WO2021070235A1 - Procédé de récupération de lithium et dispositif de récupération de lithium - Google Patents

Procédé de récupération de lithium et dispositif de récupération de lithium Download PDF

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Publication number
WO2021070235A1
WO2021070235A1 PCT/JP2019/039575 JP2019039575W WO2021070235A1 WO 2021070235 A1 WO2021070235 A1 WO 2021070235A1 JP 2019039575 W JP2019039575 W JP 2019039575W WO 2021070235 A1 WO2021070235 A1 WO 2021070235A1
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lithium
liquid
extraction
salt
electrolysis
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PCT/JP2019/039575
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English (en)
Japanese (ja)
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泰教 濃添
賢三 左右田
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日揮グローバル株式会社
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Priority to PCT/JP2019/039575 priority Critical patent/WO2021070235A1/fr
Publication of WO2021070235A1 publication Critical patent/WO2021070235A1/fr

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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
    • 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 invention relates to a lithium recovery method and a lithium recovery device capable of increasing and recovering the lithium concentration of an aqueous liquid containing a lithium salt and other salts.
  • the lithium concentration in brine (brine) collected in a salt lake is as dilute as several hundred mg / L.
  • lithium is concentrated and supplied to the recovery equipment by providing an evaporation pond by natural evaporation in the front stage. If the infrastructure to operate the recovery facility is not in place near the evaporation pond, install the recovery facility in a place away from the evaporation pond and collect the concentrated brine after concentration (volume reduction) by evaporation to the recovery facility. It may be transported.
  • Patent Document 1 describes a method for continuously recovering lithium ions from an aqueous solution, which comprises a phosphine oxide compound and a compound capable of supplying protons (hydrogen ions) under basic conditions (alcohols, ketones, fatty acids, etc.).
  • a method including a step (c) of mixing the aqueous solution remaining in the a) with the organic solvent remaining in the step (b) and reusing the aqueous solution in the step (a) is described.
  • Patent Document 2 describes a step (a) of preparing an electrolysis cell in which a partition capable of transmitting lithium ions and protons (hydrogen ions) is arranged between an anode (anode) and a cathode (cathode), and lithium.
  • a method including a step (f) of recovering a product containing lithium hydroxide from the anode and a step (g) of reusing the product on the anode side for back extraction is described.
  • the evaporation pond which is widely used in the conventional technology for recovering lithium from salt lake brine, requires a lot of time for natural evaporation and can be applied only to areas with low rainfall.
  • the construction of the evaporation pond requires large-scale civil engineering work, so the initial investment cost is also high.
  • an artificial means such as an evaporation can is used as a method for concentrating brine by evaporation, a large running cost is required for energy such as fuel.
  • Salt lake brine chloride brine
  • Salt lake brine sulfate brine, etc.
  • Salt lake brine which contains a large amount of impurities such as sulfate ions, is expected to be developed in the future because of its abundant resources.
  • Patent Document 1 in the lithium recovery technique using solvent extraction, if the lithium concentration in the brine at the time of extraction is low, the lithium recovery rate decreases.
  • Patent Document 2 in the lithium recovery technique using electrolysis, the recovery rate of lithium is determined in the pre-stage of the step (b) of obtaining an aqueous solution containing lithium by back extraction from a medium carrying lithium. Therefore, the electrolysis step described in Patent Document 2 does not solve the above-mentioned problem that the lithium recovery rate decreases when the lithium concentration in the brine is low.
  • An object of the present invention is to provide a lithium recovery method and a lithium recovery device capable of improving the lithium recovery rate even when the lithium concentration in the raw material liquid is low because concentration by evaporation cannot be used. It is to be.
  • a liquid to be extracted which comprises a lithium salt and an aqueous liquid containing at least a magnesium salt or a calcium salt, is brought into contact with a lithium salt extractant to bring at least the lithium salt in the liquid to be extracted.
  • the extraction step of extracting a part of the extract with the extractant and the extraction residual liquid remaining after separating the extract containing the extractant from the liquid to be extracted in the extraction step the residual liquid remains monovalent with respect to the divalent metal ion.
  • It has an electrolysis step of treating by electrolysis via a film body that preferentially or selectively permeates metal ions, and permeates the extract in the extraction step and the film body in the electrolysis step. It is a lithium recovery method characterized by recovering a lithium salt from a product.
  • a second aspect of the present invention is that the liquid to be extracted is a liquid that remains after removing the precipitate in a precipitation step of precipitating excess salt from a raw material liquid containing brine, and the film body in the electrolysis step.
  • the lithium recovery method according to the first aspect which comprises adding the product on the side that has permeated the mixture to the raw material liquid or the liquid to be extracted in the precipitation step.
  • a third aspect of the present invention is the lithium recovery method of the second aspect, characterized in that the raw material liquid in the pre-stage supplied to the precipitation step is acidic.
  • hydrochloric acid is synthesized from chlorine gas generated at the anode and hydrogen gas generated at the cathode in the electrolysis step when the extraction residual liquid contains chloride ions, and the hydrochloric acid is used to prepare the hydrochloric acid.
  • the method for recovering lithium according to any one of the first to third aspects, which comprises recovering a lithium salt from the extract in the extraction step by back extraction.
  • a fifth aspect of the present invention is characterized in that, prior to the electrolysis step, a divalent metal ion removing step of removing at least a part of divalent metal ions contained in the extraction residual liquid is performed. This is the lithium recovery method according to any one of the fourth aspects.
  • a sixth aspect of the present invention is that the liquid to be extracted is a liquid that remains after removing the precipitate in the precipitation step of precipitating excess salt from the raw material liquid containing salt water, and the extraction residual liquid contains sodium ions.
  • carbon dioxide is reacted with the product on the side that has permeated the membrane in the electrolysis step to generate sodium carbonate, and at least a part of the sodium carbonate is supplied to the precipitation step to supply the magnesium salt.
  • the method for recovering lithium according to any one of the first to fifth aspects, which comprises precipitating at least a part of a calcium salt.
  • the extraction residual liquid contains sodium ions
  • carbon dioxide is reacted with a product on the side that has permeated the film body to generate sodium carbonate, and the carbon dioxide is produced.
  • the lithium recovery method according to any one of the first to sixth aspects, which comprises supplying at least a part of sodium to a recovery step for recovering the lithium salt and precipitating at least a part of the lithium salt. is there.
  • An eighth aspect of the present invention is that the liquid to be extracted is a liquid that remains after removing the precipitate in the precipitation step of precipitating excess salt from the raw material liquid containing salt water, and the film body in the electrolysis step.
  • the lithium recovery method according to any one of the first to seventh aspects, wherein the product on the side that does not permeate the precipitate is used for washing the precipitate.
  • a precipitation portion for precipitating excess salt from a raw material liquid containing boiled water and a liquid remaining after removing the precipitate in the precipitation portion are composed of a lithium salt, a magnesium salt or a calcium salt.
  • the extraction unit which is brought into contact with a lithium salt extractant to extract at least a part of the lithium salt in the liquid to be extracted, and the extraction unit, as the liquid to be extracted, which comprises an aqueous liquid containing at least
  • the extract residual liquid remaining after separating the extract containing the extractant from the liquid to be extracted is electrolyzed via a film body that preferentially or selectively permeates the monovalent metal ion with respect to the divalent metal ion.
  • a lithium recovery apparatus characterized in that a lithium salt is recovered from a product that has permeated the film body in the electrolysis section.
  • the extraction residual liquid is treated by electrolysis in the electrolysis step.
  • the concentration of lithium ions, which are ions, can be increased preferentially or selectively. This makes it possible to improve the recovery rate of lithium.
  • the concentration of sulfate ions in the product on the side that has permeated the membrane can be reduced, so that the concentration of sulfate ions can be reduced. Even if the concentration of lithium ions is increased, precipitation of lithium sulfate is unlikely to occur.
  • the product that has permeated the membrane, in which the concentration of lithium ions is preferentially or selectively increased is returned to the precipitation step or the extraction step and brought into contact with the extractant. It is possible to increase the concentration of lithium in the liquid to be extracted and improve the recovery rate of lithium.
  • the present invention can be applied even if the raw material liquid in the previous stage is acidic.
  • hydrochloric acid used for back extraction can be produced by using chlorine gas and hydrogen gas obtained in the electrolysis step.
  • sodium carbonate is produced by utilizing the product obtained by electrolysis of the extraction residual liquid containing sodium ions, and this sodium carbonate is used in the precipitation step to magnesium in the raw material liquid.
  • the salt or calcium salt can be precipitated as magnesium carbonate or calcium carbonate.
  • the product obtained by electrolysis of the extraction residue containing sodium ions is used to produce sodium carbonate, and this sodium carbonate is used in the recovery step to lithium in an aqueous liquid.
  • the salt can be precipitated as lithium carbonate.
  • the product on the side that does not permeate the membrane in the electrolysis step has a high concentration of magnesium salt or calcium salt and a low concentration of lithium ions, so that the precipitate is washed in the precipitation step.
  • water having a high lithium concentration is used for washing the precipitate, it is possible to suppress the absorption of lithium in the precipitate and the loss.
  • the dissolution of the magnesium salt or the calcium salt contained in the precipitate can be suppressed.
  • the extraction residual liquid is treated by electrolysis and does not permeate the film body (
  • the concentration of lithium ion which is a monovalent metal ion that permeates the membrane (or has a relatively high permeability of the membrane) while removing divalent metal ions and the like (the permeability of the membrane is relatively low).
  • the concentration of lithium ion which is a monovalent metal ion that permeates the membrane (or has a relatively high permeability of the membrane) while removing divalent metal ions and the like (the permeability of the membrane is relatively low). Can be preferentially or selectively increased. This makes it possible to improve the recovery rate of lithium.
  • the concentration of sulfate ions in the product on the side that has permeated the membrane can be reduced, so that the concentration of sulfate ions can be reduced. Even if the concentration of lithium ions is increased, precipitation of lithium sulfate is unlikely to occur.
  • lithium in the liquid to be extracted in which the concentration of lithium ions is preferentially or selectively increased by electrolysis, is returned to the precipitation part or the extraction part and brought into contact with the extractant. It is possible to increase the concentration and improve the recovery rate of lithium.
  • FIG. 1 shows an outline of the lithium recovery method of the present embodiment.
  • the liquid to be extracted 20 composed of an aqueous liquid containing a lithium salt is brought into contact with the extractant 21, and at least a part of the lithium salt in the liquid to be extracted 20 is extracted into the extractant 21.
  • It has an extraction step X for making the extraction step X, and an electrolysis step E for treating the extraction residual liquid 23 of the extraction step X by electrolysis.
  • a precipitation step P for precipitating excess salt from the raw material liquid 10 may be provided prior to the extraction step X.
  • the lithium recovery device 100 shown in FIG. 1 includes a precipitation unit 13 for performing the precipitation step P, an extraction unit 24 for performing the extraction step X, and an electrolysis unit 35 for performing the electrolysis step E. ing.
  • the raw material liquid 10 is not particularly limited as long as it is brine containing lithium ions, and examples thereof include salt lake brine collected in a salt lake.
  • salt lakes are located in arid areas, water is naturally evaporated from the lake water trapped inland and salt is concentrated.
  • a method of collecting brine from the salt lake using, for example, a pump, a well, or the like can be used.
  • salts contained in brine include sodium chloride (NaCl), lithium chloride (LiCl), magnesium chloride (MgCl 2 ), calcium chloride (CaCl 2 ) and the like.
  • the brine collected from the salt lake is transferred to an evaporation pond and dried in the sun for about one year to concentrate the brine, increasing the lithium concentration to, for example, several wt%.
  • major salts such as sodium chloride (NaCl) and potassium chloride (KCl) are precipitated, and concentrated brine having an increased lithium concentration can be obtained as a supernatant.
  • NaCl sodium chloride
  • KCl potassium chloride
  • the increase may Sulfate ion (SO 4 2-) concentration in the brine, the lithium ions in the brine are precipitated as lithium sulfate (Li 2 SO 4), lithium concentration in the concentrated brine May decrease.
  • the method of concentrating brine by evaporation has large restrictions on time and location when using natural energy such as sun and wind power, and when using artificial means such as combustion heating. The running cost will increase.
  • the brine collected from the salt lake can be used as the raw material liquid 10 as it is.
  • Brine water that has undergone a predetermined treatment or adjustment may be used as the raw material liquid 10.
  • impurities may be extracted using an impurity extractant, and the extractant containing impurities may be separated from brine.
  • the pH, temperature, etc. of the brine may be adjusted.
  • a pH adjusting agent such as an acid or an alkali can be used.
  • the raw material liquid 10 may be heated or cooled to such an extent that it is not excessively concentrated.
  • a hydrous liquid other than brine may be added to the raw material liquid 10.
  • the raw material liquid 10 may be acidic with a pH of less than 7, neutral with a pH of about 7, or alkaline with a pH of more than 7.
  • the lithium concentration of the raw material liquid 10 When the lithium concentration of the raw material liquid 10 is low, it is preferable to perform the precipitation step P. For example, if the lithium concentration in the raw material liquid 10 is about 1700 to 1800 mg / L or more by weight, it is preferable to omit the precipitation step P. When the lithium concentration in the raw material liquid 10 is about 300 to 400 mg / L or less by weight, it is preferable to carry out the precipitation step P. When the lithium concentration in the raw material liquid 10 is between about 400 mg / L and about 1700 mg / L, it is decided whether to carry out or omit the precipitation step P in consideration of the lithium recovery rate in the extraction step X described later. You may.
  • a chemical such as a precipitating agent 11 is added to precipitate an excess salt content, and the lithium concentration in the supernatant is increased.
  • processing can be performed in a short time and at low cost as compared with the case of using an evaporation pond or an evaporation can.
  • sodium carbonate (Na 2 CO 3 ) is added to the raw material liquid 10
  • the magnesium ions of the raw material liquid 10 can be precipitated as magnesium carbonate (MgCO 3).
  • the settling section 13 used for storing the raw material liquid 10, the settling agent 11, and the like can be composed of a settling tank, a settling basin, and the like.
  • the liquid remaining after removing the precipitate 12 in the precipitation step P may be the liquid to be extracted 20 in the extraction step X.
  • the raw material liquid 10 may be used as it is as the liquid to be extracted 20.
  • a known solid-liquid separation method such as filtration or centrifugation can be used.
  • the lithium salt of the liquid to be extracted 20 is extracted using the extractant 21.
  • the extractant 21 include a liquid or solid extractant 21.
  • the extraction unit 24 used for contacting the liquid to be extracted 20 and the extraction agent 21 can be composed of an extraction tank, an extraction tower, an extraction device, and the like.
  • liquid extractant 21 examples include an extraction compound such as a phosphoric acid ester compound, a phosphonic acid ester compound, and a phosphine oxide compound, or an organic solvent containing an extraction compound.
  • an extraction compound such as a phosphoric acid ester compound, a phosphonic acid ester compound, and a phosphine oxide compound
  • organic solvent containing an extraction compound When the extraction compound is a liquid, the extraction compound containing no other organic solvent may be used as it is as the liquid extractant 21.
  • the organic solvent used in the extractant 21 can be selected in consideration of dissolving the extraction compound, easy separation from water, and the like.
  • Specific examples of the organic solvent are not particularly limited, but are compounds such as aliphatic hydrocarbons, aromatic hydrocarbons, carbon halides, halogenated hydrocarbons, ethers, ketones, phenols, esters, and amides. Examples of these are mixtures.
  • the mixture of organic solvents may be a composition such as kerosene (kerosene).
  • the extract 22 composed of the extractant 21 containing a lithium salt and the extract residue 23 remaining after the extractant 21 is removed by a liquid separation operation are performed. And can be separated.
  • the liquid separation operation it is preferable to utilize the difference in specific gravity between the extract 22 and the extraction residual liquid 23, and centrifugation may be used.
  • the extractant 21 used in the extraction step X may be a solid extractant.
  • a chemical structure such as a functional group that binds to a lithium salt can be introduced into a resin such as an ion exchange resin or a carrier such as clay or ceramics.
  • a resin such as an ion exchange resin
  • a carrier such as clay or ceramics.
  • the extract 22 composed of the extractant 21 containing a lithium salt and the extraction residual liquid remaining after the extractant 21 is removed by solid-liquid separation. 23 can be separated.
  • a known solid-liquid separation method such as filtration or centrifugation can be used.
  • the liquid to be extracted 20 made of an aqueous liquid is brought into contact with the extractant 21, so that at least a part of the lithium salt in the liquid to be extracted 20 is extracted by the extractant 21.
  • the proportion of impurities in the extract 22 can be reduced by the selectivity of the lithium salt with respect to the impurities such as magnesium salt, calcium salt and sodium salt contained in the liquid to be extracted 20. This simplifies the step of removing impurities when recovering the lithium salt from the extract 22.
  • the ratio (O / A ratio) of the organic phase to the aqueous phase is optimized to improve the concentration ratio of lithium ions in the lithium salt-containing extract 22.
  • the installed capacity when recovering the lithium salt from the extract 22 can be reduced.
  • the lithium concentration in the liquid to be extracted 20 is low, the amount of lithium extracted to the extract 22 side is small, and the amount of lithium discharged to the extraction residual liquid 23 side may be a considerable amount. Therefore, if lithium is recovered only from the extract 22, there is a problem that the lithium recovery rate is low. It is desirable to recover the lithium salt from the extraction residual liquid 23 as well, but the lithium concentration in the extraction residual liquid 23 is lower than the lithium concentration in the liquid to be extracted 20. Therefore, it is not easy to increase the recovery rate of the lithium salt by repeating the extraction step X.
  • the electrolysis step E is performed after the extraction step X, and the extraction residual liquid 23 of the extraction step X is treated by electrolysis.
  • the electrolysis unit 35 used in the electrolysis step E includes an electrolysis tank in which an ion exchange membrane is installed between the anode (anode) and the cathode (cathode).
  • the extraction residual liquid 23 is supplied to the anode chamber, which is a space on the anode side of the ion exchange membrane.
  • lithium ions can be moved toward the cathode chamber, which is a space on the cathode side of the ion exchange membrane.
  • Desalted water 30 such as distilled water and deionized water is supplied to the cathode chamber.
  • the volume ratio between the anode chamber and the cathode chamber can be appropriately designed.
  • the electric power required for the electrolysis step E is preferably obtained from a power generation method using natural energy such as solar power generation and wind power generation.
  • the ion exchange membrane used in the electrolysis step E preferentially or selects monovalent metal ions such as lithium (Li) and sodium (Na) over divalent metal ions such as magnesium (Mg) and calcium (Ca). It is a film body that is transparent to calcium. Specific examples thereof include cation exchange membranes used in known chlor-alkali projects. Specific examples of the cation exchange membrane include a fluorine-containing polymer membrane having a functional group that gives an anion such as carboxylic acid and sulfonic acid.
  • a cathode liquid 31 in which lithium salt is concentrated is obtained in the cathode chamber as a product on the side that has passed through the membrane body. Further, in the anode chamber, an anode solution 32 having a reduced lithium salt is obtained as a product on the side that does not permeate the membrane body.
  • the recovery rate of lithium can be improved by recovering the lithium salt from the cathode solution 31 as well.
  • the raw material liquid 10 or the liquid to be extracted 20 contains sulfate ions
  • the sulfate ions do not permeate the membrane body used in the electrolysis step E (or the permeability of the membrane body is relatively low), so that the cathode The sulfate ion concentration in the liquid 31 becomes low. Therefore, even if the lithium concentration in the cathode liquid 31 is increased by electrolysis, the precipitation of lithium sulfate can be suppressed.
  • the lithium concentration in the liquid to be extracted 20 can be increased to improve the recovery rate of lithium.
  • the concentration of magnesium salt or calcium salt is high and the concentration of lithium ions is low. Therefore, the anode solution 32 can be suitably used for cleaning the precipitate 12 in the precipitation step P. Compared with the case where water having a high lithium concentration is used for washing the precipitate 12, it is possible to suppress the absorption of lithium in the precipitate 12 and the loss. Further, as compared with the case where fresh water or the like is used for washing the precipitate 12, the dissolution of the magnesium salt or the calcium salt contained in the precipitate 12 can be suppressed.
  • the state of the precipitate 12 when washed with the anode solution 32 may be in the form of a slurry having a large amount of water or in the form of a cake having a small amount of water.
  • the electrolysis step E when a large amount of divalent metal ions such as magnesium ions and calcium ions contained in the extraction residual liquid 23 are present, at least a part of the divalent metal ions contained in the extraction residual liquid 23 is removed. It is preferable to carry out a valent metal ion removing step.
  • a known adsorption separation method using a chelate resin or the like can be used.
  • the extraction residual liquid 23 to be treated by electrolysis does not substantially contain divalent metal ions.
  • the electrolysis step E by moving the lithium ions from the anode side to the cathode side, the concentration of lithium ions in the cathode liquid 31 is preferentially or selectively selected while suppressing the precipitation of lithium sulfate or the like. Can be enhanced.
  • FIG. 2 shows each step that supplements the lithium recovery method of this embodiment. These steps can be appropriately added to the steps shown in FIG. In FIG. 2, the same reference numerals are used for the configurations common to those in FIG.
  • hydrochloric acid 41 is in the state of an aqueous hydrochloric acid solution because it is easy to handle.
  • An aqueous hydrochloric acid solution can be obtained by allowing water to absorb hydrogen chloride (HCl) gas obtained by burning hydrogen gas 34 in chlorine gas 33.
  • Hydrochloric acid 41 can separate the lithium-containing liquid 42 from the extractant 21 by adding it to the extract 22 in the back extraction step S in which the lithium salt is back-extracted from the extract 22.
  • the lithium-containing liquid 42 is an aqueous liquid containing a lithium salt.
  • the extractant 21 recovered in the back extraction step S can be reused in the extraction step X after undergoing treatments such as washing and purification as necessary.
  • chloride ions are also present in the extraction residual liquid 23 processed in the electrolysis step E. Therefore, by using hydrochloric acid 41 synthesized from chlorine gas 33 and hydrogen gas 34 generated by electrolysis, the cost of chemicals can be reduced.
  • the chemical used for the back extraction of the extract 22 is not limited to the hydrochloric acid 41 produced in the hydrochloric acid production step H.
  • a cathode solution 31 containing sodium ions can be supplied to the sodium carbonate synthesis step N, and carbon dioxide 51 can be reacted to synthesize a sodium carbonate-containing solution 52.
  • the sodium carbonate-containing liquid 52 contains lithium hydroxide (LiOH) together with sodium carbonate (Na 2 CO 3).
  • LiOH lithium hydroxide
  • Na 2 CO 3 sodium carbonate
  • the recovery rate of lithium can be improved or the loss of lithium can be reduced, as will be described later.
  • the sodium carbonate-containing liquid 52 is used in the recovery step R, as shown in FIG. 2, not only when lithium is recovered from the lithium-containing liquid 42 after back extraction, but also lithium from an arbitrary aqueous solution containing lithium. Can be used when collecting.
  • the magnesium salt or calcium salt in the raw material liquid 10 can be precipitated as magnesium carbonate or calcium carbonate.
  • the sodium carbonate-containing liquid 52 used as the precipitant 11 contains a lithium salt, the lithium concentration in the liquid to be extracted 20 is increased as compared with the case where an aqueous solution of the precipitant 11 not containing the lithium salt is used. Can be enhanced.
  • the lithium salt contained in the lithium-containing liquid 42 after the back extraction is recovered as a precipitate 62 containing lithium carbonate (Li 2 CO 3 ) by adding the sodium carbonate-containing liquid 52 as a precipitant 61 in the recovery step R. can do.
  • the lithium salt recovered as the precipitate 62 may be a lithium salt other than lithium carbonate, such as lithium sulfate.
  • a substance other than sodium carbonate may be used as the precipitant 61.
  • a known solid-liquid separation method such as filtration or centrifugation can be used.
  • the lithium carbonate recovered as the precipitate 62 is compared with the case where the sodium carbonate-containing liquid 52 containing no lithium salt is used. The amount can be improved.
  • the lithium concentration in the raw material liquid 10 is low, even when the ratio of lithium ions extracted in the extraction step X is relatively low.
  • the lithium ions remaining in the extraction residual liquid 23 can be recovered.
  • the cost of the evaporation pond, the evaporation can, etc. can be reduced, and even when the sulfate ion concentration in the brine is high, the lithium ion in the brine is lithium sulfate. The loss due to precipitation can be suppressed.
  • the lithium concentration in the extraction residual liquid 23 is relatively high with respect to the lithium concentration in brine, and the lithium recovery rate is as low as 29 to 41%.
  • the lithium concentration ratio represents the ratio at which the lithium concentration in the lithium-containing liquid 42 after back extraction is concentrated with respect to the lithium concentration in the brine used for the raw material liquid 10.
  • the lithium recovery rate represents the ratio of lithium recovered from the brine used in the raw material liquid 10 to the lithium-containing liquid 42 after back extraction.
  • the lithium concentration in the lithium-containing liquid 42 after the back extraction can be increased.
  • the capacity of the equipment required for removing impurities or recovering lithium in the steps after the extraction step X or the back extraction step S can be reduced.
  • the extraction step X is performed directly from the liquid to be extracted 20 having the same lithium concentration as the brine without concentrating the brine, there is a limitation in improving the lithium recovery rate. Therefore, by treating the extraction residual liquid 23 by electrolysis as in the above-described embodiment, the lithium concentration of the cathode liquid 31 is made higher than the lithium concentration of the extraction residual liquid 23, and the lithium recovery rate is improved. Is possible. Further, chlorine and hydrogen produced in the electrolysis step E can be used for producing hydrochloric acid used in the back extraction step S. The electrolysis step E and the hydrochloric acid production step H can be easily carried out by existing techniques in the same manner as the steps used in the general chlor-alkali business.
  • the present invention can be used for producing lithium compounds used in various applications such as lithium ion batteries, lithium-containing alloys, ceramic products, lithium soaps, and pharmaceuticals.
  • E Electrolysis process, F ... Supply process, H ... Hydrochloride production process, N ... Sodium carbonate synthesis process, P ... Precipitation process, R ... Recovery process, S ... Reverse extraction process, X ... Extraction process, 10 ... Raw material liquid, 11 ... Precipitant, 12 ... Precipitate, 13 ... Precipitate, 20 ... Liquid to be extracted, 21 ... Extractor, 22 ... Extract, 23 ... Extraction residue, 24 ... Extraction part, 30 ... Water, 31 ... Cathode liquid , 32 ... anode solution, 33 ... chlorine gas, 34 ... hydrogen gas, 35 ... electrolysis part, 41 ... hydrochloric acid, 42 ... lithium-containing solution, 51 ... carbon dioxide, 52 ... sodium carbonate-containing solution, 61 ... precipitant, 62 ... Precipitate, 63 ... Aqueous liquid, 100 ... Lithium recovery device.

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Abstract

Le présent procédé de récupération de lithium est caractérisé par : une étape d'extraction servant à amener un liquide cible d'extraction, comprenant un liquide aqueux contenant au moins un sel de lithium et un sel de magnésium ou un sel de calcium, en contact avec un agent d'extraction de sel de lithium, de façon à amener au moins une partie du sel de lithium dans le liquide cible d'extraction à être extrait dans l'agent d'extraction ; et une étape d'électrolyse servant à soumettre un liquide résiduel d'extraction, qui est obtenu à l'étape d'extraction après qu'un extrait contenant l'agent d'extraction a été séparé du liquide cible d'extraction, à une électrolyse à travers un corps membranaire qui laisse passer de façon préférentielle ou sélective des ions métalliques monovalents par rapport à des ions métalliques divalents, le sel de lithium étant récupéré à partir de l'extrait lors de l'étape d'extraction et d'un produit passant à travers le corps membranaire lors de l'étape d'électrolyse.
PCT/JP2019/039575 2019-10-08 2019-10-08 Procédé de récupération de lithium et dispositif de récupération de lithium WO2021070235A1 (fr)

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* Cited by examiner, † Cited by third party
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WO2023054417A1 (fr) * 2021-09-28 2023-04-06 株式会社レゾナック Agent d'extraction de sel de lithium, composition, procédé de récupération de sel de lithium et procédé de production de sel de lithium

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JPH0835080A (ja) * 1994-07-22 1996-02-06 Mitsubishi Materials Corp アルミニウム含有廃液の再生方法
JP2009269810A (ja) * 2008-05-07 2009-11-19 Kee:Kk 高純度水酸化リチウムの製造法

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JPH0835080A (ja) * 1994-07-22 1996-02-06 Mitsubishi Materials Corp アルミニウム含有廃液の再生方法
JP2009269810A (ja) * 2008-05-07 2009-11-19 Kee:Kk 高純度水酸化リチウムの製造法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023054417A1 (fr) * 2021-09-28 2023-04-06 株式会社レゾナック Agent d'extraction de sel de lithium, composition, procédé de récupération de sel de lithium et procédé de production de sel de lithium

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