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WO2024262822A1 - Procédé de préparation d'une solution de lithium à haute concentration et procédé de préparation d'un composé de lithium de haute pureté l'utilisant - Google Patents

Procédé de préparation d'une solution de lithium à haute concentration et procédé de préparation d'un composé de lithium de haute pureté l'utilisant Download PDF

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WO2024262822A1
WO2024262822A1 PCT/KR2024/007196 KR2024007196W WO2024262822A1 WO 2024262822 A1 WO2024262822 A1 WO 2024262822A1 KR 2024007196 W KR2024007196 W KR 2024007196W WO 2024262822 A1 WO2024262822 A1 WO 2024262822A1
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lithium
solution
aluminum
producing
compound
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Korean (ko)
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박인수
김희서
유정현
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Korea Institute of Geoscience and Mineral Resources KIGAM
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Korea Institute of Geoscience and Mineral Resources KIGAM
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • the present invention relates to a method for producing a high-concentration lithium solution and a method for producing a high-purity lithium compound using the same, and more specifically, to a method for selectively recovering lithium by controlling lithium precipitation process conditions from a low-concentration and low-purity lithium solution and processing the same to produce a high-concentration lithium solution and a high-purity lithium compound.
  • Lithium brine a typical low-concentration lithium solution, contains large amounts of sodium (Na), potassium ( K), boron (B), chlorine (Cl), sulfate ( SO42- ), magnesium (Mg), and calcium (Ca), which reduces the efficiency of selective lithium recovery, making it difficult to economically produce lithium from low-concentration lithium brine.
  • the precipitation process has the advantage of being relatively simple, making it suitable as a large-scale lithium production process technology.
  • LiAl-LDH Lithium Aluminum Layered Double Hydroxide
  • LiAl-LDH insoluble lithium-aluminum compound
  • the aluminum compound Al(OH) 3 produced in this process has a high reactivity with lithium ions, which causes a rapid decrease in lithium separation efficiency under high-liquid ratio conditions.
  • LiAl-LDH insoluble lithium-aluminum compounds
  • LiAl-LDH insoluble lithium-aluminum compounds
  • An object of the present invention is to provide a method for producing a high-concentration lithium solution from a low-concentration lithium solution containing impurities.
  • Another object of the present invention is to provide a method for effectively producing a lithium solution by simplifying the lithium solution production process.
  • Another object of the present invention is to provide a method for economically producing a high-concentration lithium solution by recycling materials discharged in a lithium solution production process.
  • Another object of the present invention is to provide a method for producing a high-purity lithium compound from a low-concentration lithium solution containing impurities.
  • Another object of the present invention is to provide a method for effectively producing a high-purity lithium compound by simplifying the lithium solution production process.
  • Another object of the present invention is to provide a method for economically producing a high-purity lithium compound by recycling materials discharged in a lithium solution production process.
  • a method for producing a high-concentration lithium solution comprising: (a-1) a step of adding an aluminum compound to a lithium solution; (a-2) a step of precipitating a lithium-aluminum compound from the solution produced in step (a-1); (a-3) a step of calcining the lithium-aluminum compound precipitated in step (a-2) to produce a lithium-aluminum mixture; and (a-4) a step of performing a water leaching process on the lithium-aluminum mixture produced in step (a-3).
  • the lithium solution may be characterized by including lithium and impurities, and the impurities may include at least one selected from the group consisting of sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), chlorine (Cl), sulfate (SO 4 ), and boron (B).
  • the impurities may include at least one selected from the group consisting of sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), chlorine (Cl), sulfate (SO 4 ), and boron (B).
  • the aluminum compound is sodium aluminate (NaAlO 2 ), aluminum metal (Al), aluminum hydroxide (Al(OH) 3 ), sodium aluminate hydrate (NaAl(OH) 4 ), potassium aluminate (KAlO 2 ), potassium aluminate hydrate (KAl(OH) 4 ), sodium aluminum sulfate (NaAl(SO 4 ) 2 ), potassium aluminum sulfate (KAl(SO 4 ) 2 ), aluminum sulfate (Al 2 (SO 4 ) 3 ), ammonium aluminum sulfate ((NH 4 )Al(SO 4 ) 2 ), aluminum chloride (AlCl 3 ), aluminum nitrate (Al(NO 3 ) 3 ), aluminum perchlorate (Al(ClO 4 ) 3 ), and It may be characterized by including at least one selected from the group consisting of aluminum chlorohydrate (Al 2 (OH) 5 Cl).
  • the molar ratio of aluminum ions to lithium ions may be 2.0 to 6.0.
  • the lithium-aluminum compound may be characterized as being an insoluble lithium-aluminum compound represented by the following chemical formula 1.
  • X is an anion, and n and q are each integers greater than or equal to 1.
  • the above X may be characterized by being at least one selected from the group consisting of Cl - , SO 4 2- , NO 3 - , OH - , and CO 3 2- .
  • the precipitation may be characterized as being performed for 10 minutes to 5 hours.
  • the calcination may be performed under air conditions without adding additional compounds.
  • the firing in the step (a-3) is performed at 200 to 600°C.
  • step (a-3) it may be characterized in that the firing in the step (a-3) is performed for 10 minutes to 4 hours.
  • the water leaching process in the step (a-4) may include a step of adding an aqueous solution to the lithium-aluminum mixture prepared in the step (a-3), and may be characterized in that the solid-liquid ratio of the lithium-aluminum mixture to the aqueous solution is performed at 100 g/L or more.
  • the water leaching process in the step (a-4) may be characterized in that it is performed for 4 hours or less.
  • the water leaching process in the step (a-4) may be characterized by including: a step of adding a primary aqueous solution to the lithium-aluminum mixture prepared in the step (a-3) to prepare a lithium-aluminum mixture; a step of separating the primary leaching solution and the lithium-aluminum mixture from the lithium-aluminum mixture; a step of washing the lithium-aluminum mixture separated from the primary leaching solution with a secondary aqueous solution to prepare a secondary leaching solution; and a step of combining the primary leaching solution and the secondary leaching solution to prepare a lithium leaching solution having the same volume as the primary solution.
  • the aluminum compound of the step (a-1) may be characterized as an aluminum compound converted from a non-reactive aluminum compound generated in the water leaching process of the step (a-4) through a wet process using an acid and alkaline solution and a dry process through heat treatment.
  • step (a-4) may be characterized by further including a step of removing impurities after the step (a-4).
  • a method for producing a high-purity lithium compound comprising: (b-1) a step of introducing an aluminum compound into a lithium solution; (b-2) a step of precipitating a lithium-aluminum compound from the solution produced in step (b-1); (b-3) a step of calcining the lithium-aluminum compound precipitated in step (b-2) to produce a lithium-aluminum mixture; (b-4) a step of performing a water leaching process on the lithium-aluminum mixture produced in step (b-3); (b-5) a step of removing impurities; and (b-6) a step of producing a lithium compound.
  • the lithium compound may be characterized by being at least one selected from the group consisting of lithium carbonate (Li 2 CO 3 ), lithium hydroxide monohydrate (LiOHH 2 O), lithium chloride (LiCl), lithium sulfate (Li 2 SO 4 ), lithium nitrate (LiNO 3 ), and lithium peroxide (Li 2 O 2 ).
  • the method for producing a high-concentration lithium solution according to the present invention and the method for producing a high-purity lithium compound using the same have the effect of producing a high-concentration lithium solution from a low-concentration lithium solution containing impurities without an evaporation process and a pretreatment process for removing impurities.
  • the method for producing a high-concentration lithium solution according to the present invention and the method for producing a high-purity lithium compound using the same have the effect of improving the lithium recovery rate by controlling the temperature or time of the precipitation, calcination or water leaching process of the lithium-aluminum compound.
  • the method for producing a high-concentration lithium solution according to the present invention and the method for producing a high-purity lithium compound using the same have the effect of producing a high-concentration lithium solution and a high-purity lithium compound by repeating the water leaching process.
  • the method for producing a high-concentration lithium solution according to the present invention and the method for producing a high-purity lithium compound using the same have the effect of economically producing a high-concentration lithium solution by recycling non-reactive aluminum compounds generated during water leaching.
  • Figure 1 is a process diagram of a method for producing a high-concentration lithium solution according to one embodiment of the present invention.
  • Figure 2 is a process diagram of a method for producing a high-purity lithium compound according to one embodiment of the present invention.
  • Figure 4 is a graph showing the lithium leaching rate according to pH in a lithium solution according to one embodiment of the present invention.
  • Figure 5 is a graph showing the lithium leaching rate according to the mole number of aluminum ions per lithium ion (Al/Li) in a lithium solution according to one embodiment of the present invention.
  • Figure 7 is a graph showing the lithium concentration according to the sintering temperature of a lithium-aluminum compound according to one embodiment of the present invention.
  • Figure 8 is a graph showing the lithium concentration according to the sintering time of a lithium-aluminum compound according to one embodiment of the present invention.
  • FIG. 9 is a graph showing the lithium concentration according to the solid-liquid ratio of the lithium-aluminum mixture to the aqueous solution during the water leaching process of the lithium-aluminum mixture according to one embodiment of the present invention.
  • Figure 10 is a graph showing the lithium concentration according to the water leaching process time of a lithium-aluminum mixture according to one embodiment of the present invention.
  • FIG. 11 is a process diagram showing steps of repeating a water leaching process of a lithium-aluminum mixture according to one embodiment of the present invention.
  • An object of the present invention is to provide a method for producing a high-concentration lithium solution from a low-concentration lithium solution containing impurities.
  • Another object of the present invention is to provide a method for effectively producing a lithium solution by simplifying the lithium solution production process.
  • Another object of the present invention is to provide a method for economically producing a high-concentration lithium solution by recycling materials discharged in a lithium solution production process.
  • Another object of the present invention is to provide a method for producing a high-purity lithium compound from a low-concentration lithium solution containing impurities.
  • Another object of the present invention is to provide a method for effectively producing a high-purity lithium compound by simplifying the lithium solution production process.
  • Another object of the present invention is to provide a method for economically producing a high-purity lithium compound by recycling materials discharged in a lithium solution production process.
  • the present invention provides a method for producing a high-concentration lithium solution, comprising: (a-1) a step of adding an aluminum compound to a lithium solution; (a-2) a step of precipitating a lithium-aluminum compound from the solution produced in step (a-1); (a-3) a step of calcining the lithium-aluminum compound precipitated in step (a-2) to produce a lithium-aluminum mixture; and (a-4) a step of performing a water leaching process on the lithium-aluminum mixture produced in step (a-3).
  • the lithium solution contains lithium and impurities, and the impurities may contain at least one selected from the group consisting of sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), chlorine (Cl), sulfate (SO 4 ), and boron (B).
  • the impurities may contain at least one selected from the group consisting of sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), chlorine (Cl), sulfate (SO 4 ), and boron (B).
  • Low-concentration lithium brine contains large amounts of sodium (Na), potassium (K), boron (B), chlorine (Cl), and sulfate ( SO4 ), as well as magnesium (Mg) and calcium (Ca).
  • a high-concentration lithium solution is manufactured from a lithium solution containing not only lithium but also various impurities, it can be used to produce lithium industrial raw materials, thereby meeting the increasing demand for lithium resources.
  • the aluminum compound may preferably be a reactive aluminum compound (RAC).
  • Reactive aluminum compounds refer to water-soluble or water-insoluble aluminum compounds which are highly reactive with low concentration lithium ions, and include, for example, sodium aluminate (NaAlO 2 ), aluminum metal (Al), aluminum hydroxide (Al(OH) 3 ), sodium aluminate hydrate (NaAl(OH) 4 ), potassium aluminate (KAlO 2 ), potassium aluminate hydrate (KAl(OH) 4 ), sodium aluminum sulfate (NaAl(SO 4 ) 2 ), aluminum potassium sulfate (KAl(SO 4 ) 2 ), aluminum sulfate (Al 2 (SO 4 ) 3 ), aluminum ammonium sulfate ((NH 4 )Al(SO 4 ) 2 ), aluminum chloride (AlCl 3 ), aluminum nitrate (Al(NO 3 ) 3 ), It may be at least one selected from the group consisting of aluminum perchlorate (Al( ClO4 ) 3 )
  • a non-reactive aluminum compound means a non-soluble aluminum compound having low reactivity with high concentration of lithium ions, and may be, for example, at least one selected from the group consisting of alumina hydrate (AlOOH) and aluminum oxide (Al 2 O 3 ).
  • Reactive aluminum compounds have a higher reactivity with lithium ions in a lithium solution than non-reactive aluminum compounds, and thus can react with lithium in a lithium solution to extract lithium in the form of a lithium-aluminum compound, from which a high-concentration lithium solution can be produced.
  • the molar ratio of aluminum ions to lithium ions can be 2.0 to 6.0.
  • the theoretical molar ratio of aluminum ions to lithium ions is 2.0.
  • the lithium extraction rate increases proportionally. Therefore, when the molar ratio of aluminum ions to lithium ions (Al/Li) exceeds 2.0, a high lithium extraction rate can be secured even when the lithium concentration of the lithium solution is low or contains magnesium impurities (see Fig. 5).
  • the molar ratio of aluminum ions to lithium ions (Al/Li) is less than 2.0, there is a problem that the lithium extraction rate is low, and if it exceeds 6.0, the amount of aluminum compound input increases and the lithium content in the lithium-aluminum compound decreases, which reduces process efficiency and reduces economic feasibility.
  • a step of adjusting the pH of the solution may be further included.
  • the pH of the lithium solution may be adjusted to 5 to 9.
  • the lithium extraction rate is low when the pH of the lithium solution is less than 5 or more than 9. This is because when the pH of the lithium solution is less than 5, the reaction between the lithium solution and aluminum does not occur smoothly, and when the pH of the lithium solution exceeds 9, the reactivity between the added aluminum compound and the magnesium in the lithium solution becomes excessively large.
  • the pH adjustment step can be omitted by combining different reactive aluminum compounds.
  • the above pH adjustment can be performed by adding one or more selected from the group consisting of sodium hydroxide (NaOH), sodium carbonate (Na 2 CO 3 ), potassium hydroxide (KOH), potassium carbonate (K 2 CO 3 ), calcium hydroxide (Ca(OH) 2 ), calcium oxide (CaO), and ammonium hydroxide ((NH 4 )OH).
  • NaOH sodium hydroxide
  • Na 2 CO 3 sodium carbonate
  • KOH potassium hydroxide
  • K 2 CO 3 potassium carbonate
  • Ca(OH) 2 calcium hydroxide
  • CaO calcium oxide
  • ammonium hydroxide (NH 4 )OH).
  • it can be performed by adding a mineral or natural raw material containing one or more raw materials selected from the above group.
  • the pH can be adjusted with sodium hydroxide (NaOH).
  • step (a-2) A step of precipitating a lithium-aluminum compound from the solution prepared in step (a-1).
  • the lithium-aluminum compound may be an insoluble lithium-aluminum compound represented by the following chemical formula 1.
  • X is an anion, and n and q are each integers greater than or equal to 1.
  • the above X may be at least one selected from the group consisting of Cl - , SO 4 2- , NO 3 - , OH - and CO 3 2- . Preferably, it may be Cl - , SO 4 2- or NO 3 - .
  • insoluble lithium-aluminum compounds The heat treatment effect of insoluble lithium-aluminum compounds is greatly affected by the form of the anion. That is, through heat treatment, lithium in the insoluble lithium-aluminum compound combines with X and is converted into a soluble lithium salt form, and the conversion rate is determined depending on the form of the anion.
  • the precipitation can be performed for 10 minutes to 5 hours, and preferably for 2 hours to 5 hours.
  • the lithium recovery rate is low at about 40% or less when the precipitation is performed for less than 10 minutes, and there is a problem that the increase in the lithium extraction rate is small compared to the precipitation time when the precipitation is performed for more than 5 hours.
  • the required precipitation reaction time can be reduced to less than 10 minutes.
  • a step of filtering, washing, and drying the precipitated lithium-aluminum compound may be further included.
  • the filtering may be performed using a filter and centrifugation, but is not limited thereto.
  • the washing may be performed using one or more selected from distilled water, an acidic solution, a basic solution, ethanol, and methanol, but is not limited thereto.
  • a high-purity lithium-aluminum compound powder can be manufactured through a process of washing and then drying a lithium-aluminum compound.
  • step (a-3) A step of producing a lithium-aluminum mixture by calcining the lithium-aluminum compound precipitated in step (a-2) above.
  • the calcination can be performed under air conditions without adding additional compounds.
  • the calcination can preferably be a dry reaction.
  • the present invention performs a process in which lithium and anions contained in a lithium-aluminum compound react and are converted into a water-soluble lithium salt form
  • the calcination process can be simplified by performing the process under air conditions without adding additional compounds such as sulfate, and lithium can be effectively recovered from a low-concentration lithium solution in a short period of time.
  • a high-purity lithium compound can be economically manufactured from a lithium solution through the calcination process.
  • the above-mentioned calcination may be a dry reaction. According to the above-mentioned dry reaction, there is an advantage in that lithium can be extracted economically and a high-concentration lithium solution can be obtained through a simple process.
  • the above firing can be performed using a general batch type furnace or rotary type furnace, it is not limited to the shape or heating method of the furnace (kiln).
  • the calcination can be performed at 200 to 600°C.
  • the above calcination has the effect of increasing lithium separation efficiency when performed at 200 to 600°C. If the temperature condition of calcination is less than 200°C or more than 600°C, there is a problem of low lithium separation efficiency (see Fig. 7). This is because if the temperature condition of calcination exceeds 600°C, the water-soluble lithium salt and the non-reactive aluminum compound react again, increasing insoluble lithium.
  • the firing can be performed for 10 minutes to 4 hours.
  • the lithium-aluminum mixture obtained by calcining the lithium-aluminum compound may be a mixture of a water-soluble lithium salt and an insoluble aluminum compound.
  • step (a-4) A step of performing a water leaching process on the lithium-aluminum mixture manufactured in step (a-3) above.
  • the water leaching process includes a step of adding an aqueous solution to the lithium-aluminum mixture prepared in step (a-3), and the solid-liquid ratio of the lithium-aluminum mixture to the aqueous solution can be performed at 100 g/L or more, and preferably 100 to 1000 g/L.
  • the aqueous solution can be one selected from distilled water, deionized water, water, or a low-concentration lithium solution.
  • the water leaching process can be performed for 4 hours or less, preferably 10 minutes to 4 hours, and more preferably 10 minutes to 30 minutes.
  • the water leaching process may include a step of adding a first aqueous solution to the lithium-aluminum mixture prepared in the step (a-3) to prepare a lithium-aluminum mixture; a step of separating the first leaching solution and the lithium-aluminum mixture from the lithium-aluminum mixture; a step of washing the lithium-aluminum mixture separated from the first leaching solution with a second aqueous solution to prepare a second leaching solution; and a step of combining the first leaching solution and the second leaching solution to prepare a lithium leaching solution having the same volume as the first aqueous solution.
  • the above primary aqueous solution or the above secondary aqueous solution may be one selected from distilled water, deionized water, water, or a low-concentration lithium solution.
  • the above primary leachate may be a supernatant of a lithium-aluminum mixture prepared by adding a primary aqueous solution to the lithium-aluminum mixture prepared in step (a-3).
  • the above secondary leachate may be a supernatant of a lithium-aluminum mixture prepared by adding a secondary aqueous solution to the lithium-aluminum mixture separated from the first leachate.
  • the water leaching process can be repeated using the lithium leaching solution as the primary aqueous solution, preferably 1 to 10 times, and more preferably 2 to 5 times.
  • the aluminum compound of the above step (a-1) may be an aluminum compound converted from a non-reactive aluminum compound generated in a water leaching process in this step through a wet process using an acid and alkaline solution and a dry process through heat treatment, and preferably, it may be a reactive aluminum compound converted from a non-reactive aluminum compound generated in a water leaching process in this step through a wet process using an acid and alkaline solution and a dry process through heat treatment.
  • the aluminum compound generated in the water leaching process in this step may be a non-reactive aluminum compound (NAC), and the aluminum compound in the step (a-1) may be a reactive aluminum compound (RAC).
  • NAC non-reactive aluminum compound
  • RAC reactive aluminum compound
  • Reactive aluminum compounds refer to water-soluble or water-insoluble aluminum compounds which are highly reactive with low concentration lithium ions, and include, for example, sodium aluminate (NaAlO 2 ), aluminum metal (Al), aluminum hydroxide (Al(OH) 3 ), sodium aluminate hydrate (NaAl(OH) 4 ), potassium aluminate (KAlO 2 ), potassium aluminate hydrate (KAl(OH) 4 ), sodium aluminum sulfate (NaAl(SO 4 ) 2 ), aluminum potassium sulfate (KAl(SO 4 ) 2 ), aluminum sulfate (Al 2 (SO 4 ) 3 ), aluminum ammonium sulfate ((NH 4 )Al(SO 4 ) 2 ), aluminum chloride (AlCl 3 ), aluminum nitrate (Al(NO 3 ) 3 ), It may be at least one selected from the group consisting of aluminum perchlorate (Al( ClO4 ) 3 )
  • a non-reactive aluminum compound means a non-soluble aluminum compound having low reactivity with high concentration of lithium ions, and may be, for example, at least one selected from the group consisting of alumina hydrate (AlOOH) and aluminum oxide (Al 2 O 3 ).
  • Reactive aluminum compounds have a higher reactivity with lithium ions in a lithium solution than non-reactive aluminum compounds, and thus can react with lithium in a lithium solution to extract lithium in the form of a lithium-aluminum compound, from which a high-concentration lithium solution can be produced.
  • Non-reactive aluminum compounds can be converted into reactive aluminum compounds through a wet process using acid and alkaline solutions and a dry process using heat treatment. Therefore, the non-reactive aluminum compounds can be reused, which improves economic efficiency and is environmentally friendly.
  • the step of removing the above impurities can be performed through pH control of the high-concentration lithium leaching solution and an additional evaporation concentration process, thereby producing a high-purity lithium solution.
  • the pretreatment process for removing impurities in the lithium solution in step (a-1) may be omitted, and a step for removing impurities after this step may be included.
  • Another aspect of the present invention provides a method for producing a high-purity lithium compound, comprising: (b-1) a step of introducing an aluminum compound into a lithium solution; (b-2) a step of precipitating a lithium-aluminum compound from the solution produced in step (b-1); (b-3) a step of calcining the lithium-aluminum compound precipitated in step (b-2) to produce a lithium-aluminum mixture; (b-4) a step of performing a water leaching process on the lithium-aluminum mixture produced in step (b-3); (b-5) a step of removing impurities; and (b-6) a step of producing a lithium compound.
  • the pretreatment process for removing impurities in the lithium solution in step (b-1) is omitted, and the impurities can be removed in step (b-5).
  • the lithium compound may be at least one selected from the group consisting of lithium carbonate (Li 2 CO 3 ), lithium hydroxide monohydrate (LiOHH 2 O), lithium chloride (LiCl), lithium sulfate (Li 2 SO 4 ), lithium nitrate (LiNO 3 ), and lithium peroxide (Li 2 O 2 ).
  • it may be at least one selected from the group consisting of lithium carbonate (Li 2 CO 3 ) and lithium hydroxide monohydrate (LiOHH 2 O).
  • the step of producing the lithium compound from the high-concentration, high-purity lithium solution may include at least one selected from the group consisting of a chemical process adding a chemical agent, a crystallization process, and an electrochemical process.
  • lithium carbonate Li 2 CO 3
  • lithium hydroxide monohydrate LiOHH 2 O
  • steps (b-1) to (b-4) above can be performed in the same manner as described in the method for producing a high-concentration lithium solution.
  • Table 1 shows the composition of lithium solutions containing lithium and impurities to be used in the examples below.
  • a lithium solution containing lithium and impurities consisting of Li (350 mg/L), Na (87,500 mg/L), K (7,200 mg/L), Ca (544.2 mg/L), Mg (6,500 mg/L), Cl (156,900 mg/L), SO 4 (8,500 mg/L), and B (200 mg/L) and having an initial pH of 6.5 was prepared.
  • the lithium extraction rate is 12% at pH 5.6, and as the pH of the lithium solution increases from 5.6 to 7.2, the lithium extraction rate increases, reaching the highest lithium extraction rate of 69% at pH 7.2, and then decreasing as the pH of the lithium solution increases.
  • the reason why the lithium extraction rate decreases at pH 7.2 or higher of the lithium solution is because the added aluminum compound becomes more reactive with magnesium in the lithium solution.
  • the lithium concentration in the supernatant obtained through the above water leaching is measured through inductively coupled plasma-optical emission spectroscopy (ICP-OES) analysis.
  • ICP-OES inductively coupled plasma-optical emission spectroscopy
  • the lithium-aluminum compound obtained by the above repeated washing and drying was calcined at a temperature of 400°C for 0 to 4 hours in a box furnace under air conditions.
  • the lithium-aluminum mixture obtained through calcination at each of the above times is subjected to water leaching with deionized water at a high-liquid ratio of 100 g/L for 2 hours while stirring at 25°C.
  • the lithium concentration in the supernatant obtained through the above water leaching is measured through inductively coupled plasma-optical emission spectroscopy (ICP-OES) analysis.
  • ICP-OES inductively coupled plasma-optical emission spectroscopy
  • the lithium-aluminum compound obtained by the above repeated washing and drying was calcined at 400°C for 30 minutes in a box furnace under atmospheric conditions.
  • the lithium-aluminum mixture obtained through the above calcination is subjected to water leaching with deionized water at a high-liquid ratio of 100 to 500 g/L while stirring at 25°C for 2 hours.
  • the lithium concentration in the supernatant obtained through the above water leaching is measured through inductively coupled plasma-optical emission spectroscopy (ICP-OES) analysis.
  • ICP-OES inductively coupled plasma-optical emission spectroscopy
  • the lithium concentration was 1,381 mg/L at a solid-liquid ratio of 100 g/L of the lithium-aluminum mixture and deionized water, and the lithium concentration was 6,590 mg/L at a solid-liquid ratio of 500 g/L of the lithium-aluminum mixture and deionized water. That is, as the solid-liquid ratio of the lithium-aluminum mixture and distilled water increases, the lithium concentration in the lithium solution increases linearly. These results imply that the lithium separation efficiency is similar regardless of the solid-liquid ratio of the lithium-aluminum mixture and distilled water.
  • the preferred high-liquid ratio condition in the water leaching process may be 100 g/L or more, and preferably 100 to 500 g/L.
  • the lithium-aluminum compound obtained by the above repeated washing and drying was calcined at a temperature of 400°C for 30 minutes in a box furnace under air conditions.
  • the lithium concentration in the lithium leaching solution obtained after the three-time water leaching process was confirmed to be 13,449 mg/L.
  • the lithium concentration in the lithium leaching solution obtained after the three-time water leaching process increased by 38.4 times compared to the lithium solution not prepared according to the present invention, but the magnesium increased by about 2 times and the concentrations of other impurities decreased.
  • the method for producing a high-concentration lithium solution according to the present invention and the method for producing a high-purity lithium compound using the same have the effect of producing a high-concentration lithium solution from a low-concentration lithium solution containing impurities without an evaporation process and a pretreatment process for removing impurities.
  • the method for producing a high-concentration lithium solution according to the present invention and the method for producing a high-purity lithium compound using the same have the effect of improving the lithium recovery rate by controlling the aluminum/lithium ion molar ratio or pH in the lithium solution and the aluminum compound solution.
  • the method for producing a high-concentration lithium solution according to the present invention and the method for producing a high-purity lithium compound using the same have the effect of improving the lithium recovery rate by controlling the temperature or time of the precipitation, calcination or water leaching process of the lithium-aluminum compound.
  • the method for producing a high-concentration lithium solution according to the present invention and the method for producing a high-purity lithium compound using the same have the effect of economically producing a high-concentration lithium solution by recycling non-reactive aluminum compounds generated during water leaching.

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Abstract

La présente invention concerne un procédé de préparation d'une solution de lithium à haute concentration et un procédé de préparation d'un composé de lithium de haute pureté l'utilisant et, plus spécifiquement, des procédés de préparation d'une solution de lithium à haute concentration et d'un composé de lithium de haute pureté par récupération sélective de lithium à partir d'une solution de lithium à faible concentration et de faible pureté par la commande de conditions de processus de précipitation de lithium et traitement de celle-ci.
PCT/KR2024/007196 2023-06-23 2024-05-28 Procédé de préparation d'une solution de lithium à haute concentration et procédé de préparation d'un composé de lithium de haute pureté l'utilisant Pending WO2024262822A1 (fr)

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KR102810327B1 (ko) * 2024-11-22 2025-05-26 한국지질자원연구원 응집제를 사용하여 리튬용액으로부터 리튬을 회수하는 방법

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KR102208040B1 (ko) 2019-06-11 2021-01-27 주식회사 셀젠 흡착재를 이용한 리튬의 고농도화 방법

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KR20120014828A (ko) * 2010-08-10 2012-02-20 재단법인 포항산업과학연구원 염수를 이용한 탄산리튬 제조방법
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