CN111153419B - Method for extracting lithium - Google Patents
Method for extracting lithium Download PDFInfo
- Publication number
- CN111153419B CN111153419B CN201811525345.3A CN201811525345A CN111153419B CN 111153419 B CN111153419 B CN 111153419B CN 201811525345 A CN201811525345 A CN 201811525345A CN 111153419 B CN111153419 B CN 111153419B
- Authority
- CN
- China
- Prior art keywords
- lithium
- acid
- impurities
- solution
- phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for extracting lithium, which comprises the following steps: preparing lithium phosphate containing impurities; dissolving the lithium phosphate and impurities in an acid; the lithium ion battery is characterized in that an additive is added to a solution in which the lithium phosphate and impurities are dissolved in acid to obtain a lithium-containing solution, the additive is a substance that simultaneously precipitates phosphate anions and impurities, and the lithium-containing solution obtained by the additive is alkaline.
Description
Technical Field
The invention relates to a method for extracting lithium.
Background
In recent years, lithium secondary batteries have been variously used as power sources for IT devices such as mobile phones and notebook computers, have attracted attention as power sources for electric vehicles, and are expected to rapidly develop in the coming years in electric vehicles and new renewable energy power Storage systems (electric Storage systems), and thus, the demand for lithium secondary batteries has sharply increased.
Lithium used as a raw material of an anode material, a cathode material, and an electrolyte, which are important accessories of electric vehicles and power storage systems, is mainly lithium carbonate (Li) 2 CO 3 ) The method (2) is used. Therefore, in order to manufacture electric vehicles and power storage systems, for which a demand is expected to increase greatly, at low cost and to smoothly supply them to the market, it is necessary to develop a technology capable of economically manufacturing lithium carbonate.
Generally, lithium carbonate is produced by naturally evaporating natural Brine (Brine) containing lithium of about 0.2 to 1.5g/L to concentrate the natural Brine into lithium of about 60g/L, adding carbonate, and adding lithium carbonate (Li) 2 CO 3 ) The form of (2) is precipitated and produced. However, due to the high solubility of lithium carbonate (13g/L), it is necessary to evaporate and concentrate the brine for a long time of one year or more in order to concentrate lithium to a level of 60g/L, and a large amount of lithium is precipitated and lost in the evaporation and concentration process.
To solve the problems, lithium phosphate (Li) capable of minimizing a natural evaporation process was developed 3 PO 4 ) The extraction method of (Korea granted patent No. 10-1363342). When lithium is extracted in the form of lithium phosphate by the extraction method of lithium phosphate, the evaporation and concentration process of brine for a long time can be eliminated or greatly shortened due to the low solubility (0.39g/L) characteristic of lithium phosphate, and lithium loss generated in the evaporation and concentration process can be suppressed, thereby extracting lithium at a high recovery rate. However, as described above, in order toLithium phosphate is used as a raw material for a secondary lithium battery, and it is necessary to convert lithium phosphate into lithium carbonate.
In recent years, a technique for producing lithium carbonate has been developed in which Ca (OH) is mixed into a lithium phosphate-water suspension (slurry) at a high temperature (90 ℃ or higher) 2 Preparing a low-concentration lithium hydroxide solution having a lithium concentration of 5g/L or less, evaporating and concentrating the lithium hydroxide solution to prepare a high-concentration lithium hydroxide solution having a lithium concentration of 30g/L or more, and then charging carbon dioxide (CO) 2 ) Gas to produce lithium carbonate.
However, when lithium phosphate is converted into lithium carbonate by the above method, it is necessary to perform a long-time reaction after heating a lithium phosphate suspension at a high temperature, and also it is necessary to evaporate and concentrate a low-concentration lithium hydroxide solution, so that there is a problem in that energy costs are increased (korean patent laid-open No. 10-1405486).
Also, a method for producing lithium carbonate has been developed in which lithium phosphate is dissolved in acid to produce a lithium solution having a lithium concentration of 0.05g/L to 0.16g/L, then divalent alkaline earth metal and phosphorus are removed with an ion exchange resin, and an aqueous lithium hydroxide solution having a lithium concentration of 3.5g/L to 4.5g/L obtained by bipolar membrane electrodialysis is reacted with carbon dioxide gas to obtain lithium carbonate.
However, when lithium carbonate is manufactured using the method, since the concentration of lithium in a lithium solution is excessively low, the recovery rate of lithium is low, and an expensive large-sized electrolysis apparatus is required, and the manufacturing cost is greatly increased as a large amount of electricity is used (korean patent laid-open No. 10-1888181).
Further, a method for producing lithium carbonate has been developed in which an acid is added to a mixed suspension of a lithium phosphate-metal compound (one of iron, copper, aluminum, zinc, manganese, calcium, cerium, yttrium, or lanthanum compounds) to dissolve the mixed suspension, an alkali hydroxide is added to the mixed suspension to adjust the pH to 1 to 10, thereby producing a high-concentration lithium solution from which metal and phosphorus are removed, and a carbonate is added to the high-concentration lithium solution to produce lithium carbonate. However, when the method is used, the amount of acid used increases in order to dissolve all of lithium phosphate and the metal compound. Further, when an alkali is added to introduce and precipitate metal ions in an acidic solution in which lithium phosphate is dissolved, heavy metal ions may not be completely removed as the pH of the reaction solution is limited to 1 to 10, and after the lithium phosphate-metal compound mixture is dissolved, the pH is adjusted by adding the alkali, so that the process becomes complicated and the amount of raw materials used increases, thereby decreasing the economical efficiency (japanese patent granted JP5632169B2& JP5528153B 2).
As described above, when the currently developed method for manufacturing lithium carbonate using lithium phosphate is used, there is a problem in that economical efficiency is reduced due to low lithium recovery rate, high energy cost and high equipment investment cost, excessively high raw material cost, complexity of process, and the like. Therefore, there is an urgent need to develop a technology capable of economically producing lithium carbonate using lithium phosphate.
Disclosure of Invention
Technical problem to be solved
It is therefore an object of the present invention to provide a method for extracting lithium with a high lithium recovery rate.
In addition, the method has low energy consumption, raw material cost and equipment investment cost, and simple process, thereby being capable of economically producing lithium compounds from lithium phosphate.
(II) technical scheme
In one embodiment of the present invention, there is provided a method of extracting lithium, the method comprising the steps of: preparing lithium phosphate containing impurities; dissolving the lithium phosphate and impurities in an acid (acid); the lithium-containing solution is obtained by adding an additive, which is a substance that simultaneously precipitates phosphate anions and impurities, to a solution in which the lithium phosphate and impurities are dissolved in an acid, and the lithium-containing solution obtained by the additive is alkaline.
Wherein the impurities may comprise alkaline earth metals.
Wherein the alkaline earth metal can Be beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra) or a combination thereof.
Wherein the concentration of lithium in the solution in which the lithium phosphate and impurities are dissolved in acid may be 10 to 35 g/L.
Wherein, in the step of dissolving the lithium phosphate and the impurities in an acid (acid), the acid may be hydrochloric acid, hypochlorous acid, nitric acid, acetic acid, or a combination thereof.
Wherein a pH of a dissolving solution in which the lithium phosphate and impurities are dissolved in an acid may be-0.1 to 4.5.
Wherein, the additive can be oxide or hydroxide.
Wherein the additive may be an oxide or hydroxide of a cation of beryllium, magnesium, calcium, strontium, barium, radium, or combinations thereof.
More specifically, the additive may be calcium hydroxide (Ca (OH) 2 ) Magnesium hydroxide (Mg (OH) 2 ) Or a combination thereof.
Thus, phosphate anions and impurities can be precipitated from the hardly soluble precipitate.
Wherein the insoluble precipitate may be hydroxyapatite (Ca) 5 (PO 4 ) 3 OH), calcium hydrogen phosphate (Brushite, CaHPO) 4 ·2H 2 O), amorphous calcium-phosphorus compounds, calcium hydroxide, magnesium phosphate (MgHPO) 4 ·3H 2 O), Magnesium phosphate (Mg) 3 (PO 4 ) 2 ) Amorphous magnesium-phosphorus compounds and magnesium hydroxide or combinations thereof.
Wherein in the step of adding an additive to a solution in which the lithium phosphate and impurities are dissolved in an acid to obtain a lithium-containing solution, the pH of the obtained lithium-containing solution may be 9 or more.
Wherein in the step of adding an additive to a solution in which the lithium phosphate and impurities are dissolved in an acid to obtain a lithium-containing solution, the pH of the obtained lithium-containing solution may be 11 or more.
In the lithium-containing solution obtained above, a carbonic acid supply substance may be added to obtain lithium carbonate.
Wherein the carbonic acid supplying substance may be sodium carbonate (Na) 2 CO 3 ) Potassium carbonate (K) 2 CO 3 ) Ammonium carbonate ((NH) 4 ) 2 CO 3 ) Sodium bicarbonate (NaHCO) 3 ) Potassium bicarbonate (KHCO) 3 ) Or a combination thereof.
The method also comprises the step of washing and drying the obtained lithium carbonate.
(III) advantageous effects
In one embodiment of the present invention, a method of extracting lithium from lithium phosphate containing impurities (more specifically, alkaline earth metals) is provided, thereby enabling economical production of a lithium compound (such as lithium carbonate) with high lithium recovery rate, low raw material cost, low energy cost, and low equipment cost.
Drawings
Fig. 1 and table 1 show the pH and lithium concentration of the reaction filtrate obtained by mixing 0.1L of hydrochloric acid aqueous solutions having different degrees of acidity with 10g of lithium phosphate containing magnesium, stirring the mixture for 60 minutes at room temperature, and then filtering the mixture, in order to produce a high-concentration lithium solution having a lithium concentration of 10 g/L.
Table 2 shows the chemical content and pH of the reaction filtrate obtained by adding 10g of lithium phosphate containing magnesium to 0.1L of a hydrochloric acid aqueous solution at room temperature to prepare a lithium phosphate solution containing magnesium having a pH of 4.33, adding 2.3g to 23.8g of calcium hydroxide, stirring for 2 hours, and filtering.
Fig. 2 shows an X-ray diffraction pattern of a precipitate obtained by charging 10g of lithium phosphate containing magnesium into 0.1L of a hydrochloric acid aqueous solution at room temperature to prepare a lithium phosphate solution containing magnesium having a pH of 4.33, then charging 2.3g to 23.8g of calcium hydroxide, stirring for 2 hours, filtering, washing, and drying.
FIG. 3 shows that 6.478g of Na was put into 0.1L of a phosphoric acid solution at room temperature from which magnesium and phosphorus were removed 2 CO 3 And stirred for 2 hours, filtered, washed and dried to obtain a precipitate having an X-ray diffraction pattern.
Detailed Description
Various embodiments of the present invention are described in detail below to enable those skilled in the art to easily practice the invention. The invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
For clarity of explanation of the present invention, portions that are not relevant to the explanation are omitted, and the same reference numerals are used for the same or similar components throughout the specification.
In addition, when a part of the specification is referred to as "including" a certain component, unless otherwise specified, it means that other components may be included instead of being excluded.
Also, in one embodiment of the present invention, there is provided a method for extracting lithium, the method including the steps of: preparing lithium phosphate containing impurities; dissolving the lithium phosphate and impurities in an acid (acid); the lithium-containing solution is obtained by adding an additive, which is a substance that simultaneously precipitates phosphate anions and impurities, to a solution in which the lithium phosphate and impurities are dissolved in an acid, and the lithium-containing solution obtained by the additive is alkaline.
An embodiment of the present invention is specifically described by taking, as an example, a method of dissolving lithium phosphate containing impurities (such as alkaline earth metals) at normal temperature using a hydrochloric acid aqueous solution as an example of the acidic solution, and obtaining a high-concentration lithium phosphate solution; calcium hydroxide, which is an example of the additive, is charged at normal temperature and impurities and phosphorus are removed.
In the following steps, a method will be described in which sodium carbonate, which is an example of a carbonate, is charged into the lithium-containing solution obtained at normal temperature to obtain lithium carbonate; the lithium carbonate is washed with tap water and dried at a high temperature (e.g., 105 c), thereby economically manufacturing the lithium carbonate.
The process of dissolving lithium phosphate containing impurities (magnesium as one of alkaline earth metals) using an aqueous hydrochloric acid solution according to one embodiment of the present invention may be performed by the following reaction formula 1.
[ reaction formula 1]
(Mg,Li)PO 4 +2HCl+3H 2 O→Li + +Mg 2+ +H 2 PO 4 - +2Cl - +3H 2 O
That is, the lithium phosphate containing magnesium is dissolved in hydrochloric acid at normal temperature and converted to contain Li + 、 Mg 2+ 、H 2 PO 4 - 、Cl - The lithium phosphate solution of (1).
Specific examples of the acid for dissolving the lithium phosphate may be hydrochloric acid, hypochlorous acid, nitric acid, acetic acid, or a combination thereof. Although sulfuric acid reacts with alkaline earth metals such as calcium to generate precipitates and also generates acid sludge, it is preferable not to use sulfuric acid in order to reduce removal cost because phosphorus contained in phosphoric acid is a substance that needs to be removed finally. But it is also possible to selectively use part of the sulfuric acid by a combination of various impurities.
The lithium carbonate had a solubility of 13g/L and a concentration of 2.5g/L in terms of lithium. Therefore, when lithium carbonate is produced by precipitating lithium carbonate from the lithium phosphate solution, the lithium concentration in the lithium phosphate solution should be 10g/L or more in order to obtain a high lithium recovery rate of 75% or more.
Therefore, in the present invention, the lithium concentration of the lithium phosphate dissolution liquid is controlled to be 10g/L or more. Further, when the lithium concentration of the lithium phosphate dissolution solution is 30g/L, the lithium recovery rate is 91.7%, which is more preferable.
As shown in the following examples, in order to obtain a lithium phosphate solution having a lithium concentration of 10g/L or more, the pH of a reaction solution obtained by mixing lithium phosphate with an aqueous acid solution should be 4.5 or less. This is explained in further detail in the embodiments described later.
The removal of the alkaline earth metal and the phosphorus according to one embodiment of the present invention may be performed by the following reaction formula 2 or reaction formula 3.
[ reaction formula 2]
Li + +Mg 2+ +H 2 PO 4 - +2Cl - +3H 2 O+Ca(OH) 2 →Li + +H + +2Cl - + Mg(OH) 2 +CaHPO 4 ·2H 2 O+H 2 O
[ reaction formula 3]
3Li + +3Mg 2+ +3H 2 PO 4 - +6Cl - +9H 2 O+5Ca(OH) 2 →3Li + +Cl - + 2OH - +3Mg(OH) 2 +Ca 5 (PO 4 ) 3 ·OH+10H 2 O+5HCl(g)
The additive for removing the alkaline earth metal and the phosphorus may be an additive which reacts with phosphorus at normal temperature to generate a sparingly soluble compound and at the same time generates hydroxide ions (OH) for generating the alkaline earth metal and the sparingly soluble compound - ) The substance of (1). This makes it possible to simultaneously precipitate phosphorus and an alkaline earth metal as impurities.
More specifically, the additive may be an alkaline earth metal oxide or hydroxide.
As a specific example, the cation of the additive may be beryllium, magnesium, calcium, strontium, barium, radium, or a combination thereof, and the additive may be an oxide or hydroxide thereof.
For example, the additive may be calcium hydroxide, magnesium hydroxide, or a combination thereof. As another example, calcium oxide or magnesium oxide may also be used.
For example, calcium carbonate (CaCO) may be heated 3 ) Or magnesium carbonate (MgCO) 3 ) Thereby obtaining calcium oxide or magnesium oxide. When water is added to the calcium oxide or magnesium oxide thus obtained, calcium hydroxide and magnesium hydroxide can be obtained.
In order to remove impurities (such as alkaline earth metals) and phosphorus from the lithium phosphate dissolved solution containing the impurities (such as alkaline earth metals), calcium hydroxide, which is one example of an additive, may be added at normal temperature.
In the specific example, magnesium may be precipitated as sparingly soluble magnesium hydroxide, and phosphorus may be precipitated as sparingly soluble hydroxyapatite (Ca) 5 (PO 4 ) 3 OH) or calcium hydrogen phosphate (Brushite, CaHPO) 4 ·2H 2 O) is precipitated. Which can be removed from the lithium phosphate dissolution solution by filtration.
In order to completely remove phosphorus present in the lithium phosphate dissolution solution, the amount of the additive to be added may be 1 equivalent or more of the phosphorus content. When the range is satisfied, phosphorus can be completely removed, and it is also advantageous in terms of reaction speed.
The amount of the additive to be added may be an amount capable of maintaining the pH of the lithium phosphate dissolution solution at 9 or more, or preferably at 11 or more, so that the alkaline earth metal and phosphorus in the lithium phosphate dissolution solution are precipitated and completely removed.
The lithium carbonate according to the embodiment of the present invention may be manufactured by the following reaction formula 4.
In order to precipitate lithium carbonate from the lithium-containing solution at normal temperature from which the alkaline earth metal and phosphorus are removed according to the embodiment of the present invention, sodium carbonate, which is an example of a carbonic acid supply substance, may be charged.
[ reaction formula 4]
6Li + +2Cl - +4OH - +20H 2 O+3Na 2 CO 3 →3Li 2 CO 3 +6Na + +2Cl - +4OH - +20H 2 O
That is, the sodium carbonate reacts with lithium at normal temperature to generate and precipitate lithium carbonate. Further, when the lithium-containing solution from which the alkaline earth metal and phosphorus are removed is charged by 1 equivalent or more, lithium carbonate can be obtained at a high recovery rate of 75% or more.
Specific examples of the carbonate are sodium carbonate, potassium carbonate, ammonium carbonate and the like.
More specifically, the carbonate salt may be sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, ammonium carbonate, or a combination thereof.
The lithium carbonate may be charged in an amount of 1 equivalent or more to the content of lithium in the lithium-containing solution. When the range is satisfied, it may be advantageous in terms of reaction speed.
In the present specification, the normal temperature does not mean a predetermined temperature, but means a temperature in a state where external energy is not applied. Therefore, the room temperature can be changed depending on the place and time.
The present invention will be described below with reference to specific examples. The scope of the present invention is not limited to the following examples.
[ example 1]
To produce a high-concentration lithium solution having a lithium concentration of 10g/L, 0.1L of aqueous hydrochloric acid solutions having different degrees of acidity were mixed with 10g of lithium magnesium phosphate, respectively, and stirred at room temperature for 60 minutes.
After completion of the stirring, the reaction solution was filtered, and pH and lithium concentration were measured, and the results thereof are shown in fig. 1 and table 1.
As shown in fig. 1, as the pH of the reaction solution decreases, lithium phosphate is dissolved, and thus the concentration of lithium gradually increases. When the pH of the reaction filtrate reached 4.5 or less, it was found that the lithium concentration showed about 10g/L, and the lithium concentration did not increase even if the pH of the reaction filtrate was reduced to 4.5 or less.
From this, it was found that all the lithium phosphate charged was dissolved in the reaction filtrate having a pH of 4.5 or less. Further, when the pH of the reaction filtrate is excessively lowered to-1.0 or less, all lithium phosphate can be dissolved, but there is a problem that the amount of hydrochloric acid used excessively increases.
[ Table 1]
[ example 2]
10g of lithium phosphate containing magnesium was put into 0.1L of a hydrochloric acid aqueous solution at normal temperature and stirred for 1 hour, thereby producing a lithium phosphate dissolved solution containing magnesium having a pH of 4.33.
2.3 to 23.8g of calcium hydroxide was charged into each of the lithium phosphate solutions and stirred for 2 hours, and then precipitates were filtered.
As shown in table 2 below, it was found that phosphorus and magnesium were completely removed when the pH of the reaction filtrate was 11 or more. Although phosphorus and magnesium can be completely removed by charging a large amount of calcium hydroxide to increase the pH of the reaction solution to 14 or more, the cost of raw materials increases, interlayer water exists between unreacted precipitates, and the lithium recovery rate decreases, so that the pH of the lithium phosphate solution charged with the alkaline earth metal oxide or hydroxide can be preferably controlled to 11 to 14 or less.
Further, the precipitate filtered from the reaction solution was washed with tap water and then dried at 105 ℃ for 24 hours. The mineral phase of the precipitate showing a pH of 11.35 of the reaction solution was analyzed by an X-ray diffraction analyzer, and the result thereof is shown in fig. 2.
As shown in fig. 2, magnesium was precipitated as poorly soluble magnesium hydroxide, most of phosphorus was precipitated as poorly soluble hydroxyapatite, and a part of phosphorus was precipitated as lithium phosphate, and thus, magnesium was completely removed from the magnesium-containing lithium phosphate solution.
[ Table 2]
[ example 3]
64.78g of Na was put into 1L of a lithium-containing solution at room temperature from which magnesium and phosphorus were removed 2 CO 3 Thereafter, the mixture was stirred for 2 hours and reacted, and then the precipitate was filtered.
After the precipitate filtered from the reaction solution was washed with tap water, dried at 105 ℃ for 24 hours, and subjected to mineral phase analysis using an X-ray diffraction analyzer. The results of the analysis are shown in fig. 3. As shown in fig. 3, since the precipitate was a single phase of lithium carbonate, it was found that the synthesis of lithium carbonate was successful.
The present invention is not limited to the embodiments described above, and can be implemented in various different ways from each other, and those skilled in the art to which the present invention pertains can understand that the present invention can be implemented in other specific ways without changing the technical idea or necessary technical features of the present invention. The embodiments described above are therefore to be considered in all respects as illustrative and not restrictive.
Claims (9)
1. A method of extracting lithium comprising the steps of:
preparing lithium phosphate containing impurities;
dissolving the lithium phosphate and impurities in an acid;
adding an additive to a solution in which the lithium phosphate and impurities are dissolved in an acid to obtain a lithium-containing solution,
wherein the additive is a substance which simultaneously precipitates phosphate anions and impurities, the lithium-containing solution obtained by the additive is alkaline,
the impurities comprise an alkaline earth metal and, optionally,
and the step of removing impurities for removing alkaline earth metals as impurities is not performed before the step of dissolving the lithium phosphate and impurities in acid,
the acid is hydrochloric acid, hypochlorous acid, nitric acid, acetic acid or their combination.
2. The method for extracting lithium according to claim 1,
the alkaline earth metal is beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra) or the combination thereof.
3. The method for extracting lithium according to claim 1,
the concentration of lithium in the solution in which the lithium phosphate and impurities are dissolved in acid is 10 to 35 g/L.
4. The method for extracting lithium according to claim 1,
the pH of the solution in which the lithium phosphate and impurities are dissolved in acid is-0.1 to 4.5.
5. The method for extracting lithium according to claim 1,
the additive is an oxide or hydroxide.
6. The method for extracting lithium according to claim 5,
the additive is an oxide or hydroxide of a cation of beryllium, magnesium, calcium, strontium, barium, radium, or a combination thereof.
7. The method for extracting lithium according to claim 1,
and a step of adding an additive to a solution in which the lithium phosphate and impurities are dissolved in an acid to obtain a lithium-containing solution, wherein the pH of the obtained lithium-containing solution is 9 to 14.
8. The method for extracting lithium according to claim 1,
a carbonic acid supply substance is charged into the lithium-containing solution to obtain lithium carbonate.
9. The method for extracting lithium according to claim 8,
the carbonic acid supplying substance is sodium carbonate (Na) 2 CO 3 ) Potassium carbonate (K) 2 CO 3 ) Ammonium carbonate ((NH) 4 ) 2 CO 3 ) Sodium bicarbonate (NaHCO) 3 ) Potassium bicarbonate (KHCO) 3 ) Or a combination thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2018-0135864 | 2018-11-07 | ||
| KR1020180135864A KR102145110B1 (en) | 2018-11-07 | 2018-11-07 | Method of extracting lithium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111153419A CN111153419A (en) | 2020-05-15 |
| CN111153419B true CN111153419B (en) | 2022-08-09 |
Family
ID=70555640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811525345.3A Active CN111153419B (en) | 2018-11-07 | 2018-12-13 | Method for extracting lithium |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR102145110B1 (en) |
| CN (1) | CN111153419B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021153816A1 (en) * | 2020-01-29 | 2021-08-05 | 전웅 | Lithium extraction method |
| KR102489066B1 (en) * | 2022-04-08 | 2023-01-18 | 전웅 | Extraction method of lithium, method for preparing lithium carbonate, and method for preparing lithium hydroxide |
| US11873228B2 (en) | 2022-04-08 | 2024-01-16 | Uong CHON | Method of extracting lithium, method of preparing lithium carbonate and method of preparing lithium hydroxide |
| KR102558188B1 (en) * | 2022-12-17 | 2023-07-20 | 전웅 | Economical method removing impurities from waste phosphor-containg lithium battery materials |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011168461A (en) * | 2010-02-22 | 2011-09-01 | Eco-System Recycling Co Ltd | Method for producing high-concentration lithium liquid from lithium-containing liquid and method for producing lithium carbonate |
| CN104220371A (en) * | 2012-04-05 | 2014-12-17 | Posco公司 | Method for manufacturing lithium hydroxide and method using the lithium hydroxide for manufacturing lithium carbonate |
| CN106745099A (en) * | 2016-12-05 | 2017-05-31 | 天津二八科技股份有限公司 | A kind of method that utilization lithium phosphate prepares lithium carbonate |
| WO2018027266A1 (en) * | 2016-08-08 | 2018-02-15 | Enirgi Know-How Pte Ltd | A process for the conversion of lithium phosphate into a low phosphate lithium solution suitable as feedstock for the production of saleable lithium products and for the recovery of phosphorous for re-use in the production of lithium phosphate |
| WO2018110974A1 (en) * | 2016-12-15 | 2018-06-21 | 주식회사 포스코 | Method for producing lithium hydroxide from lithium phosphate |
| CN108285156A (en) * | 2017-11-24 | 2018-07-17 | 中南大学 | A method of extracting pure Lithium Carbonate or lithium hydroxide from phosphoric acid lithium waste residue |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101700684B1 (en) * | 2015-04-30 | 2017-01-31 | 재단법인 포항산업과학연구원 | Method and apparatus for manufacturing lithium hydroxide, and lithium carbonate |
| KR101888181B1 (en) * | 2016-12-23 | 2018-08-13 | 주식회사 포스코 | Method for manufacturing lithium hydroxide and lithium carbonate |
-
2018
- 2018-11-07 KR KR1020180135864A patent/KR102145110B1/en active IP Right Grant
- 2018-12-13 CN CN201811525345.3A patent/CN111153419B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011168461A (en) * | 2010-02-22 | 2011-09-01 | Eco-System Recycling Co Ltd | Method for producing high-concentration lithium liquid from lithium-containing liquid and method for producing lithium carbonate |
| CN104220371A (en) * | 2012-04-05 | 2014-12-17 | Posco公司 | Method for manufacturing lithium hydroxide and method using the lithium hydroxide for manufacturing lithium carbonate |
| WO2018027266A1 (en) * | 2016-08-08 | 2018-02-15 | Enirgi Know-How Pte Ltd | A process for the conversion of lithium phosphate into a low phosphate lithium solution suitable as feedstock for the production of saleable lithium products and for the recovery of phosphorous for re-use in the production of lithium phosphate |
| CN106745099A (en) * | 2016-12-05 | 2017-05-31 | 天津二八科技股份有限公司 | A kind of method that utilization lithium phosphate prepares lithium carbonate |
| WO2018110974A1 (en) * | 2016-12-15 | 2018-06-21 | 주식회사 포스코 | Method for producing lithium hydroxide from lithium phosphate |
| KR20180069736A (en) * | 2016-12-15 | 2018-06-25 | 주식회사 포스코 | Manufacturing method for lithium hydroxide from lithium phosphate |
| CN108285156A (en) * | 2017-11-24 | 2018-07-17 | 中南大学 | A method of extracting pure Lithium Carbonate or lithium hydroxide from phosphoric acid lithium waste residue |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111153419A (en) | 2020-05-15 |
| KR20200058611A (en) | 2020-05-28 |
| KR102145110B1 (en) | 2020-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111153419B (en) | Method for extracting lithium | |
| JP7334356B2 (en) | Lithium extraction method | |
| KR101238898B1 (en) | Method for recovering with high purity lithium, lithium carbonate, lithium hydroxide and synthetic method of cathod material for lithium secondary battery from sea water | |
| US8936711B2 (en) | Method of extracting lithium with high purity from lithium bearing solution by electrolysis | |
| KR101126286B1 (en) | Manufacturing method of lithium carbonate with high purity | |
| KR101944519B1 (en) | High-efficiency method of recovering lithium from lithium solution | |
| CN107012339A (en) | The method that lithium is economically extracted from lithium-containing solution | |
| CN110683525B (en) | Method for extracting lithium | |
| CN114655969A (en) | Method for preparing lithium carbonate and iron phosphate by recycling high-impurity lithium iron phosphate positive electrode waste | |
| KR101944522B1 (en) | Manufacturing method of high-concentration lithium solution from lithium phosphate | |
| CN114524572B (en) | Comprehensive treatment method for wastewater generated in iron phosphate production | |
| KR101944518B1 (en) | Manufacturing method of high-concentration lithium solution from lithium carbonate | |
| US10173897B2 (en) | Method of synthesizing phosphate salt of high purity | |
| KR101438272B1 (en) | Method for recovering metal from electrode material | |
| JP7442617B2 (en) | Method for producing lithium hydroxide | |
| CN115799696A (en) | Method for pretreating waste electrolyte after disassembling lithium ion battery and method for fully recovering lithium, fluorine and phosphorus in waste electrolyte | |
| RU2787034C1 (en) | Method for extraction of lithium | |
| KR102489066B1 (en) | Extraction method of lithium, method for preparing lithium carbonate, and method for preparing lithium hydroxide | |
| RU2793756C1 (en) | Method for lithium extraction, method for obtaining lithium carbonate and method for obtaining lithium hydroxide | |
| US11873228B2 (en) | Method of extracting lithium, method of preparing lithium carbonate and method of preparing lithium hydroxide | |
| KR102523560B1 (en) | Manufacturing method of lithium carbonate from waste solution of lithium | |
| US20240051838A1 (en) | Method for producing lithium hydroxide | |
| CN116891227A (en) | Method for extracting lithium, method for preparing lithium carbonate, and method for preparing lithium hydroxide | |
| TW202243308A (en) | Process for cathode active material precursor preparation | |
| CN115321505A (en) | Method for preparing lithium iron phosphate by comprehensively recovering lithium-containing wastewater and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |