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WO2024192617A1 - Dispositif d'extraction de lithium et procédé d'extraction de lithium - Google Patents

Dispositif d'extraction de lithium et procédé d'extraction de lithium Download PDF

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Publication number
WO2024192617A1
WO2024192617A1 PCT/CN2023/082451 CN2023082451W WO2024192617A1 WO 2024192617 A1 WO2024192617 A1 WO 2024192617A1 CN 2023082451 W CN2023082451 W CN 2023082451W WO 2024192617 A1 WO2024192617 A1 WO 2024192617A1
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WO
WIPO (PCT)
Prior art keywords
lithium
electrode region
positive electrode
negative electrode
lithium extraction
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.)
Pending
Application number
PCT/CN2023/082451
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English (en)
Chinese (zh)
Inventor
余海军
李爱霞
谢英豪
李长东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Original Assignee
Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Publication date
Application filed by Hunan Brunp Recycling Technology Co Ltd, Guangdong Brunp Recycling Technology Co Ltd filed Critical Hunan Brunp Recycling Technology Co Ltd
Priority to CN202380008406.1A priority Critical patent/CN116724134B/zh
Priority to PCT/CN2023/082451 priority patent/WO2024192617A1/fr
Priority to ARP240100282A priority patent/AR131793A1/es
Publication of WO2024192617A1 publication Critical patent/WO2024192617A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/02—Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/02—Electrolytic production, recovery or refining of metals by electrolysis of solutions of light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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

Definitions

  • the present application belongs to the technical field of lithium extraction, and specifically, relates to a lithium extraction device and a lithium extraction method.
  • the methods currently developed include adsorption, precipitation, solvent extraction, electrodialysis and electrochemical deintercalation.
  • the precipitation method is suitable for brine with a low Mg/Li ratio; the life of the extractant in the solvent extraction method is short and it is not suitable for industrial production; electrodialysis separation requires a high cost; the electrochemical deintercalation method cannot be produced continuously, and the electrolyte or electrode position needs to be replaced after adsorption saturation, and impurity ions adsorbed on the electrode, such as Mg 2+, are difficult to remove.
  • One of the purposes of the present application includes providing a lithium extraction device, which can continuously enrich and extract lithium ions while removing some impurity ions, effectively improving the removal rate of impurities (such as Mg 2+ ) in the lithium extraction process and improving the purity of lithium ions.
  • impurities such as Mg 2+
  • the second purpose of the present application includes providing a method for extracting lithium using the above-mentioned lithium extraction device, which method is simple to operate, has low cost and high lithium extraction efficiency.
  • the first solution of the present application includes providing a lithium extraction device, which includes an electrolytic cell and a lithium ion screen, wherein the electrolytic cell includes a negative electrode region, a positive electrode region, and a lithium-containing liquid injection region;
  • the negative electrode region and the positive electrode region are arranged relatively spaced apart, and the lithium-containing liquid injection region is located between the negative electrode region and the positive electrode region; a cation exchange membrane is arranged between the negative electrode region and the lithium-containing liquid injection region, and an anion exchange membrane is arranged between the lithium-containing liquid injection region and the positive electrode region;
  • the negative electrode region and the positive electrode region are respectively used to connect to the negative electrode and the positive electrode of the power supply. During use, both the negative electrode region and the positive electrode region have electrolyte.
  • Lithium ion sieve is used in the process of lithium extraction to first undergo a reduction reaction in the negative electrode area to adsorb Li + and include some cationic impurities, and then undergo an oxidation reaction in the positive electrode area to precipitate the cations.
  • the positive electrode region of the lithium extraction device is also provided with a discharge port, and the discharge port is provided with a filtering device for separating the precipitate formed by the precipitated cations and the anions in the positive electrode region from the electrolyte.
  • the lithium extraction device further includes a lithium ion sieve cleaning tank, the inlet of the lithium ion sieve cleaning tank is connected to the positive electrode area, and the outlet of the lithium ion sieve cleaning tank is connected to the negative electrode area.
  • the lithium extraction device further includes a power source, and the power source includes a positive electrode for connecting to the positive electrode region and a negative electrode for connecting to the negative electrode region.
  • the second scheme of the present application includes providing a lithium extraction method, which uses the above-mentioned lithium extraction device to extract lithium from the lithium-containing liquid to be treated.
  • the lithium-containing liquid includes at least one of brine, seawater, waste battery leaching solution, lithium precipitation mother liquor and ore lithium extraction leaching solution.
  • the electrolyte includes a lithium-free electrolyte or a lithium-containing electrolyte.
  • the electrolyte is a lithium-free electrolyte or a lithium-reduced electrolyte.
  • the electrolyte is a lithium-free electrolyte.
  • the electrolyte includes at least one of a NaCl solution and a KCl solution.
  • the electrolyte contains an oxidant.
  • the lithium extraction process includes at least one processing cycle, and each processing cycle includes:
  • the power-on condition in each step independently includes: voltage>0V and ⁇ 1.5V.
  • the total power-on time of S1 and S2 is 0.5-1h.
  • S3 is performed under power-on conditions, and the power-on time of S3 is 0.5-1h.
  • the lithium ion sieve just put into the negative electrode region is a desorbed lithium ion sieve
  • the lithium ion sieve just transferred to the positive electrode region is a lithium-rich lithium ion sieve.
  • the lithium ion sieve is a manganese iron phosphate lithium ion sieve.
  • the cleaning method is ultrasonic cleaning.
  • the cleaning time is 0.5-1 h.
  • the lithium-containing solution when the Li + concentration in the positive electrode region reaches a preset concentration, the lithium-containing solution is collected and the precipitate is removed.
  • the preset concentration is not less than 0.7 g/L.
  • the lithium extraction process further includes: precipitating Li + in the collected lithium-containing solution after removing the precipitate in the form of crystals.
  • precipitating crystals includes: mixing a lithium-containing solution with a readily soluble carbonate or bicarbonate, and heating.
  • the readily soluble carbonate includes Na 2 CO 3 .
  • the readily soluble bicarbonate salt comprises NaHCO 3 .
  • precipitating crystals includes: mixing a lithium-containing solution with lithium phosphate and heating.
  • the heating temperature is 55-65°C.
  • the lithium extraction device provided in the present application enriches the anions in the lithium-containing liquid in the positive electrode region and the cations in the negative electrode region under power-on conditions, and the ion exchange membrane can prevent the anions from entering the negative electrode region and prevent the cations from entering the positive electrode region; during the lithium extraction process, the lithium ion sieve contained in the device first undergoes a reduction reaction in the negative electrode region to adsorb Li + and entrain some cationic impurities (such as Mg2 +, etc.), and then transfers to the positive electrode region to undergo an oxidation reaction to precipitate the cations. At this time, some of the precipitated cations can form a precipitate together with the anions in the positive electrode region (such as Mg2 + and CO32- together to form MgCO3 precipitate) and be removed.
  • the lithium ion sieve contained in the device first undergoes a reduction reaction in the negative electrode region to adsorb Li + and entrain some cationic impurities (such
  • the lithium extraction device can continuously enrich and extract lithium ions while removing some impurity ions (such as Mg 2+ ), thereby improving the purity of lithium ions.
  • the corresponding lithium extraction method is simple to operate, low in cost, and high in lithium extraction efficiency.
  • FIG1 is a schematic diagram of the structure of the lithium extraction device provided by the present application in the first stage
  • FIG2 is a schematic diagram of the structure of the lithium extraction device provided in the present application in the second stage.
  • Icons 10-electrolytic cell; 11-negative electrode area; 12-positive electrode area; 13-electrolyte; 14-lithium-containing solution injection area; 15-lithium-containing solution; 16-cation exchange membrane; 17-anion exchange membrane; 20-lithium ion sieve; 30-power supply; 31-negative electrode of power supply; 32-positive electrode of power supply; 40-lithium ion sieve cleaning tank.
  • the inventor proposes that when the lithium ion sieve 20 is used to enrich the lithium ions in the lithium-containing liquid during the lithium extraction process, impurity ions such as Mg 2+ present in the liquid will be mixed in, thereby reducing the lithium extraction effect.
  • the present application proposes a lithium extraction device and method that can continuously enrich and extract lithium ions while removing some impurity ions.
  • the lithium extraction device proposed in the present application includes an electrolytic cell 10 and a lithium ion sieve 20.
  • the electrolytic cell 10 includes a negative electrode region 11, a positive electrode region 12, and a lithium-containing liquid injection region 14.
  • the negative electrode region 11 and the positive electrode region 12 are arranged relatively spaced apart, and the lithium-containing solution injection region 14 is located between the negative electrode region 11 and the positive electrode region 12; a cation exchange membrane 16 is provided between the negative electrode region 11 and the lithium-containing solution injection region 14, and an anion exchange membrane 17 is provided between the lithium-containing solution injection region 14 and the positive electrode region 12.
  • the negative electrode region 11 and the positive electrode region 12 are respectively used to connect to the negative electrode 31 and the positive electrode 32 of the power supply. During use, the negative electrode region 11 and the positive electrode region 12 both have electrolyte 13 .
  • the lithium-containing feed solution 15 may include at least one of brine, seawater, waste battery leaching solution, lithium precipitation mother liquor and ore lithium extraction leaching solution.
  • the cations contained therein may include Li + , Mg 2+ , K + , Ca 2+ and Na +, etc.
  • the anions contained therein may include CO 3 2- , SO 4 2- and Cl - , etc., which are exemplary but not limited.
  • the electrolyte 13 may be a lithium-free electrolyte or a lithium-containing electrolyte (preferably, the lithium content in the lithium-containing electrolyte does not exceed 0.7 g/L).
  • the electrolyte 13 is a lithium-free electrolyte or a low-lithium electrolyte (preferably, the lithium content in the low-lithium electrolyte does not exceed 0.1 g/L), and more preferably a lithium-free electrolyte (such as a NaCl solution). At least one of solution and KCl solution) is used to avoid affecting the accuracy of the final lithium content detection result.
  • the lithium ion sieve 20 is used to first undergo a reduction reaction in the negative electrode region 11 to adsorb Li + and include some cationic impurities during the lithium extraction process, and then undergo an oxidation reaction in the positive electrode region 12 to precipitate the cations.
  • the lithium ion sieve 20 just put into the negative electrode area 11 is in a desorbed state, and after absorbing Li + and mixing with some cationic impurities, it is in a lithium-rich state; correspondingly, the lithium ion sieve 20 just transferred to the positive electrode area 12 is in a lithium-rich state, and after precipitating cations, it is in a desorbed state. Therefore, the lithium ion sieve 20 can be recycled in the above manner.
  • the transfer of the lithium ion sieve 20 can be carried out in a conventional manner.
  • FIG1 corresponds to the stage where the lithium ion sieve 20 has just been put into the negative electrode area 11
  • FIG2 corresponds to the stage where part of the lithium ion sieve 20 is transferred to the positive electrode area 12 during use.
  • the lithium ion sieve 20 may be a manganese iron phosphate lithium ion sieve 20. In other embodiments, the lithium ion sieve 20 may also be other common types of lithium ion sieves 20, which are not limited here.
  • the above-mentioned "oxidation reaction occurs” can be achieved by applying electricity. In other optional embodiments, the above-mentioned “oxidation reaction occurs” can be achieved by using an electrolyte 13 containing an oxidant.
  • the oxidant used in the electrolyte 13 may include at least one of an organic oxidant and an inorganic oxidant.
  • the organic oxidant may include an organic peroxide, such as at least one of performic acid and peracetic acid.
  • the inorganic oxidant may include at least one of hydrogen peroxide, a gas containing O2 , and a high-valent oxide of a multivalent element (such as potassium permanganate).
  • the positive electrode region 12 of the lithium extraction device provided in the present application is also provided with a discharge port (not shown in the figure), and the discharge port is provided with a filtering device (such as a filter mesh, not shown in the figure) for separating the lithium ion sieve 20 and the precipitate formed by the precipitated cations and the anions in the positive electrode region 12 from the electrolyte 13.
  • a filtering device such as a filter mesh, not shown in the figure
  • the lithium extraction device provided in the present application also includes a lithium ion sieve cleaning tank 40 , the inlet of the lithium ion sieve cleaning tank 40 is connected to the positive electrode area 12 , and the outlet of the lithium ion sieve cleaning tank 40 is connected to the negative electrode area 11 .
  • the lithium ion sieve 20 after cations are precipitated in the positive electrode region 12 can be transferred to the lithium ion sieve cleaning tank 40 for cleaning to further remove impurities and other substances adsorbed on the lithium ion sieve 20 (such as calcium carbonate, magnesium carbonate, etc. produced by precipitation) to improve the adsorption capacity of the lithium ion sieve 20.
  • the cleaned lithium ion sieve 20 can continue to be used, such as being recycled into the negative electrode region 11.
  • the present application scheme does not exclude the possibility of not cleaning the lithium ion sieve 20 , but adding a new lithium ion sieve 20 into the negative electrode region 11 during subsequent processing.
  • the lithium extraction device further includes a power source 30 , which includes a positive electrode for connecting to the positive electrode region 12 and a negative electrode for connecting to the negative electrode region 11 .
  • the electrolytic cell 10 and the power source 30 together form an electrolysis system, and lithium extraction from the lithium-containing liquid 15 can be achieved through the principle of electrodialysis.
  • the present application also provides a lithium extraction method, which uses the above-mentioned lithium extraction device to perform lithium extraction treatment on the lithium-containing liquid 15 to be treated.
  • the lithium extraction process includes at least one treatment cycle, and the specific number of treatment cycles required depends on the Li + concentration contained in the solution in the positive electrode region 12 after treatment.
  • Each processing cycle includes:
  • the lithium extraction device is powered on so that the positive electrode region 12 and the negative electrode region 11 respectively enrich the anions and cations in the lithium-containing solution 15 .
  • the enrichment of anions and cations is achieved in the positive electrode region 12 and the negative electrode region 11 respectively through the electrodialysis principle and the electric field on the migration of anions and cations. That is, the cations (such as Li + , Mg 2+ , K + , Ca 2+ and Na +, etc.) in the lithium-containing solution 15 enter the negative electrode region 11, and the anions (such as CO 3 2- , SO 4 2- and Cl -, etc.) in the lithium-containing solution 15 enter the positive electrode region 12.
  • the cations such as Li + , Mg 2+ , K + , Ca 2+ and Na +, etc.
  • the lithium-containing liquid injection area 14 is injected with lithium-containing liquid 15, the positive electrode area 12 and the negative electrode area 11 are both injected with electrolyte 13, and there is a lithium ion sieve 20 in the negative electrode area 11 (preferably a clean desorbed lithium ion sieve 20, such as a clean desorbed manganese iron phosphate lithium ion sieve 20).
  • the voltage of the power supply is >0V and ⁇ 1.5V, such as 0.5V, 0.6V, 0.7V, 0.8V, 0.9V, 1.0V, 1.1V, 1.2V, 1.3V, 1.4V or 1.5V, etc., or it can be any other value within the range of >0V and ⁇ 1.5V.
  • the voltage is greater than 1.5V, on the one hand, it is easy to make the voltage and current larger, resulting in concentration polarization; on the other hand, it will greatly increase energy consumption.
  • the desorbed lithium ion sieve 20 in the electrolyte 13 of the negative electrode region 11 undergoes a reduction reaction, and while combining with Li +, it also contains other impurity cations (such as Mg2 +, etc.), thereby forming a lithium-rich lithium ion sieve 20 that is enriched with lithium ions and other impurity cations.
  • the total power-on time of S1 and S2 may be 0.5-1 h, such as 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h or 1 h, etc.
  • the specific time may be determined according to the adsorption of cations by the lithium ion sieve 20 .
  • the lithium ion sieve 20 undergoes an oxidation reaction, and the cations are reduced and precipitated from the lithium ion sieve 20. After the cations are precipitated, the lithium ion sieve 20 is in a desorbed state again, and the precipitated cationic impurities such as Mg 2+ and Ca 2+ can combine with the anions (such as CO 3 2-, etc.) in the positive electrode region 12 to form precipitation.
  • the precipitated cationic impurities such as Mg 2+ and Ca 2+ can combine with the anions (such as CO 3 2-, etc.) in the positive electrode region 12 to form precipitation.
  • the power-on state is always maintained during the above process from S2 to S3.
  • the power-on voltage during the process from S1 to S3 is the same.
  • the power-on time in S3 may be 0.5-1 h, such as 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h or 1 h, etc.
  • the specific time may be determined according to the precipitation of cations by the lithium ion sieve 20 .
  • each processing cycle may also include:
  • the cleaning method may be ultrasonic cleaning.
  • the cleaning time may be 0.5-1 hour for example but not limitation.
  • the cleaning liquid used for cleaning may be pure water.
  • the power supply 30 can be turned off to save energy.
  • the Li + concentration in the positive electrode region 12 reaches a preset concentration (eg, the Li + concentration is not less than 0.7 g/L)
  • the lithium-containing solution after removing the precipitate is collected for subsequent processing.
  • the Li + concentration of the solution in the positive electrode region 12 reaches the preset concentration after only one treatment cycle, the lithium-containing solution after the precipitation is collected and removed after S3. Further, the desorbed lithium ion sieve 20 obtained in S3 can be subjected to step S4.
  • steps S1 to S4 can be performed in sequence until the Li + concentration of the solution in the positive electrode region 12 reaches the preset concentration in a certain treatment cycle.
  • the lithium-containing solution after the precipitation is collected and removed. Further, the desorbed lithium ion sieve 20 obtained in S3 in the treatment cycle can be subjected to step S4.
  • the lithium extraction process provided in the present application also includes: precipitating the Li + in the collected lithium-containing solution after removing the precipitate in the form of crystals. For example, this can be achieved by mixing the lithium-containing solution with a soluble carbonate or bicarbonate and then heating it, or by mixing the lithium-containing solution with lithium phosphate and then heating it.
  • the lithium-containing solution may be mixed with a readily soluble carbonate (such as Na 2 CO 3 ) and heated to precipitate Li + in the form of crystals (such as Li 2 CO 3 crystals).
  • the lithium-containing solution may be mixed with a readily soluble bicarbonate (such as NaHCO 3 ) and heated to precipitate Li + in the form of crystals (such as Li 2 CO 3 crystals).
  • the lithium-containing solution may also be mixed with lithium phosphate to precipitate Li + in the form of crystals (such as Li 3 PO 4 crystals).
  • the heating temperature may be 55-65°C, such as 55°C, 58°C, 60°C, 62°C or 65°C, etc., or any other value within the range of 55-65°C.
  • the lithium extraction device and method provided by the present application can repeatedly clean the lithium ion screen 20 and continuously recycle it, which can not only effectively improve the lithium extraction efficiency, but also greatly reduce the cost. Lithium, this method can more effectively remove impurities (especially Mg 2+ ), thereby improving the purity of extracted lithium ions.
  • This embodiment provides a lithium extraction device, please refer to FIG. 1 and FIG. 2 , which includes a power source 30 , an electrolytic cell 10 and a lithium ion sieve 20 .
  • the electrolytic cell 10 includes a negative electrode region 11 , a positive electrode region 12 , a lithium-containing solution injection region 14 , and a lithium ion sieve cleaning tank 40 .
  • the negative electrode region 11 and the positive electrode region 12 are arranged relatively spaced apart, and the lithium-containing solution injection region 14 is located between the negative electrode region 11 and the positive electrode region 12; a cation exchange membrane 16 is provided between the negative electrode region 11 and the lithium-containing solution injection region 14, and an anion exchange membrane 17 is provided between the lithium-containing solution injection region 14 and the positive electrode region 12.
  • the negative electrode region 11 and the positive electrode region 12 are respectively used to connect to the negative electrode 31 and the negative electrode 31 of the power supply. During use, both the negative electrode region 11 and the positive electrode region 12 contain an electrolyte 13 (NaCl solution).
  • the lithium ion sieve 20 (manganese iron phosphate lithium ion sieve 20) is used to first adsorb Li + and entrain some cationic impurities in the negative electrode area 11 during the lithium extraction process, and then precipitate the cations in the positive electrode area 12 under the action of electrolysis.
  • the lithium ion sieve 20 just put into the negative electrode area 11 is in a desorbed state, and is in a lithium-rich state after adsorbing Li + and entraining some cationic impurities; correspondingly, the lithium ion sieve 20 just transferred to the positive electrode area 12 is in a lithium-rich state, and is in a desorbed state after precipitating cations.
  • the inlet of the lithium ion sieve cleaning tank 40 is connected to the positive electrode area 12 , and the outlet of the lithium ion sieve cleaning tank 40 is connected to the negative electrode area 11 .
  • the positive electrode of the power source 30 is connected to the positive electrode region 12
  • the negative electrode of the power source 30 is connected to the negative electrode region 11 .
  • electrolyte 13 contains an oxidant (hydrogen peroxide).
  • This embodiment provides a method for extracting lithium from salt lake brine (high Mg/Li ratio), which uses the lithium extraction device in Example 1 in the following manner:
  • the lithium extraction device is energized (1.5V) so that the positive electrode region 12 and the negative electrode region 11 respectively enrich the anions and cations in the lithium-containing solution 15.
  • the cations such as Li + , Mg 2+ , K + , Ca 2+ and Na +, etc.
  • the anions such as CO 3 2- , SO 4 2- and Cl -, etc.
  • the lithium-containing liquid injection area 14 is injected with salt lake brine (Mg 2+ concentration is 10 g/L, Li + concentration is 0.2 g/L, CO 3 2- concentration is 0.16 g/L), the positive electrode area 12 and the negative electrode area 11 are both injected with NaCl solution, and the negative electrode area 11 contains a clean desorbed manganese iron phosphate lithium ion sieve 20 (particle size is 10 ⁇ m).
  • salt lake brine Mg 2+ concentration is 10 g/L, Li + concentration is 0.2 g/L, CO 3 2- concentration is 0.16 g/L
  • the positive electrode area 12 and the negative electrode area 11 are both injected with NaCl solution
  • the negative electrode area 11 contains a clean desorbed manganese iron phosphate lithium ion sieve 20 (particle size is 10 ⁇ m).
  • the total energization time of S1 and S2 is 0.5h.
  • the lithium ion sieve 20 (lithium-rich lithium ion sieve 20) is transferred from the negative electrode area 11 to the positive electrode area 12, and the cations adsorbed by the lithium ion sieve 20 are precipitated under power-on state (1.5V). Some of the precipitated cations form precipitates together with the anions in the positive electrode area 12 (such as Mg 2+ and CO 3 2- forming precipitates together). After the cations are precipitated, the lithium ion sieve 20 is in a desorbed state again.
  • the cleaning method is ultrasonic cleaning, the cleaning time is 0.5h, and the cleaning liquid used is pure water.
  • This embodiment provides a method for extracting lithium from salt lake brine (low Mg/Li ratio), which uses the lithium extraction device in Example 1 in the following manner:
  • the lithium extraction device is energized (1.2V) so that the positive electrode region 12 and the negative electrode region 11 respectively enrich the anions and cations in the lithium-containing solution 15.
  • the cations such as Li + , Mg 2+ , K + , Ca 2+ and Na +, etc.
  • the anions such as CO 3 2- , SO 4 2- and Cl -, etc.
  • the lithium-containing liquid injection area 14 is injected with salt lake brine (Mg 2+ concentration is 5 g/L, Li + concentration is 0.2 g/L, CO 3 2- concentration is 0.04 g/L), the positive electrode area 12 and the negative electrode area 11 are both injected with NaCl solution, and the negative electrode area 11 contains a clean desorbed manganese iron phosphate lithium ion sieve 20 (particle size is 10 ⁇ m).
  • salt lake brine Mg 2+ concentration is 5 g/L, Li + concentration is 0.2 g/L, CO 3 2- concentration is 0.04 g/L
  • the positive electrode area 12 and the negative electrode area 11 are both injected with NaCl solution
  • the negative electrode area 11 contains a clean desorbed manganese iron phosphate lithium ion sieve 20 (particle size is 10 ⁇ m).
  • the total energization time of S1 and S2 is 0.5h.
  • the lithium ion sieve 20 (lithium-rich lithium ion sieve 20) is transferred from the negative electrode region 11 to the positive electrode region 12. Under the electric state (1.2V), the cations adsorbed by the lithium ion sieve 20 are precipitated, and part of the precipitated cations form a precipitate together with the anions in the positive electrode region 12 (such as Mg 2+ and CO 3 2- forming a precipitate together). After the cations are precipitated, the lithium ion sieve 20 is in a desorbed state again.
  • the cleaning method is ultrasonic cleaning, the cleaning time is 0.5h, and the cleaning liquid used is pure water.
  • the difference between this embodiment and embodiment 2 is that the total power-on time of S1 and S2 is 1 hour, and the power-on time of S3 is 1 hour.
  • Example 3 The difference between this comparative example and Example 3 is that a conventional electrodialysis lithium extraction device is used to extract lithium, and the specific method is as follows:
  • the positive electrode region 12 is provided with circulating brine (Mg 2+ concentration is 10 g/L, Li + concentration is 0.2 g/L, CO 3 2- concentration is 0.16 g/L), the negative electrode region 11 is a KCl solution, the positive and negative electrode regions 11 are separated by a lithium ion solid electrolyte, a voltage of 1.0 V is applied, and the power is turned on for 0.5 h, and Li + is enriched in the negative electrode region 11. After multiple enrichments, the negative electrode solution is taken out, and NaOH powder is added to the solution and the solution is heated to 60°C for evaporation, so that Li + is precipitated in the form of LiOH crystals. The process does not use a lithium ion sieve 20.
  • Example 4 The difference between this comparative example and Example 4 is that a conventional electrodialysis lithium extraction device is used to extract lithium, and the specific method is as follows:
  • circulating brine (Mg 2+ concentration is 5g/L, Li + concentration is 0.2g/L, CO 3 2- concentration is 0.04g/L) is provided, and the negative electrode region 11 is a KCl solution.
  • the positive and negative electrode regions 11 are separated by a lithium ion solid electrolyte. A voltage of 1.0V is applied and the power is turned on for 0.5h. Li + is enriched in the negative electrode region 11. After multiple enrichments, the negative electrode solution is taken out, and NaOH powder is added to the solution and the solution is heated to 60°C for evaporation, so that Li + is precipitated in the form of LiOH crystals.
  • the lithium ion sieve 20 is not used in this process.
  • Example 3 can have a higher Mg 2+ removal rate than Comparative Example 1
  • Example 4 of the present application can have a higher Mg 2+ removal rate than Comparative Example 2. This indicates that the lithium extraction method provided in the present application can effectively enrich and extract lithium ions while effectively removing Mg 2+ .
  • Example 3 has a better effect than Example 4, which shows that in the lithium extraction process, the lithium extraction device provided in the present application is more effective in removing magnesium ion impurities in high-magnesium-lithium brine.
  • the lithium extraction device provided in the present application can enrich and extract lithium ions while removing some impurity ions (such as Mg 2+ ), thereby improving the purity of lithium ions.
  • the corresponding lithium extraction method is simple to operate, low in cost, and high in lithium extraction efficiency.
  • the lithium device provided in the present application can continuously enrich and extract lithium ions while removing some impurity ions (such as Mg 2+ ), thereby improving the purity of lithium ions.
  • the corresponding lithium extraction method is simple to operate, low in cost, and high in lithium extraction efficiency.

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Abstract

La présente demande se rapporte au domaine technique de l'extraction de lithium dans des lacs de sel et divulgue un dispositif d'extraction de lithium et un procédé d'extraction de lithium. Le dispositif comprend une cellule électrolytique et un tamis d'ions lithium, et la cellule électrolytique comprend une région d'électrode négative, une région d'électrode positive et une région d'injection de solution d'alimentation contenant du lithium ; la région d'électrode négative, la région d'injection de solution d'alimentation contenant du lithium et la région d'électrode positive sont séquentiellement séparées par une membrane d'échange de cations et une membrane d'échange d'anions, la région d'électrode négative et la région d'électrode positive sont respectivement connectées à une électrode négative d'alimentation électrique et à une électrode positive d'alimentation électrique, et un électrolyte est disposé à la fois dans la région d'électrode négative et dans la région d'électrode positive dans le processus d'utilisation ; et le tamis d'ions lithium subit d'abord une réaction de réduction dans la région d'électrode négative pour adsorber Li+ et piéger certaines impuretés cationiques, puis subit une réaction d'oxydation dans la région d'électrode positive pour précipiter les cations. Le dispositif peut enrichir et extraire en continu des ions lithium tout en éliminant certains ions d'impureté, peut améliorer efficacement le taux d'élimination d'impuretés (telles que Mg2+) dans le processus d'extraction de lithium à partir de lacs de sel, et augmente la pureté des ions lithium. Le procédé d'extraction de lithium correspondant implique des opérations simples, et présente un faible coût et une efficacité d'extraction de lithium élevée.
PCT/CN2023/082451 2023-03-20 2023-03-20 Dispositif d'extraction de lithium et procédé d'extraction de lithium Pending WO2024192617A1 (fr)

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