WO2012077610A1 - Procédé de séparation et de récupération de métal alcalin, et appareil de séparation et de récupération de métal alcalin - Google Patents

Procédé de séparation et de récupération de métal alcalin, et appareil de séparation et de récupération de métal alcalin Download PDF

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WO2012077610A1
WO2012077610A1 PCT/JP2011/077975 JP2011077975W WO2012077610A1 WO 2012077610 A1 WO2012077610 A1 WO 2012077610A1 JP 2011077975 W JP2011077975 W JP 2011077975W WO 2012077610 A1 WO2012077610 A1 WO 2012077610A1
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alkali metal
nanofiltration membrane
water
membrane unit
separation
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PCT/JP2011/077975
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English (en)
Japanese (ja)
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谷口　雅英
寛生 高畠
佐々木　崇夫
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東レ株式会社
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Priority to CN201180058613.5A priority Critical patent/CN103249471B/zh
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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
    • 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
    • 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
    • B01D61/0271—Nanofiltration comprising multiple nanofiltration steps
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2317/00—Membrane module arrangements within a plant or an apparatus
    • B01D2317/02—Elements in series
    • B01D2317/022—Reject series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2317/00—Membrane module arrangements within a plant or an apparatus
    • B01D2317/02—Elements in series
    • B01D2317/025—Permeate series
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/24—Treatment of water, waste water, or sewage by flotation
    • 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
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • 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
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • 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
    • C02F1/447—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by membrane distillation
    • 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
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C02F3/1236—Particular type of activated sludge installations
    • C02F3/1268—Membrane bioreactor systems
    • C02F3/1273—Submerged membrane bioreactors
    • 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
    • Y02W10/10—Biological treatment of water, waste water, or sewage
    • 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. More specifically, the present invention efficiently recovers alkali metals using a multi-stage nanofiltration membrane. It is related with the method and apparatus for doing.
  • 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 are contained in salt lake brine and ore, and it is advantageous to recover resources from salt lake brine in terms of production cost.
  • the composition is largely 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 Document 1-2 a method using an adsorbent
  • the cost is difficult, and it has been established as a technique for stably recovering lithium at a low cost.
  • 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.
  • electrodialysis and membrane filtration are being studied (Non-Patent Document 1), but they have not been put into practical use.
  • An object of the present invention is to provide a method and an apparatus for efficiently recovering alkali metals such as lithium and potassium from lake water, groundwater, industrial wastewater and the like.
  • the present invention relates to the following embodiments (1) to (15).
  • an alkali metal separation / recovery method wherein the nanofiltration membrane unit is configured in at least two stages, and the concentrated water of the preceding nanofiltration membrane unit is used as supply water for the latter nanofiltration membrane unit.
  • the ratio of the sulfate ion permeability to the alkali metal permeability in the first-stage nanofiltration membrane unit is smaller than the ratio of the sulfate ion permeability to the alkali metal permeability in the final-stage nanofiltration membrane unit.
  • the nanofiltration membrane in the first-stage nanofiltration membrane unit contains an aliphatic polyamide as a main component, and the nanofiltration membrane in the final-stage nanofiltration membrane unit has an aromatic polyamide as a main component.
  • the method further comprises a permeate concentration step of concentrating the permeate of at least one nanofiltration membrane unit, and after that step, the alkali metal is recovered by post-treatment.
  • At least the permeated water of the nanofiltration membrane unit at the final stage is subjected to a permeated water concentration step, and then the alkali metal is recovered by post-treatment after removing the purification inhibitor (7) or ( The alkali metal separation and recovery method according to 8).
  • An alkali metal separation and recovery device for separating permeated water containing alkali metal from raw water containing alkali metal using a nanofiltration membrane and recovering the alkali metal contained in the permeated water by post-treatment.
  • the apparatus includes at least two nanofiltration membrane units, and the concentrated water line of the preceding nanofiltration membrane unit is connected to the supply water line of the subsequent nanofiltration membrane unit. Recovery device.
  • the present invention makes it possible to efficiently recover alkali metals such as lithium and potassium from water in which various solutes coexist.
  • FIG. 1 is a schematic flowchart showing one embodiment of the alkali metal separation and recovery method according to the present invention (the above embodiments (1) to (5)).
  • FIG. 2 is a schematic flow diagram showing one embodiment of pressurizing the second-stage feed water of the nanofiltration membrane unit according to the present invention (the above embodiment (6)).
  • FIG. 3 is a schematic flowchart showing one embodiment of a method for separating and recovering alkali metal after concentrating the permeated water of the nanofiltration membrane according to the present invention (the above embodiments (7) and (8)). ).
  • FIG. 4 is a schematic flow diagram showing an embodiment of a method for separating and recovering alkali metal after removing the purification inhibitor after concentrating the final permeate of the nanofiltration membrane unit according to the present invention.
  • FIG. 5 is a schematic flow diagram showing one embodiment of adding an acid to the feed water of the nanofiltration membrane according to the present invention (the above embodiment (10)).
  • FIG. 6 is a schematic flow diagram showing an embodiment in which the purification inhibitor is removed from the final concentrated water of the nanofiltration membrane according to the present invention and then refluxed to the raw water containing the alkali metal (the above embodiment ( 11)).
  • FIG. 7 is a schematic flow diagram showing one embodiment of mixing diluted water with the feed water of the nanofiltration membrane according to the present invention (the above embodiment (12)).
  • FIG. 8 is a schematic flow diagram showing an embodiment in which the permeated water produced by concentrating the permeated water of the nanofiltration membrane according to the present invention is used for dilution of the nanofiltration membrane feed water (the above embodiment ( 13)).
  • FIG. 9 is a schematic flow diagram showing one embodiment of heating the feed water of the nanofiltration membrane according to the present invention (the above embodiment (14)).
  • the number of nanofiltration membrane units can be three or more, and the scope of the present invention is not limited to these embodiments.
  • 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 is temporarily stored in a raw water tank 2 and then processed by a pretreatment unit 3 by a raw water supply pump 4.
  • the concentrated water of the first-stage nanofiltration membrane unit 6 is sent to the second-stage nanofiltration membrane unit 7, the alkali metal is permeated and separated as in the first stage, and the final concentrated water 8 is discharged out of the system.
  • the nanofiltration membrane permeated water is sent to the recovery unit 9, and the alkali metal is recovered (the above embodiment (1)).
  • the alkali metal that is the subject of the present invention is preferably one containing at least lithium, and in salt lake brine etc. for carrying out the method of the present invention, among alkali metals such as sodium, potassium, rubidium, cesium and the like in addition to lithium.
  • At least one metal, alkaline earth metal such as magnesium, calcium, strontium, typical elements (aluminum, tin, lead, etc.), transition elements (iron, copper, cobalt, manganese, etc.), and one or more conjugates
  • a compound composed of a salt with a base for example, chloride ion, nitrate ion, sulfate ion, carbonate ion, acetate ion, etc.
  • a base for example, chloride ion, nitrate ion, sulfate ion, carbonate ion, acetate ion, etc.
  • the concentration of each of these components is not particularly limited, but the lithium ion concentration is preferably in the range of 0.5 ppm or more and 10,000 ppm or less, more preferably in the range of 5 ppm or more and 5000 ppm or less, and more preferably, from the viewpoint of the efficiency of separation and recovery.
  • the magnesium ion concentration in the alkali metal salt aqueous solution serving as raw water is preferably 1000 times or less as compared with the lithium ion concentration. More preferably, it is efficient when it is 500 times or less, and more preferably 100 times or less.
  • the magnesium ion concentration in the aqueous solution containing the alkali metal salt is 7 times or less than the lithium ion concentration in the aqueous solution. It is preferable to perform a removal treatment using a separation membrane. If this ratio exceeds 7 times, the recovery efficiency of the purified alkali metal salt is significantly reduced.
  • the weight of the purification inhibiting substance at this time is calculated based on the weight in terms of ions such as magnesium ions and sulfate ions.
  • the weight in terms of lithium ion and the weight of the purification inhibitor can be determined by quantifying various ion concentrations in an aqueous solution containing an alkali metal salt, for example, by ion chromatography.
  • the content of the purification inhibitor in the raw water is different depending on the composition and concentration of the purification inhibitor depending on the properties of the raw water.
  • salt lake brine contains magnesium ions and sulfate ions in the range of 100 ppm to 30,000 ppm.
  • the nanofiltration membrane referred to here is a membrane defined by IUPAC as “a pressure-driven membrane in which particles and polymers of a size smaller than 2 nm are blocked”, but is effective for application to the present invention.
  • the membrane has a charge on the membrane surface, and has improved ion separation efficiency by a combination of separation by pores (size separation) and electrostatic separation by charge on the membrane surface. It is preferable to apply a nanofiltration membrane that is capable of removing polymers by size separation while separating metal ions and other ions having different charge characteristics by charging.
  • the glucose removal rate is particularly good when permeating a 1000 ppm isopropyl alcohol aqueous solution of 25 ° C. and pH 6.5 and a 1000 ppm glucose aqueous solution of 25 ° C. and pH 6.5 at an operating pressure of 0.5 MPa.
  • a nanofiltration membrane that is 90% or more and the difference between the glucose removal rate and the isopropyl alcohol removal rate is 30% or more, alkali metal salts, especially lithium salts and purification inhibitors, are not affected by the total salt concentration. Separation is particularly preferred because it is achieved with very high efficiency.
  • the purified alkali metal salt can be separated and recovered by a crystallization operation induced by concentration of an aqueous solution, heating, cooling, or addition of a nucleating agent. It is preferred that the sulfate is removed. Therefore, the removal rate of magnesium sulfate is 90% or more 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, preferably 95%.
  • % Or more more preferably 97% or more, and using a nanofiltration membrane having a lithium chloride removal rate of 70% or less, preferably 50% or less, more preferably 30% or less, depending on the total salt concentration. Separation of lithium salt and purification inhibitor is achieved with extremely high efficiency. Further, it is preferable to recover the purified alkali metal salt by concentration of the alkali metal salt after the step of the separation membrane of the present invention.
  • the temperature dependency of the solubility is used, or recovery is performed by a known method of recovering potassium chloride by 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 per 100 mL of water), whereas the solubility of lithium carbonate is only 1.33 g per 100 mL of water at 25 ° C, and the solubility is higher at higher temperatures. It uses the decline.
  • the nanofiltration membrane unit is composed of a modularized nanofiltration membrane, for example, one or a plurality of spiral nanofiltration membrane elements connected in a container and connected in series or in parallel. Refers to things.
  • the low-concentration water 11 after the alkali metal is recovered by the recovery unit 9 can be drained or returned to the raw water depending on the alkali metal content. Moreover, since the final concentrated water 8 of the nanofiltration membrane has pressure energy, it is preferable to apply an energy recovery unit because it saves energy.
  • the pretreatment unit 3 is not particularly limited, and can be appropriately selected depending on the raw aqueous state, such as removal of turbid components and sterilization.
  • 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.
  • certain fungicides may not have chemical durability. In that case, add as much upstream as possible to the feed water, and further, near the feed water inlet side of the semipermeable membrane unit. It is preferable to disable the disinfectant. For example, in the case of 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.
  • Supply water suitable for passing through the latter semipermeable membrane unit can be obtained.
  • 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 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-based 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, may be applied.
  • MLR membrane-based activated sludge method
  • the organic matter when the supply water contains a lot of soluble organic matter, the organic matter can be decomposed by adding chlorine gas or sodium hypochlorite. Removal is possible.
  • 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 nanofiltration membrane unit is different from the first stage to the last stage (the above embodiment (2)).
  • the molecular weight and charge characteristics of the nanofiltration membrane are optimized according to the water supply quality gradually changing at each stage of the nanofiltration membrane. Therefore, it is possible to increase the separation efficiency.
  • the permeation amount decreases due to the pressure loss due to flow resistance and the decrease in effective filtration pressure due to the increase in feed water concentration from the previous stage to the latter stage, the pure water permeability performance of the latter nanofiltration membrane is larger than the previous stage. Is preferable (the above embodiment (3)).
  • the pure water feeding performance here can be measured by allowing pure water applied with pressure (usually 0.3 to 0.5 MPa) to pass through the nanofiltration membrane, and is measured at a standard temperature (usually 25 ° C.). It is a value obtained by measuring the membrane area and the amount of water permeated per unit time.
  • the concentration of the feed water increases as the latter stage, but not a small amount of alkali metal ions permeate the nanofiltration membrane, so that the latter feed water contains other solutes (alkaline earth metals and sulfate ions) with respect to the alkali metal concentration.
  • the ratio of such multivalent ions) is increased, and the alkali metal content of the permeated water is also decreased from the previous stage. Therefore, it is preferable to use a nanofiltration membrane with higher separation performance as the latter stage.
  • 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.
  • Such a nanofiltration membrane can be realized by increasing the pore diameter (fractionated molecular weight) while increasing the surface charge of the latter nanofiltration membrane as compared with the previous stage.
  • a method for increasing the surface charge for example, as shown in the literature (Photoinduced grafting of ultrafiltration membranes: comparison of poly (ether sulfone) and poly (sulfone), B. Kaeselev et al., 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.
  • the nanofiltration membrane in the preceding nanofiltration membrane unit that requires high separation efficiency is mainly composed of aliphatic polyamide (that is, the number of amide bonds of aliphatic polyamide is larger than that of aromatic polyamide).
  • the nanofiltration membrane in the latter nanofiltration membrane unit that requires high permeation performance preferably contains aromatic polyamide as a main component (the above embodiment (5)).
  • piperazine-based amines and derivatives thereof represented by the formula [I] are preferable, and piperazine, 2,5-dimethylpiperazine, 2-methylpiperazine, 2,6-dimethylpiperazine, 2,3,5- Examples include trimethylpiperazine, 2,5-diethylpiperazine, 2,3,5-triethylpiperazine, 2-n-propylpiperazine, 2,5-di-n-butylpiperazine and the like. Among them, it is particularly preferable to use piperazine or 2,5-dimethylpiperazine, which can obtain a nanofiltration membrane having higher solute removal performance and water permeation performance with a wide composition ratio.
  • R1 to R8 are selected from H, OH, COOH, SO 3 H, NH 2 or C1 to C4 linear or cyclic saturated or unsaturated aliphatic groups.
  • 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, and in particular, having a dense and rigid structure, can provide a membrane having excellent blocking performance and water permeability performance, and further excellent durability and particularly heat resistance. It is also preferable that an easy m-aromatic diamine or p-aromatic diamine is contained.
  • 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. This makes it possible to obtain the liquid separation membrane of the present invention that satisfies the desired water permeation 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.
  • there is no particular limitation as long as it forms a layer For example, 1,3,5-cyclohexanetricarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3 -A mixture of benzenedicarboxylic acid and acid halide of 1,4-benzenedicarboxylic acid.
  • dicarboxylic acids and tricarboxylic acids represented by the formulas [II] and [III] are preferable, particularly good for economics, because the film-forming property is good, the entire solute blocking performance is uniform, and there are few defects and variations.
  • trimesic acid chloride which is an acid halide of 1,3,5-benzenetricarboxylic acid, is preferable.
  • R is selected from H or a C1-C3 hydrocarbon.
  • R is selected from 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.
  • Trimellitic anhydride halides and derivatives thereof represented by the following general formula [IV] are preferably used.
  • X1 and X2 are any of C1 to C3 linear or cyclic saturated, unsaturated aliphatic group, H, OH, COOH, SO 3 H, COF, COCl, COBr, COI. To be elected. Alternatively, an acid anhydride may be formed between X1 and X2.
  • X3 is selected from any of C1 to C3 linear or cyclic saturated or unsaturated aliphatic groups, H, OH, COOH, SO 3 H, COF, COCl, COBr, and COI.
  • Y is selected from H, F, Cl, Br, I or C1-C3 hydrocarbons.
  • the permeate concentration usually does not become higher than that of the raw water, so that the alkali metal can be efficiently recovered in the post-treatment. It is also a preferred embodiment to add a step of concentrating the permeated water of the nanofiltration membrane (permeated water concentrating step) (the above embodiment (7)).
  • the permeated water concentration step can include various methods such as distillation, membrane separation, adsorption / desorption, and ion exchange, but the alkali metal is non-volatile and has a very small size.
  • the reverse osmosis membrane having high blocking performance refers to a reverse osmosis membrane having an alkali metal removal rate of 95% or more.
  • FIG. 3 illustrates a case where a reverse osmosis membrane is used as the concentration unit 14.
  • components such as alkaline earth metals are concentrated, and as a result, the concentration of the alkaline earth metal contained in the permeated water becomes higher.
  • a method of removing the alkaline earth metal by the earth metal removal unit 17 and then recovering the alkali metal in the post-treatment 9 is also a preferred embodiment (the above embodiment (9)).
  • permeated water 15 is obtained as fresh water, which can be discharged out of the system, or can be reused as process water and the like.
  • the alkaline earth metal concentration in the concentrated water gradually increases, and depending on the operating conditions, it becomes a scale and precipitates on the surface of the nanofiltration membrane. If such a danger is expected, the pH is lowered by adding acid to the raw water or the concentrated water in the previous stage to prevent scale precipitation. It is preferable (the above embodiment (10)). Of course, it is possible to add a scale inhibitor. However, since there are risks such as environmental impact and possible leakage of the scale inhibitor, caution is required in the addition.
  • FIG. 5 shows an embodiment in which the acid 19 is added to the feed water in the latter stage (concentrated water in the former stage).
  • the concentrated water 8 of the nanofiltration membrane contains an alkaline earth metal or the like at a high concentration, but generally contains alkali metal ions at a concentration higher than the raw water concentration although the ratio is smaller than other components. 6, after the alkaline earth metal is removed by the alkali metal removal unit 17, the recovery rate of the alkali metal in the raw water can be increased by refluxing the raw water (the above embodiment (11)).
  • the dilution water 20 may be water having a lower concentration than the raw water, such as natural water such as river water, ground water, rainwater, or tap water, but the concentration units 14 and 14 'as shown in FIGS.
  • the permeated water 15 it is very preferable because the water can be efficiently recovered and reused (the embodiment (13); see FIG. 8).
  • the raw water and the nanofiltration membrane supply water are heated in advance. It is preferable as a means for improving efficiency. (Embodiment (14) above).
  • the heat source is not particularly limited, but it is efficient to heat the system to which the present invention is applied using waste heat such as an evaporation method or a membrane distillation method, or heat generated by a pressure pump.
  • 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 more particularly to an alkali metal efficiently using a multi-stage nanofiltration membrane.
  • alkali metals such as lithium and potassium
  • 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 more particularly to an alkali metal efficiently using a multi-stage nanofiltration membrane.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé de séparation et de récupération de métal alcalin qui comprend la séparation d'un perméat contenant un métal alcalin d'eau brute contenant des métaux alcalins en utilisant une membrane de nanofiltration et la récupération du métal alcalin contenu dans le perméat en utilisant un post-traitement. Le procédé est caractérisé en ce que l'unité de membrane de nanofiltration est conçue en au moins deux étages et l'eau concentrée de l'unité de membrane de nanofiltration précédente est utilisée comme eau alimentée dans l'unité de membrane de nanofiltration suivante.
PCT/JP2011/077975 2010-12-06 2011-12-02 Procédé de séparation et de récupération de métal alcalin, et appareil de séparation et de récupération de métal alcalin WO2012077610A1 (fr)

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CN105925799A (zh) * 2016-05-26 2016-09-07 四川思达能环保科技有限公司 一种湿法冶金膜浓缩工艺
EP3436411A4 (fr) * 2016-03-31 2019-09-18 Technion Research & Development Foundation Limited Procédé de séparation d'ions de calcium et de magnésium d'eau salée, permettant d'améliorer la qualité d'eaux douces et dessalées
EP3641918A4 (fr) * 2017-07-21 2020-07-01 Larry Lien Récupération de lithium à partir d'une solution acide
EP3700866A4 (fr) * 2017-10-26 2021-05-19 International Battery Metals, Ltd. Appareil d'extraction modulaire
WO2021215484A1 (fr) * 2020-04-21 2021-10-28 東レ株式会社 Procédé de récupération de sel de métal rare
WO2023058548A1 (fr) * 2021-10-05 2023-04-13 東レ株式会社 Procédé de récupération d'ions métalliques monovalents
WO2024117236A1 (fr) * 2022-11-30 2024-06-06 東レ株式会社 Procédé de récupération de sel de métal alcalin et appareil de récupération de sel de métal alcalin

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WO2017039724A1 (fr) * 2015-08-28 2017-03-09 Albemarle Corporation Procédés de récupération de valeurs de lithium à partir de saumures contenant du lithium
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JP7133429B2 (ja) * 2018-10-19 2022-09-08 日東電工株式会社 水処理システム及び水処理方法
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US10174404B2 (en) 2012-08-23 2019-01-08 Chemetics Inc. Hydrometallurgical process using multi-stage nanofiltration
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EP3436411A4 (fr) * 2016-03-31 2019-09-18 Technion Research & Development Foundation Limited Procédé de séparation d'ions de calcium et de magnésium d'eau salée, permettant d'améliorer la qualité d'eaux douces et dessalées
US11279643B2 (en) 2016-03-31 2022-03-22 Technion Research & Development Foundation Limited Method for separation of magnesium and calcium ions from saline water, for improving the quality of soft and desalinated waters
CN105925799A (zh) * 2016-05-26 2016-09-07 四川思达能环保科技有限公司 一种湿法冶金膜浓缩工艺
EP3926062A1 (fr) * 2017-07-21 2021-12-22 Larry Lien Récupération de graphite à partir d'une solution d'acide
EP3641918A4 (fr) * 2017-07-21 2020-07-01 Larry Lien Récupération de lithium à partir d'une solution acide
JP2020527196A (ja) * 2017-07-21 2020-09-03 ラリー リーン 酸溶液からのリチウムの回収方法
RU2739764C1 (ru) * 2017-07-21 2020-12-28 Ларри ЛИН Извлечение лития из кислого раствора
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EP3700866A4 (fr) * 2017-10-26 2021-05-19 International Battery Metals, Ltd. Appareil d'extraction modulaire
US11498031B2 (en) 2017-10-26 2022-11-15 International Battery Metals, Ltd. Mobile extraction array with brine constituent separation, purification, and concentration
WO2021215484A1 (fr) * 2020-04-21 2021-10-28 東レ株式会社 Procédé de récupération de sel de métal rare
JP7095807B2 (ja) 2020-04-21 2022-07-05 東レ株式会社 レアメタル塩の回収方法
CN115443342A (zh) * 2020-04-21 2022-12-06 东丽株式会社 稀有金属盐的回收方法
JPWO2021215484A1 (fr) * 2020-04-21 2021-10-28
US11905180B2 (en) 2020-04-21 2024-02-20 Toray Industries, Inc. Method for recovering rare metal salt
CN115443342B (zh) * 2020-04-21 2023-07-18 东丽株式会社 稀有金属盐的回收方法
WO2023058548A1 (fr) * 2021-10-05 2023-04-13 東レ株式会社 Procédé de récupération d'ions métalliques monovalents
JP7375953B2 (ja) 2021-10-05 2023-11-08 東レ株式会社 一価金属イオンの回収方法
JPWO2023058548A1 (fr) * 2021-10-05 2023-04-13
WO2024117236A1 (fr) * 2022-11-30 2024-06-06 東レ株式会社 Procédé de récupération de sel de métal alcalin et appareil de récupération de sel de métal alcalin

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