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WO2013146391A1 - Procédé de séparation et de récupération d'un métal alcalin et appareil de séparation et de récupération d'un métal alcalin - Google Patents

Procédé de séparation et de récupération d'un métal alcalin et appareil de séparation et de récupération d'un métal alcalin Download PDF

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WO2013146391A1
WO2013146391A1 PCT/JP2013/057539 JP2013057539W WO2013146391A1 WO 2013146391 A1 WO2013146391 A1 WO 2013146391A1 JP 2013057539 W JP2013057539 W JP 2013057539W WO 2013146391 A1 WO2013146391 A1 WO 2013146391A1
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Prior art keywords
water
alkali metal
ion
divalent
nanofiltration membrane
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English (en)
Japanese (ja)
Inventor
寛生 高畠
谷口　雅英
佐々木　崇夫
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Toray Industries Inc
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Toray Industries Inc
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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
    • 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
    • C22B7/006—Wet processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/25—Recirculation, recycling or bypass, e.g. recirculation of concentrate into the feed
    • B01D2311/252—Recirculation of concentrate
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • the present invention relates to a method and apparatus for recovering alkali metals such as lithium and potassium from lake water, groundwater, industrial wastewater and the like.
  • lithium carbonate is used for a surface acoustic wave filter in addition to an electrode material of a lithium ion battery and a heat-resistant glass additive.
  • High purity products are used as filters and transmitters for mobile phones and car navigation systems.
  • Lithium bromide is used as a refrigerant absorbent for large-scale air-conditioning absorption refrigerators in buildings and factories, and lithium hydroxide is used as a raw material for grease and lithium batteries (primary and secondary) for automobiles.
  • Applications of metallic lithium include foil as a negative electrode material for primary batteries and raw materials for butyl lithium for synthetic rubber catalysts.
  • salt lake brine and ore is contained in salt lake brine and ore, and it is advantageous to recover resources from salt lake brine in terms of production cost.
  • Salt lake brackish water exists mainly in Chile, Peru, and Argentina and has a large reserve.
  • the composition is broadly classified into chloride brine, sulfate brine, carbonate brine, and calcium brine.
  • sulfate brine which has the largest amount of resources, has a low solubility of sulfate during the purification process. Many of them form salts or contain a lot of alkaline earth metal salts or sulfates, and it is difficult to efficiently recover lithium.
  • Patent Documents 1 and 2 As a measure to solve this, a method using an adsorbent (for example, refer to Patent Documents 1 and 2) has been proposed, but the cost is difficult, and as a technique for stably recovering lithium at a low cost. Not established. Conventional low-cost methods include drying the brine in the sun and removing impurities while concentrating, but when the lithium concentration is low or the alkaline earth metal salt or sulfate concentration is high, etc. There was a problem that it was difficult to apply. Furthermore, electrodialysis methods and membrane filtration methods are being studied (for example, see Non-Patent Document 1), but have not yet been put into practical use.
  • An object of the present invention is to provide a method and an apparatus for efficiently recovering alkali metal from raw water containing alkali metal such as lithium and potassium such as lake water, groundwater, industrial wastewater.
  • the present invention relates to the following (1) to (7).
  • (1) Permeating and separating raw water containing alkali metal and divalent ions using a nanofiltration membrane to obtain permeated water and concentrated water; and at least part of the alkali metal contained in the permeated water
  • An alkali metal separation and recovery method comprising recovering, By removing divalent ions contained in the concentrated water, divalent ion-removed water having a larger ratio of alkali metal ion equivalent weight concentration to divalent ion weight concentration than the concentrated water is obtained.
  • the turbidity-treated water is obtained by turbidizing at least a part of the raw water, and at least a part of the turbidity-treated water is permeated and separated using the nanofiltration membrane.
  • a nanofiltration membrane unit that permeates and separates raw water containing alkali metal and divalent ions using a nanofiltration membrane to obtain permeated water and concentrated water, and at least alkali metal contained in the permeated water
  • a recovery unit for recovering a part
  • a divalent ion removal unit for removing at least a part of the divalent ions contained in the concentrated water
  • An alkali metal separation and recovery apparatus wherein at least a part of the divalent ion-removed water obtained by the divalent ion removal unit is refluxed to the raw water.
  • alkali metals such as lithium and potassium can be efficiently recovered from raw water in which various solutes coexist.
  • FIG. 1 is a schematic flowchart showing an alkali metal separation and recovery method according to an embodiment of the present invention.
  • FIG. 1 An example of the execution flow of the alkali metal recovery of the present invention is shown in FIG.
  • raw water 1 containing alkali metal or the like is temporarily stored in a raw water tank 2 and then sent to a pretreatment unit 4 by a supply pump 3 for processing.
  • the pretreated feed water is sent to the nanofiltration membrane unit 6 by the booster pump 5, and the nanofiltration membrane permeated water (hereinafter also simply referred to as “permeated water”) 7 and the nanofiltration membrane from which the alkali metal is permeated and separated.
  • Concentrated water hereinafter simply referred to as “concentrated water” 8 is obtained.
  • the nanofiltration membrane permeated water 7 is sent to the recovery unit 11 and the alkali metal 12 is recovered.
  • the nanofiltration membrane concentrated water 8 is sent to the divalent ion removal unit 9, and at least a part of the divalent ions 14 contained in the nanofiltration membrane concentrated water 8 is removed and discharged.
  • the divalent ion-removed water 10 having a large ratio of the alkali metal ion equivalent weight concentration to the divalent ion weight concentration is obtained, and at least a part of the divalent ion-removed water 10 is refluxed to the raw water 1.
  • the raw water 1 to be treated by the method of the present invention includes at least one kind of alkali metals such as lithium, sodium, potassium, rubidium and cesium, alkaline earth metal ions such as magnesium ions, calcium and strontium, sulfate ions, At least one kind of anions such as carbonate ions is included.
  • alkali metals such as lithium, sodium, potassium, rubidium and cesium
  • alkaline earth metal ions such as magnesium ions, calcium and strontium
  • sulfate ions At least one kind of anions such as carbonate ions is included.
  • typical elements aluminum, tin, lead, etc.
  • transition elements iron, copper, cobalt, manganese, etc.
  • one or more conjugate bases A compound composed of a salt with (for example, chloride ion, nitrate ion, sulfate ion, carbonate ion, acetate ion, etc.) is dissolved.
  • concentration of each of these components is not particularly limited, but the alkali metal ion equivalent weight concentration and / or divalent ion weight concentration of water supplied to the nanofiltration membrane unit is 0.5 ppm or more and 10,000 ppm or less from the viewpoint of the efficiency of separation and recovery.
  • a desired purified alkali metal salt such as lithium carbonate or potassium chloride is separated and recovered by subjecting the nanofiltration membrane permeated water 7 obtained by permeating and separating the raw water 1 as a purification inhibitor.
  • divalent ions such as alkaline earth metal ions, magnesium ions, sulfate ions, etc. that are likely to form hardly soluble salts are exemplified.
  • the divalent ion weight concentration in the raw water 1 is 1000 times or less compared to the alkali metal ion equivalent weight concentration.
  • the content of the purification inhibitor such as divalent ions in the raw water 1 varies depending on the composition of the purification inhibitor and the properties of the raw water.
  • magnesium ions and sulfate ions are in the range of 100 ppm to 30000 ppm, respectively. Included.
  • the alkali metal ion refers to lithium ion, sodium ion, potassium ion, rubidium ion, and cesium ion
  • the alkali metal ion equivalent weight concentration refers to one or more alkalis selected from these alkali metal ion groups. It refers to the ion equivalent weight concentration of metal ions, or the sum thereof.
  • the divalent ion refers to beryllium ion, magnesium ion, calcium ion, strontium ion, sulfate ion, and carbonate ion.
  • the divalent ion weight concentration refers to one or more selected from these divalent ion groups.
  • alkali metal ion equivalent weight concentration and divalent ion weight concentration can be determined, for example, by quantifying various ion concentrations of an aqueous solution containing an alkali metal salt by ion chromatography.
  • the nanofiltration membrane permeate 7 and the nanofiltration membrane concentrated water 8 are obtained by treating the supply water with the nanofiltration membrane unit 6.
  • the nanofiltration membrane has a low removal rate of alkali metal ions, but preferably has a property of high removal rate of divalent ions.
  • the nanofiltration membrane permeated water 7 having a higher alkali metal ion equivalent weight concentration with respect to the divalent ion weight concentration than the supply water can be obtained, whereby the alkali metal recovery efficiency in the recovery unit 11 is increased.
  • the removal treatment by the nanofiltration membrane unit 6 is performed until the magnesium ion concentration in the aqueous solution containing the alkali metal salt (the nanofiltration membrane permeated water 7) is 7 times or less than the lithium ion concentration in the aqueous solution. Preferably it is done. If this ratio exceeds 7 times, the recovery efficiency of the purified alkali metal salt is significantly reduced.
  • the recovery unit 11 functions as a purification inhibitor for alkali metal recovery when divalent ions such as alkaline earth metal ions, magnesium ions, and sulfate ions are contained in a certain ratio or more with respect to the alkali metal. Therefore, the nanofiltration membrane concentrated water 8 containing a high concentration of divalent ions is generally drained, but the proportion of alkali metal ions in the nanofiltration membrane concentrated water 8 is smaller than that of other components. Since it is contained more than the raw water concentration, it is preferably refluxed to the raw water 1.
  • the nanofiltration membrane concentrated water 8 is recirculated to the raw water 1 as divalent ion-removed water 10 having a large ratio of the alkali metal ion equivalent weight concentration to the divalent ion weight concentration.
  • the recovery rate of the alkali metal 12 from the raw water 1 can be increased while suppressing alkali metal recovery inhibition.
  • the nanofiltration membrane is a membrane defined by IUPAC as “a pressure-driven membrane in which particles and polymers having a size of less than 2 nm are blocked”.
  • the nanofiltration membrane effective for application to the present invention has a charge on the membrane surface, and particularly improves the separation efficiency of ions by the combination of pore separation (size separation) and electrostatic separation by membrane surface charge. It is preferable to apply a nanofiltration membrane capable of removing polymers by size separation while separating alkali metal ions to be collected and other ions having different charge characteristics by charging.
  • nanofiltration membrane suitable for the present invention, glucose removal particularly when permeating a 1000 ppm isopropyl alcohol aqueous solution at 25 ° C. and pH 6.5 and a 1000 ppm glucose aqueous solution at 25 ° C. and pH 6.5 at an operating pressure of 0.5 MPa, respectively.
  • a nanofiltration membrane with a rate of 90% or more and a difference between the glucose removal rate and the isopropyl alcohol removal rate of 30% or more, alkali metal salts, especially lithium salts, and purification inhibition are inhibited regardless of the total salt concentration. This is particularly preferred since the separation of substances is achieved with very high efficiency.
  • the nanofiltration membrane unit 6 is composed of modularized nanofiltration membranes. For example, one or a plurality of spiral nanofiltration membrane elements connected to each other and housed in a container, or connected in series or in parallel. Refers to
  • nanofiltration membrane unit 6 With respect to the nanofiltration membrane unit 6, one-stage processing is also possible, and in the case of increasing the recovery rate, there is no problem in making the so-called multistage in which the concentrated water is further processed by the next nanofiltration membrane unit 6. It is possible to set appropriately so that the performance of the filtration membrane can be expressed highly.
  • the nanofiltration membrane unit 6 has different performance at each stage.
  • it is easy to make the separation performance such as the pore diameter of the nanofiltration membrane different.
  • the molecular weight and charge characteristics of the nanofiltration membrane are changed according to the supply water quality gradually changing in each stage of the nanofiltration membrane unit 6. It is possible to increase the separation efficiency by optimizing.
  • the permeation amount decreases due to pressure loss due to flow resistance and decrease in effective filtration pressure due to an increase in feed water concentration from the previous stage to the subsequent stage, the pure water permeability of the nanofiltration membrane in the subsequent stage is improved. The larger one is preferable.
  • the pure water permeation performance as used herein can be measured by allowing pure water applied with a pressure of 0.5 MPa to pass through the nanofiltration membrane, and water permeated per unit membrane area and unit time at 25 ° C. It is a value obtained by measuring the amount.
  • the concentration of the feed water rises as the latter stage, not a small amount of alkali metal ions permeate the nanofiltration membrane, so that the other solutes (alkaline earth metals and The ratio of the concentration of polyvalent ions such as sulfate ions) increases, and the alkali metal content of the permeated water also decreases from the previous stage. Therefore, it is preferable to use a nanofiltration membrane with higher separation performance as the latter stage. Specifically, regarding the ratio of the sulfate ion permeability to the alkali metal permeability, the ratio of the first stage nanofiltration membrane unit is smaller than the ratio of the final stage nanofiltration membrane unit, thereby making the present invention more efficient. Can be realized.
  • Such a nanofiltration membrane can be realized by increasing the pore diameter (fractionated molecular weight) while increasing the surface charge of the nanofiltration membrane in the subsequent stage as compared with the previous stage.
  • B. ⁇ Kaeselev et al. “Photoinduced grafting of ultrafiltration membranes: comparison of poly (ether sulfone) and poly (sulfone)” (Journal of Membrane Science) Examples thereof include a method in which radicals (active sites) are produced by UV, electron beam, plasma, etc., and graft polymerization is performed, and a method in which a polymer chain is cleaved with an oxidizing agent or the like.
  • a polycondensation reaction between a polyfunctional amine and a polyfunctional acid halide is performed from the viewpoint of achieving both high water permeability and separation performance and high potential for comprehensive membrane performance.
  • a composite semipermeable membrane having an ultrathin film layer of the obtained crosslinked polyamide on a microporous support membrane is preferred.
  • aliphatic polyamide is the main component (that is, the number of amide bonds of aliphatic polyamide is larger than that of aromatic polyamide), and high permeation performance is required.
  • an aromatic polyamide is a main component.
  • piperazine-based amines represented by the following formula [I] and derivatives thereof are preferable.
  • Piperazine, 2,5-dimethylpiperazine, 2-methylpiperazine, 2,6-dimethylpiperazine, 2,3,5 -Trimethylpiperazine, 2,5-diethylpiperazine, 2,3,5-triethylpiperazine, 2-n-propylpiperazine, 2,5-di-n-butylpiperazine and the like are exemplified.
  • R1 to R8 independently represent H, OH, COOH, SO 3 H, NH 2 , or C1 to C4 linear or cyclic saturated or unsaturated aliphatic group. .
  • the polyfunctional amine is an amine having two or more amino groups in one molecule, and includes an o-aromatic diamine having two amino groups in the ortho position (o-). Those are preferred. Further, the polyfunctional amines include m-aromatic diamines having two amino groups at the meta position (m-), p-aromatic diamines having two amino groups at the para position (p-), and aliphatic systems. At least one selected from the group consisting of amines and derivatives thereof is more preferable, and among them, a dense and rigid structure has excellent potential for blocking performance and water permeability, and further has excellent durability, particularly heat resistance. More preferably, it contains m-aromatic diamine and p-aromatic diamine, which are easy to obtain.
  • o-phenylenediamine is preferably used as the o-aromatic diamine.
  • m-aromatic diamine m-phenylenediamine is preferable, but 3,5-diaminobenzoic acid, 2,6-diaminopyridine and the like can also be used.
  • p-aromatic diamine p-phenylenediamine is preferable, but 2,5-diaminobenzenesulfonic acid, p-xylylenediamine and the like can also be used.
  • the molar ratio of these polyfunctional amines in the film-forming stock solution can be appropriately selected depending on the amine and acid halide used. However, the higher the addition ratio of o-aromatic diamine, the better the water permeability. On the other hand, the blocking performance of the entire solute is reduced. Moreover, the separation performance of multivalent ions and monovalent ions is improved by increasing the number of aliphatic polyfunctional amines. As a result, it is possible to obtain the liquid separation membrane (filtration membrane) of the present invention that satisfies the intended water permeability performance, ion separation performance, and blocking performance of the entire solute.
  • the heat stability is lowered. Therefore, when heat resistance is important, the heat resistance can be improved by reducing the number of aliphatic amines.
  • polyfunctional acid halides are acid halides or polyfunctional acid anhydride halides having two or more carbonyl halide groups in one molecule, and the function of separating crosslinked polyamide by reaction with the above polyfunctional amine.
  • the polyfunctional acid halide include 1,3,5-cyclohexanetricarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4.
  • -Acid halides such as benzenetricarboxylic acid, 1,3-benzenedicarboxylic acid, and 1,4-benzenedicarboxylic acid, and mixtures thereof.
  • a dicarboxylic acid represented by the following formula [II] or a tricarboxylic acid represented by the following formula [III] which has a good film forming property and is capable of easily obtaining a film having uniform solute blocking performance and less defects and variations.
  • An acid is preferred, and in particular, trimesic acid chloride, which is an acid halide of 1,3,5-benzenetricarboxylic acid, is preferred from the viewpoints of economy, ease of handling, ease of reaction, and the like.
  • R represents H or a C1-C3 hydrocarbon.
  • R represents H or a C1-C3 hydrocarbon.
  • the polyfunctional acid anhydride halide is a carbonyl halide of benzoic anhydride or phthalic anhydride having one or more acid anhydride moieties and one or more halogenated carbonyl groups in one molecule.
  • a trimellitic anhydride halide represented by the following general formula [IV] and derivatives thereof are preferably used.
  • X1 and X2 are independently of each other a C1-C3 linear or cyclic saturated or unsaturated aliphatic group, H, OH, COOH, SO 3 H, COF, COCl, COBr, Alternatively, it represents COI and may form an acid anhydride between X1 and X2.
  • X3 is a C1-C3 linear or cyclic saturated or unsaturated aliphatic group, H, OH, COOH, SO 3 represents H, COF, COCl, COBr, or COI, and Y represents H, F, Cl, Br, I, or a C1-C3 hydrocarbon.
  • the feed water of each stage it is also preferable to pressurize the feed water of each stage.
  • the pressure is increased by a booster pump or the like to increase the processing performance of the subsequent stage.
  • the water permeability of the rear stage can be substantially increased.
  • the magnesium sulfate removal rate when passing through a 2000 ppm magnesium sulfate aqueous solution at 25 ° C. and pH 6.5 and a 2000 ppm lithium chloride aqueous solution at 25 ° C. and pH 6.5 at an operating pressure of 0.5 MPa is preferably 90% or more, preferably
  • the lithium chloride removal rate is 70% or less, preferably 50% or less, more preferably 30% or less, the total salt concentration can be reduced. Regardless, the separation of alkali metal and divalent ions is achieved with extremely high efficiency.
  • the energy recovery apparatus includes a pump-integrated type in which liquid discharged from the discharge side of the booster pump 5 directly flows into the energy recovery apparatus, and a part of the supplied water flows into the booster pump 5 and the remaining part of the energy is supplied to the energy recovery apparatus.
  • a pump separation type mold which flows in, in this invention, if the pressure energy of the nanofiltration membrane concentrated water 8 is utilized, it will not specifically limit.
  • Specific examples include a turbine (Francis type, Pelton type), a reverse pump, a hydro turbocharger, and a pressure exchanger (piston type, rotor type).
  • the nanofiltration membrane permeated water 7 containing alkali metal is obtained by the nanofiltration membrane unit 6 and the nanofiltration membrane concentrated water 8 obtained at the same time contains a large amount of divalent ions, which are alkali metal purification inhibitors, and is drained.
  • the nanofiltration membrane concentrated water 8 is removed by divalent ions because the alkali metal ions to be recovered are contained at a concentration higher than the raw water concentration although the ratio is smaller than that of the other components.
  • At least a part of the divalent ions is removed by the unit 9, and the obtained divalent ion-removed water 10 is refluxed to the raw water.
  • the divalent ion-removed water 10 may be refluxed downstream of the pretreatment unit 4, but inside the nanofiltration membrane unit 6 or the divalent ion removal unit 9. It is more preferable to return to the upstream side of the pretreatment unit 4 on the assumption that the divalent ion-removed water 10 contains a solid content due to the biological growth of
  • the divalent ion removal unit 9 as long as it produces divalent ion-removed water having a larger ratio of the alkali metal ion equivalent weight concentration to the divalent ion weight concentration than the nanofiltration membrane concentrated water 8, although not limited, For example, a crystallization process, an adsorption process, an ion exchange process, etc. are mentioned.
  • Crystallization treatment uses a difference between the solubility of alkali metal and the solubility of divalent ions to crystallize more divalent ions than alkali metal, and remove the crystallized solids by solid-liquid separation. Is the method.
  • the crystallization method is determined based on the relationship between the target alkali metal and divalent ions, and the means is not particularly limited.
  • heat is applied to the nanofiltration membrane concentrated water 8 to evaporate some water. Examples thereof include cooling the concentrated water to lower the water temperature, and adding a pH adjusting agent such as acid or alkali to the concentrated water to change the pH.
  • the method of evaporating moisture by applying heat to the nanofiltration membrane concentrated water 8 is preferable because it simultaneously increases the alkali metal concentration and improves the alkali metal recovery efficiency by the alkali metal recovery unit.
  • the amount of heat and time, the cooling temperature and time, the amount of acid and alkali added, and the like added during evaporation be appropriately determined according to the type and concentration of the target alkali metal and divalent ions.
  • Examples of the solid-liquid separation in the crystallization process include sedimentation separation and membrane separation.
  • the solid-liquid separation treatment is omitted, and the divalent ion-removed water is refluxed upstream of the turbidity treatment step.
  • Solid-liquid separation may also be used.
  • the adsorption treatment is a method of adsorbing and removing divalent ions from the nanofiltration membrane concentrated water by bringing the adsorbent that adsorbs the divalent ions to be removed into contact with the nanofiltration membrane concentrated water.
  • Adsorbents include polar adsorbents such as silica and alumina, and nonpolar adsorbents such as activated carbon, but polar adsorbents capable of selectively adsorbing divalent ions are preferable.
  • the ion exchange treatment is not particularly limited as long as the ion exchange resin has a function of taking in divalent ions contained in the nanofiltration membrane concentrated water and releasing another kind of ions instead.
  • the material include organic materials and inorganic materials.
  • the ion species to be removed include a cation exchange resin and an anion exchange resin, which are appropriately selected according to the material to be removed. At that time, it is preferable that the ions to be released do not reduce the efficiency of the nanofiltration membrane unit 6 and the recovery unit 11 that recovers the alkali metal.
  • the recovery alkali metal salt in the nanofiltration membrane permeated water 7 is recovered by the recovery unit 11.
  • the purified alkali metal salt can be recovered by a known method of recovering potassium chloride by utilizing the temperature dependency of solubility or adding a poor solvent such as ethanol.
  • a lithium salt it is recovered as lithium carbonate, for example, by adding a carbonate to an aqueous solution, taking advantage of its low solubility compared to other alkali metal salts. This is because sodium carbonate and potassium carbonate have a sufficiently high solubility in water (20 g or more with respect to 100 mL of water), whereas the solubility of lithium carbonate is only 1.33 g with respect to 100 mL of water at 25 ° C. This is to take advantage of the decrease.
  • the recovered residual liquid 13 after recovering the alkali metal by the recovery unit 11 can be drained or can be refluxed in the supply water (raw water) depending on the alkali metal content.
  • the pretreatment unit 4 is not particularly limited, and can be appropriately selected such as removal of turbid components and sterilization depending on the raw aqueous state.
  • pretreating raw water and modifying it to a water quality suitable for the nanofiltration membrane supply water it is possible to reduce the burden on the nanofiltration membrane and to operate while stably holding the nanofiltration membrane.
  • a turbidity treatment such as sand filtration, microfiltration membrane, ultrafiltration membrane, etc.
  • a turbidity treatment such as sand filtration, microfiltration membrane, ultrafiltration membrane, etc.
  • Chlorine is preferably used as the disinfectant, and for example, chlorine gas or sodium hypochlorite may be added to the feed water as free chlorine so as to be in the range of 1 to 5 mg / l.
  • chlorine gas or sodium hypochlorite may be added to the feed water as free chlorine so as to be in the range of 1 to 5 mg / l.
  • the specific bactericidal agent does not have chemical durability.
  • the disinfectant ineffective near the feed water inlet side of the nanofiltration membrane unit 6.
  • free chlorine its concentration is measured, and the addition amount of chlorine gas and sodium hypochlorite is controlled based on this measured value, or a reducing agent such as sodium bisulfite is added.
  • a flocculant such as polyaluminum chloride, sulfate band, iron (III) chloride.
  • the agglomerated supply water is then subjected to sand filtration after settling on an inclined plate or the like, or by filtration through a microfiltration membrane or an ultrafiltration membrane in which a plurality of hollow fiber membranes are bundled. It can be set as the feed water suitable for letting the latter nanofiltration membrane unit 6 pass.
  • sand filtration when sand filtration is used for pretreatment, it is possible to apply gravity-type filtration that naturally flows down, or it is possible to apply pressure-type filtration in which a pressure tank is filled with sand. .
  • sand to be filled single-component sand can be applied.
  • anthracite, silica sand, garnet, pumice, and the like can be combined to increase the filtration efficiency.
  • the microfiltration membrane and the ultrafiltration membrane are not particularly limited, and a flat membrane, a hollow fiber membrane, a tubular membrane, a pleated shape, or any other shape can be used as appropriate.
  • the material of the membrane is not particularly limited, and it is possible to use an inorganic material such as polyacrylonitrile, polyphenylene sulfone, polyphenylene sulfide sulfone, polyvinylidene fluoride, polypropylene, polyethylene, polysulfone, polyvinyl alcohol, cellulose acetate, or ceramic. it can. Moreover, even if it is a filtration system, any of the pressure filtration system which pressurizes and filters supply water, and the suction filtration system which sucks and filters the permeation
  • agglomerated membrane filtration or membrane separation activated sludge method in which a microfiltration membrane or an ultrafiltration membrane is immersed in a coagulation sedimentation tank or a biological treatment tank for filtration, is applied.
  • MLR membrane separation activated sludge method
  • the organic matter when the supply water (raw water) contains a lot of soluble organic matter, the organic matter can be decomposed by adding chlorine gas or sodium hypochlorite. Can also be removed.
  • a chelating agent such as an organic polymer electrolyte or sodium hexametaphosphate may be added, or exchanged with soluble ions using an ion exchange resin or the like.
  • iron or manganese when iron or manganese is present in a soluble state, it is preferable to use an aeration oxidation filtration method or a contact oxidation filtration method.
  • the present invention relates to an apparatus for recovering alkali metals such as lithium and potassium from lake water, groundwater, industrial wastewater and the like, and a method for operating the same, and is concentrated by adding divalent ion-removed water to raw water containing alkali metals.
  • alkali metals can be efficiently separated and recovered from water containing various solutes that are difficult to separate and recover.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Geology (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Hydrology & Water Resources (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)
  • Water Treatment By Sorption (AREA)
  • Manufacture And Refinement Of Metals (AREA)
PCT/JP2013/057539 2012-03-30 2013-03-15 Procédé de séparation et de récupération d'un métal alcalin et appareil de séparation et de récupération d'un métal alcalin Ceased WO2013146391A1 (fr)

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CN106276987A (zh) * 2016-08-05 2017-01-04 四川思达能环保科技有限公司 锂浸出液的浓缩方法
WO2017013536A1 (fr) * 2015-07-23 2017-01-26 I.D.E. Technologies Ltd Procédé d'osmose inverse ou de nano-filtration amélioré pour la purification d'eau
JPWO2015141693A1 (ja) * 2014-03-18 2017-04-13 東レ株式会社 半透膜分離装置および半透膜分離装置の運転方法
JP2017176969A (ja) * 2016-03-29 2017-10-05 アクアス株式会社 原水の処理方法
JP2020020016A (ja) * 2018-08-02 2020-02-06 住友金属鉱山株式会社 リチウムの精製方法
WO2020158456A1 (fr) * 2019-01-30 2020-08-06 東洋紡株式会社 Système de concentration et procédé de concentration
WO2021159144A1 (fr) * 2020-02-06 2021-08-12 Schlumberger Technology Corporation Extraction de lithium intégrée
EP3885031A4 (fr) * 2018-12-26 2022-07-27 Toray Industries, Inc. Procédé de fabrication de sel de métal alcalin
KR20220147157A (ko) * 2020-04-21 2022-11-02 도레이 카부시키가이샤 레어 메탈염의 회수 방법
WO2023196348A1 (fr) * 2022-04-04 2023-10-12 Energy Exploration Technologies, Inc. Systèmes et procédés destinés à la production de métal à partir de solutions de saumure
JPWO2025070624A1 (fr) * 2023-09-29 2025-04-03
KR102887009B1 (ko) 2018-12-26 2025-11-17 도레이 카부시키가이샤 알칼리 금속염의 제조 방법

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CN112850851B (zh) * 2021-02-01 2022-04-15 中国科学院青海盐湖研究所 一种提高硫酸钠亚型盐湖卤水中的Li+收率的方法

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JPWO2015141693A1 (ja) * 2014-03-18 2017-04-13 東レ株式会社 半透膜分離装置および半透膜分離装置の運転方法
WO2017013536A1 (fr) * 2015-07-23 2017-01-26 I.D.E. Technologies Ltd Procédé d'osmose inverse ou de nano-filtration amélioré pour la purification d'eau
EA036084B1 (ru) * 2015-07-23 2020-09-24 Ай.Ди.И. ТЕКНОЛОДЖИЗ ЛТД. Усовершенствованный способ обратного осмоса или нанофильтрации для очистки воды
JP2017176969A (ja) * 2016-03-29 2017-10-05 アクアス株式会社 原水の処理方法
CN106276987A (zh) * 2016-08-05 2017-01-04 四川思达能环保科技有限公司 锂浸出液的浓缩方法
CN106282557B (zh) * 2016-08-05 2018-08-28 四川思达能环保科技有限公司 锂浸出液的浓缩方法
CN106282557A (zh) * 2016-08-05 2017-01-04 四川思达能环保科技有限公司 锂浸出液的浓缩方法
JP2020020016A (ja) * 2018-08-02 2020-02-06 住友金属鉱山株式会社 リチウムの精製方法
JP7115123B2 (ja) 2018-08-02 2022-08-09 住友金属鉱山株式会社 リチウムの精製方法
EP3885031A4 (fr) * 2018-12-26 2022-07-27 Toray Industries, Inc. Procédé de fabrication de sel de métal alcalin
KR102887009B1 (ko) 2018-12-26 2025-11-17 도레이 카부시키가이샤 알칼리 금속염의 제조 방법
JPWO2020158456A1 (ja) * 2019-01-30 2021-12-02 東洋紡株式会社 濃縮システムおよび濃縮方法
WO2020158456A1 (fr) * 2019-01-30 2020-08-06 東洋紡株式会社 Système de concentration et procédé de concentration
WO2021159144A1 (fr) * 2020-02-06 2021-08-12 Schlumberger Technology Corporation Extraction de lithium intégrée
US12157929B2 (en) 2020-02-06 2024-12-03 Schlumberger Technology Corporation Integrated lithium extraction
KR20220147157A (ko) * 2020-04-21 2022-11-02 도레이 카부시키가이샤 레어 메탈염의 회수 방법
KR102528926B1 (ko) * 2020-04-21 2023-05-09 도레이 카부시키가이샤 레어 메탈염의 회수 방법
WO2023196348A1 (fr) * 2022-04-04 2023-10-12 Energy Exploration Technologies, Inc. Systèmes et procédés destinés à la production de métal à partir de solutions de saumure
JPWO2025070624A1 (fr) * 2023-09-29 2025-04-03
WO2025070624A1 (fr) * 2023-09-29 2025-04-03 東レ株式会社 Procédé et dispositif de récupération d'ions de métal alcalin et d'ions hydroxyde

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