate product can be obtained after stirring and washing at 90 -98 C , centrifugal separating, and drying to a moisture content of lower than 0.1%.
Mother solutions obtained by centrifugal separation in step c of all embodiments of the invention can be reused for preparing LiOH solution in step a.
The beneficial effects of the invention are as follows: battery-grade lithium hydroxide monohydrate can be used as a raw material to simply and conveniently prepare high-purity lithium carbonate with a purity of 99.99% by the method of the invention without further purification.
Brief Description of the Drawing Figure 1 is the process flow chart of a method for preparing high-purity lithium carbonate of the invention.
Description of the Preferred Embodiment One embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared a solution with 50 -90g/L Li20;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Li20 concentration of the solution decreases to 40g/L; the flow rate of CO2 is lowered down to 0.8 - 1.2L/s when the Li2O concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry.
This has not only saved the consumption of CO2 gas, also ensured the precipitated Li2CO3 won't be hydrogenated into LiHCO3 that will affect the primary yield of lithium, while avoided the inclusion of lithium carbonate; and
6 :A 02820112 2013-08-05 c. Separating. High-purity lithium carbonate can be gained by separating, washing and drying (at 105 C) the lithium carbonate slurry obtained in step b to a moisture content of lower than 0.1%.
Another embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared into a solution with 50 -90g/L Li20, Ca2+ and Mg2+ contents of which are removed by conventional methods, usually adding lithium phosphate, lithium dihydrogen phosphate, oxalic acid or EDTA to reach this goal, and the insoluble impurities in the solutions is filtered out by filter pressing;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Liz() concentration of the solution decreases to 40g/L; the flow rate of CO2 is lowered down to 0.8 - 1.2L/s when the Li20 concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry.
This has not only saved the consumption of CO2 gas, also ensured the precipitated Li2CO3 won' t be hydrogenated into LiHCO3 that will affect the primary yield of lithium, while avoided the inclusion of lithium carbonate; and c. Separating. High-purity lithium carbonate can be gained by separating, washing and drying the lithium carbonate slurry obtained in step b to a moisture content of lower than 0.1%.
Another embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared a solution with 50 -90g/L Li2O, Ca2+ and Mg2+ contents of which are removed by conventional methods, usually adding lithium phosphate, lithium dihydrogen phosphate, oxalic acid or EDTA to reach this goal, and the insoluble impurities in the solutions is filtered out by filter pressing;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Li20 concentration of the solution decreases to 40g/L; the flow rate of CO2 is lowered down to 0.8 - 1.2L/s when the Li2O concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry;
The stirring rate is kept at 60 - 80rpm during gas introduction. The Li2CO3 obtained has large particle size and is less likely to generate secondary aggregation by controlling the
Another embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared into a solution with 50 -90g/L Li20, Ca2+ and Mg2+ contents of which are removed by conventional methods, usually adding lithium phosphate, lithium dihydrogen phosphate, oxalic acid or EDTA to reach this goal, and the insoluble impurities in the solutions is filtered out by filter pressing;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Liz() concentration of the solution decreases to 40g/L; the flow rate of CO2 is lowered down to 0.8 - 1.2L/s when the Li20 concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry.
This has not only saved the consumption of CO2 gas, also ensured the precipitated Li2CO3 won' t be hydrogenated into LiHCO3 that will affect the primary yield of lithium, while avoided the inclusion of lithium carbonate; and c. Separating. High-purity lithium carbonate can be gained by separating, washing and drying the lithium carbonate slurry obtained in step b to a moisture content of lower than 0.1%.
Another embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared a solution with 50 -90g/L Li2O, Ca2+ and Mg2+ contents of which are removed by conventional methods, usually adding lithium phosphate, lithium dihydrogen phosphate, oxalic acid or EDTA to reach this goal, and the insoluble impurities in the solutions is filtered out by filter pressing;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Li20 concentration of the solution decreases to 40g/L; the flow rate of CO2 is lowered down to 0.8 - 1.2L/s when the Li2O concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry;
The stirring rate is kept at 60 - 80rpm during gas introduction. The Li2CO3 obtained has large particle size and is less likely to generate secondary aggregation by controlling the
7 :A 02820112 2013-08-05 =
stirring rate. Too slow rotation speed is unfavorable for collision between ions, affecting reaction speed, and too fast rotation speed easily causes generated lithium carbonate particles to be smashed, affecting product quality.
c. Separating. High-purity lithium carbonate can be gained by separating, washing and drying the lithium carbonate slurry obtained in step b to a moisture content of lower than 0.1%.
Another embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared into a solution with 50 -90g/L Li20, Calf and Mg2+ contents of which are removed by conventional methods, usually adding lithium phosphate, lithium dihydrogen phosphate, oxalic acid or EDTA to reach this goal, and the insoluble impurities in the solutions is filtered out by filter pressing;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Li20 concentration of the solution decreases to 40WL; the flow rate of CO2 is lowered down to 0.8 - 1.2L/s when the Liz() concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 gas stops to obtain a lithium carbonate slurry; The stirring rate is kept at 60 - 80rpm during gas introduction. The temperature is risen to 80 - 120 C after stopping introducing CO2 gas, and the temperature is held for 20 -50min for crystal grain growth; and c. Separating. High-purity lithium carbonate can be gained by separating, washing and drying the lithium carbonate slurry obtained in step b to a moisture content of lower than 0.1%.
Another embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared into a solution with 50 -90g/L Li20, Ca2+ and Mg2+ contents of which are removed by conventional methods, usually adding lithium phosphate, lithium dihydrogen phosphate, oxalic acid or EDTA to reach this goal, and the insoluble impurities in the solutions is filtered out by filter pressing;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Li2O
concentration of the solution decreases to 40g/L; the flow rate of CO2 is lowered down to 0.8 - 1.2L/s when the Liz() concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry. The stirring rate is kept at 60 - 80rpm during gas introduction. The temperature is risen to 80 - 120 C after stopping introducing CO2 gas, and the temperature is held for 20 -= =
:A 02820112 2013-08-05 50min for crystal grain growth; and c. After the lithium carbonate slurry obtained in step b is separated, water is added into the solid according to the solid-to-liquid ratio (weight ratio) of 1:2 ¨
4.The lithium carbonate product can be obtained after stirring and washing at 90 - 98 C, centrifugal separating, and drying to a moisture content of lower than 0.1%.
Example 1 Preparation of high-purity lithium carbonate by the method of the invention The method comprises the following steps (refer to Figure 1): approximately 600kg battery-grade lithium hydroxide monohydrate is added to distilled water in a reaction kettle for the preparation of lithium hydroxide solution with 80g/L Li20. The new solution is stirred to react for a period of time. Then EDTA is added with excessive 3%
based on Calf and Mg2+ concentration of the lithium hydroxide solution for complexing with Ca2+ and Mg2+ in the solution to obtain the purified lithium hydroxide solution. The insoluble impurities of which is filtered out by filter pressing to obtain lithium hydroxide filtrate with Ca2+ concentration of the product to be lower than 3ppm and Mg2+ concentration of the product to be lower than lppm.
Lithium hydroxide filtrate is added to a reaction vessel and CO2 gas is introduced at the flow rate of CO2 of 3L/s. The flow rate of CO2 is lowered down to 2L/s when the Li20 concentration of the solution decreases to 40g/L; the flow rate of CO2 is lowered down to 1L/s when the Liz() concentration of the solution decreases to 20g/L. And the solution should be stirred at a rate of 70rpm while the CO2 gas is introducing. When massive solid appears in the solution, the introduction of CO2 stops and the temperature is risen to 100 C
for duration of 30 min. The coarse lithium carbonate is obtained by centrifugal separation.
Water is added into the coarse lithium carbonate according to solid-to-liquid ratio of 1:3. A wet lithium carbonate is obtained after stirring and rising temperature to 95 C, centrifugal separating under the heat. The wet lithium carbonate is placed into a double cone rotary vacuum drier for drying, when the moisture content is lower than 0.1%
drying stops.
The high-purity lithium carbonate with main content of 99.991% is obtained after crushed with a jet mill to average particle size less than 61.1m. Then the high-purity lithium carbonate product is packaged with cleaned Vacuum package.
Examples 2 to 8 Preparation of high-purity lithium carbonate by the method of the invention . .
:A 02820112 2013-08-05 .
Methods in examples 2 to 8 are the same as the method in example 1, and the only difference is the flow rate of CO2. See Table 1 for detailed results.
Example Concentration of Flow rate of Flow rate of CO2 Flow rate of CO2 Content of lithium carbonate CO2 at the first at the second at the third stage, lithium solution, Li20 g/L stage, Lis stage, LA L/s carbonate Example 1 80 3 2 1-99.991%
Example 2 80 5 3 1 99.990%
Example 3 80 4 2 1 99.991%
Example 4 80 4 3 1 99.990%
Example 5 80 5 2 1 99.990%
Example 6 80 3 3 1 99.990%
Example 7 80 4 1.5 1 99.991%
Example 8 80 4 1.5 1 99.991%
Comparison 80 6 4 2 99.982%
example 1 Comparison 80 6 99.97%
example 2 It can be seen from Table 2 that 99.99% high-purity lithium carbonate can be realized in one step without further purification by controlling the flow rate of CO2 during introduction of CO2 in the invention.
The inventor of the invention can obtain high-purity lithium carbonate with content of lithium carbonate of 99.99% within 50 - 90g/L Li20 concentration by adjusting the concentration of lithium hydroxide. When the concentration of lithium hydroxide is too low at 45g/L, lithium recovery is low and equipment utilization rate is low due to increase of _ mother solution, and when the concentration of lithium hydroxide is higher than 90g/L, the quality requirement of 99.99% high-purity lithium carbonate can not be reached due to incomplete dissolution of lithium hydroxide and high impurity concentration.
stirring rate. Too slow rotation speed is unfavorable for collision between ions, affecting reaction speed, and too fast rotation speed easily causes generated lithium carbonate particles to be smashed, affecting product quality.
c. Separating. High-purity lithium carbonate can be gained by separating, washing and drying the lithium carbonate slurry obtained in step b to a moisture content of lower than 0.1%.
Another embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared into a solution with 50 -90g/L Li20, Calf and Mg2+ contents of which are removed by conventional methods, usually adding lithium phosphate, lithium dihydrogen phosphate, oxalic acid or EDTA to reach this goal, and the insoluble impurities in the solutions is filtered out by filter pressing;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Li20 concentration of the solution decreases to 40WL; the flow rate of CO2 is lowered down to 0.8 - 1.2L/s when the Liz() concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 gas stops to obtain a lithium carbonate slurry; The stirring rate is kept at 60 - 80rpm during gas introduction. The temperature is risen to 80 - 120 C after stopping introducing CO2 gas, and the temperature is held for 20 -50min for crystal grain growth; and c. Separating. High-purity lithium carbonate can be gained by separating, washing and drying the lithium carbonate slurry obtained in step b to a moisture content of lower than 0.1%.
Another embodiment of the invention is:
a. Battery-grade lithium hydroxide monohydrate is prepared into a solution with 50 -90g/L Li20, Ca2+ and Mg2+ contents of which are removed by conventional methods, usually adding lithium phosphate, lithium dihydrogen phosphate, oxalic acid or EDTA to reach this goal, and the insoluble impurities in the solutions is filtered out by filter pressing;
b. CO2 gas is introduced at a flow rate of 3 - 5L/s into the lithium hydroxide solution described in step a, the flow rate of CO2 is lowered down to 2 - 3L/s when the Li2O
concentration of the solution decreases to 40g/L; the flow rate of CO2 is lowered down to 0.8 - 1.2L/s when the Liz() concentration of the solution decreases to 20g/L;
when massive solid appears in the solution, the introduction of CO2 stops to obtain a lithium carbonate slurry. The stirring rate is kept at 60 - 80rpm during gas introduction. The temperature is risen to 80 - 120 C after stopping introducing CO2 gas, and the temperature is held for 20 -= =
:A 02820112 2013-08-05 50min for crystal grain growth; and c. After the lithium carbonate slurry obtained in step b is separated, water is added into the solid according to the solid-to-liquid ratio (weight ratio) of 1:2 ¨
4.The lithium carbonate product can be obtained after stirring and washing at 90 - 98 C, centrifugal separating, and drying to a moisture content of lower than 0.1%.
Example 1 Preparation of high-purity lithium carbonate by the method of the invention The method comprises the following steps (refer to Figure 1): approximately 600kg battery-grade lithium hydroxide monohydrate is added to distilled water in a reaction kettle for the preparation of lithium hydroxide solution with 80g/L Li20. The new solution is stirred to react for a period of time. Then EDTA is added with excessive 3%
based on Calf and Mg2+ concentration of the lithium hydroxide solution for complexing with Ca2+ and Mg2+ in the solution to obtain the purified lithium hydroxide solution. The insoluble impurities of which is filtered out by filter pressing to obtain lithium hydroxide filtrate with Ca2+ concentration of the product to be lower than 3ppm and Mg2+ concentration of the product to be lower than lppm.
Lithium hydroxide filtrate is added to a reaction vessel and CO2 gas is introduced at the flow rate of CO2 of 3L/s. The flow rate of CO2 is lowered down to 2L/s when the Li20 concentration of the solution decreases to 40g/L; the flow rate of CO2 is lowered down to 1L/s when the Liz() concentration of the solution decreases to 20g/L. And the solution should be stirred at a rate of 70rpm while the CO2 gas is introducing. When massive solid appears in the solution, the introduction of CO2 stops and the temperature is risen to 100 C
for duration of 30 min. The coarse lithium carbonate is obtained by centrifugal separation.
Water is added into the coarse lithium carbonate according to solid-to-liquid ratio of 1:3. A wet lithium carbonate is obtained after stirring and rising temperature to 95 C, centrifugal separating under the heat. The wet lithium carbonate is placed into a double cone rotary vacuum drier for drying, when the moisture content is lower than 0.1%
drying stops.
The high-purity lithium carbonate with main content of 99.991% is obtained after crushed with a jet mill to average particle size less than 61.1m. Then the high-purity lithium carbonate product is packaged with cleaned Vacuum package.
Examples 2 to 8 Preparation of high-purity lithium carbonate by the method of the invention . .
:A 02820112 2013-08-05 .
Methods in examples 2 to 8 are the same as the method in example 1, and the only difference is the flow rate of CO2. See Table 1 for detailed results.
Example Concentration of Flow rate of Flow rate of CO2 Flow rate of CO2 Content of lithium carbonate CO2 at the first at the second at the third stage, lithium solution, Li20 g/L stage, Lis stage, LA L/s carbonate Example 1 80 3 2 1-99.991%
Example 2 80 5 3 1 99.990%
Example 3 80 4 2 1 99.991%
Example 4 80 4 3 1 99.990%
Example 5 80 5 2 1 99.990%
Example 6 80 3 3 1 99.990%
Example 7 80 4 1.5 1 99.991%
Example 8 80 4 1.5 1 99.991%
Comparison 80 6 4 2 99.982%
example 1 Comparison 80 6 99.97%
example 2 It can be seen from Table 2 that 99.99% high-purity lithium carbonate can be realized in one step without further purification by controlling the flow rate of CO2 during introduction of CO2 in the invention.
The inventor of the invention can obtain high-purity lithium carbonate with content of lithium carbonate of 99.99% within 50 - 90g/L Li20 concentration by adjusting the concentration of lithium hydroxide. When the concentration of lithium hydroxide is too low at 45g/L, lithium recovery is low and equipment utilization rate is low due to increase of _ mother solution, and when the concentration of lithium hydroxide is higher than 90g/L, the quality requirement of 99.99% high-purity lithium carbonate can not be reached due to incomplete dissolution of lithium hydroxide and high impurity concentration.
Claims (6)
1. A method for preparing lithium carbonate having a purity of 99.99% or greater, comprising the steps of:
(a) preparing a lithium hydroxide solution with an equivalent Li2O
concentration of 50-90 g/L from a battery-grade lithium hydroxide monohydrate;
(b) introducing CO2 gas into the lithium hydroxide solution described in step (a) at a flow rate of 3-5 L/s to precipitate lithium carbonate and obtain a lithium carbonate slurry, the flow rate of CO2 being lowered down to 2-3 L/s when the equivalent Li2O
concentration of the solution decreases to 40 g/L; and the flow rate of CO2 being lowered down to 0.8-1.2 L/s when the equivalent Li2O concentration of the solution decreases to 20 g/L;
(c) washing and drying the lithium carbonate slurry obtained in step (b) to a moisture content of lower than 0.1% by weight.
(a) preparing a lithium hydroxide solution with an equivalent Li2O
concentration of 50-90 g/L from a battery-grade lithium hydroxide monohydrate;
(b) introducing CO2 gas into the lithium hydroxide solution described in step (a) at a flow rate of 3-5 L/s to precipitate lithium carbonate and obtain a lithium carbonate slurry, the flow rate of CO2 being lowered down to 2-3 L/s when the equivalent Li2O
concentration of the solution decreases to 40 g/L; and the flow rate of CO2 being lowered down to 0.8-1.2 L/s when the equivalent Li2O concentration of the solution decreases to 20 g/L;
(c) washing and drying the lithium carbonate slurry obtained in step (b) to a moisture content of lower than 0.1% by weight.
2. The method according to claim 1, wherein the lithium hydroxide solution comprises Ca2+ or Mg2+, and the method further comprises a step of adding lithium phosphate, lithium dihydrogen phosphate, oxalic acid or EDTA to the lithium hydroxide solution prior to step (b) to remove the Ca2+ and Mg2+.
3. The method according to claim 2, further comprising a step of filtering insoluble impurities from the lithium hydroxide solution, wherein the filtering is performed by filter pressing.
4. The method according to any one of claims 1 to 3, wherein prior to step (c) introduction of CO2 gas is ceased, and the lithium hydroxide solution temperature is raised to 80-120°C for 20-50 min.
5. The method according to any one of claims 1 to 4, wherein following step (b), the lithium hydroxide solution from which lithium carbonate has been precipitated is used to prepare the lithium hydroxide solution in step (a).
6. The method according to any one of claims 1 to 5, wherein the washing in step (c) comprises adding water at a lithium carbonate to water weight ratio of between 1:2 and 1:4 to obtain a mixture, stirring the mixture, and maintaining the mixture temperature at 90-98°C
during stirring.
during stirring.
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| CN2010106008028A CN102020295B (en) | 2010-12-22 | 2010-12-22 | Preparation method of high-purity lithium carbonate |
| CN201010600802.8 | 2010-12-22 | ||
| PCT/CN2011/076978 WO2012083678A1 (en) | 2010-12-22 | 2011-07-08 | Method for preparing high-purity lithium carbonate |
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| CN102020295B (en) * | 2010-12-22 | 2012-07-25 | 四川天齐锂业股份有限公司 | Preparation method of high-purity lithium carbonate |
| CN102807237B (en) * | 2011-06-01 | 2014-11-05 | 上海中锂实业有限公司 | Method for preparing anhydrous lithium nitrate |
| CN102267707B (en) * | 2011-07-01 | 2013-06-12 | 清华大学 | Process for preparing nanometer lithium carbonate particle by precipitation |
| CN102583453B (en) * | 2011-08-31 | 2013-10-16 | 四川长和华锂科技有限公司 | Industrial method for producing battery-grade lithium carbonate or high-purity lithium carbonate |
| CN102515212A (en) * | 2011-11-14 | 2012-06-27 | 山东瑞福锂业有限公司 | Method for preparing battery-grade lithium carbonate |
| EP2841623B1 (en) | 2012-04-23 | 2020-10-28 | Nemaska Lithium Inc. | Processes for preparing lithium hydroxide |
| EP3363930B1 (en) | 2012-05-30 | 2024-03-13 | Nemaska Lithium Inc. | Processes for preparing lithium carbonate |
| US20160032471A1 (en) | 2013-03-15 | 2016-02-04 | Nemaska Lithium Inc. | Processes for preparing lithium hydroxide |
| CN103351010B (en) * | 2013-06-29 | 2015-10-28 | 西北矿冶研究院 | Preparation process of battery-grade lithium carbonate |
| CN105849047B (en) | 2013-10-23 | 2018-11-13 | 内玛斯卡锂公司 | The method for preparing lithium carbonate |
| CN105849317B (en) | 2013-10-23 | 2018-11-27 | 内玛斯卡锂公司 | Prepare the method and system of lithium hydroxide |
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| CN110331417A (en) | 2014-02-24 | 2019-10-15 | 内玛斯卡锂业有限公司 | The method for handling lithium-containing materials |
| TWI563716B (en) * | 2014-07-16 | 2016-12-21 | Prologium Technology Co Ltd | Anode electrode |
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| CN106025253A (en) * | 2016-05-12 | 2016-10-12 | 天津普兰能源科技有限公司 | Method for preparing lithium titanate |
| CA2940509A1 (en) | 2016-08-26 | 2018-02-26 | Nemaska Lithium Inc. | Processes for treating aqueous compositions comprising lithium sulfate and sulfuric acid |
| CN106365182B (en) * | 2016-08-30 | 2017-09-29 | 荆门市格林美新材料有限公司 | The method that the industrial level lithium carbonate of pulsed hydrogenation prepares battery-level lithium carbonate |
| CN106517258B (en) * | 2016-11-23 | 2017-09-29 | 荆门市格林美新材料有限公司 | The preparation method of battery-level lithium carbonate |
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| CA3083136C (en) | 2017-11-22 | 2022-04-12 | Nemaska Lithium Inc. | Processes for preparing hydroxides and oxides of various metals and derivatives thereof |
| CN109970085A (en) * | 2019-04-26 | 2019-07-05 | 核工业北京化工冶金研究院 | A kind of new process preparing lithium product from lepidolite leachate |
| CN113003588A (en) * | 2019-12-20 | 2021-06-22 | 中核北方核燃料元件有限公司 | Nuclear pure grade Li2CO3Chemical conversion method |
| CN111533144A (en) * | 2020-03-27 | 2020-08-14 | 白银中天化工有限责任公司 | Method for purifying low-grade lithium fluoride |
| CN113526531A (en) * | 2020-04-17 | 2021-10-22 | 中国石油化工股份有限公司 | Method for recovering high-purity submicron lithium carbonate from lithium battery ternary material washing liquid |
| CN111547748A (en) * | 2020-06-17 | 2020-08-18 | 赣州有色冶金研究所 | Method for preparing battery-grade lithium carbonate by efficiently decarbonizing lithium bicarbonate solution |
| CN112299455A (en) * | 2020-11-12 | 2021-02-02 | 萍乡市拓源实业有限公司 | Method for directly preparing industrial grade or battery grade lithium carbonate by using crude lithium carbonate |
| CN113461035A (en) * | 2021-08-03 | 2021-10-01 | 四川国理锂材料有限公司 | Method for preparing battery-grade lithium carbonate from high-calcium crude lithium carbonate |
| CN114368765B (en) * | 2021-08-20 | 2023-09-22 | 山东泰普锂业科技有限公司 | Morphology control method of smooth-surface lithium carbonate nanosheets for lithium supplementing of positive electrode in lithium ion battery |
| CN114361431A (en) * | 2021-08-20 | 2022-04-15 | 山东瑞福锂业有限公司 | Process and method for regulating and controlling structure of regular micron sheet lithium carbonate material for ternary positive electrode material in lithium ion battery |
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| CN114291831A (en) * | 2021-12-20 | 2022-04-08 | 江西永兴特钢新能源科技有限公司 | Method for producing battery-grade lithium carbonate by continuously precipitating lithium through extracting lithium from lepidolite |
| CN116789153A (en) * | 2023-06-30 | 2023-09-22 | 江西金辉锂业有限公司 | Method for preparing high-purity lithium carbonate from crude lithium carbonate |
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| JPH08217438A (en) * | 1995-02-13 | 1996-08-27 | Nippon Chem Ind Co Ltd | Production of lithium carbonate |
| US6048507A (en) * | 1997-12-09 | 2000-04-11 | Limtech | Process for the purification of lithium carbonate |
| JP2004196607A (en) * | 2002-12-19 | 2004-07-15 | Nippon Chem Ind Co Ltd | Method for manufacturing high purity lithium carbonate |
| RU2247695C1 (en) * | 2003-09-11 | 2005-03-10 | Открытое акционерное общество "Новосибирский завод химконцентратов" | Method for production of spectral-pure lithium carbonate |
| CN100595150C (en) * | 2006-12-31 | 2010-03-24 | 比亚迪股份有限公司 | Method for preparing nano-scale lithium carbonate for battery |
| JP4896109B2 (en) * | 2008-10-24 | 2012-03-14 | 日本化学工業株式会社 | Method for producing high purity lithium carbonate |
| JP4896108B2 (en) * | 2008-10-24 | 2012-03-14 | 日本化学工業株式会社 | Method for producing high purity lithium carbonate |
| CN102020295B (en) * | 2010-12-22 | 2012-07-25 | 四川天齐锂业股份有限公司 | Preparation method of high-purity lithium carbonate |
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|---|---|---|---|
| EEER | Examination request |
Effective date: 20130605 |