WO2013005694A1 - 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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WO2013005694A1
WO2013005694A1 PCT/JP2012/066798 JP2012066798W WO2013005694A1 WO 2013005694 A1 WO2013005694 A1 WO 2013005694A1 JP 2012066798 W JP2012066798 W JP 2012066798W WO 2013005694 A1 WO2013005694 A1 WO 2013005694A1
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water
alkali metal
nanofiltration membrane
unit
concentration
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PCT/JP2012/066798
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English (en)
Japanese (ja)
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寛生 高畠
谷口　雅英
佐々木　崇夫
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東レ株式会社
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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • 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
    • 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
    • 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 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 Documents 1 and 2 As measures to solve this, methods using adsorbents (Patent Documents 1 and 2) and the like have been proposed. However, the cost is difficult, and it has been established as a technique for stably recovering lithium at a low cost. Absent. 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 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 from raw water containing alkali metals such as lithium and potassium such as lake water, groundwater, and industrial wastewater.
  • the present invention relates to the following (1) to (7).
  • the nanofiltration membrane is used to permeate and separate the raw water containing alkali metal to obtain nanofiltration membrane permeated water and nanofiltration membrane concentrated water, and the nanofiltration membrane permeated water is permeated and separated using a concentration unit. To obtain concentrated unit concentrated water, and recover at least part of the alkali metal contained in the concentrated unit concentrated water.
  • the concentration unit comprises any one of a reverse osmosis membrane unit, a distillation unit, and a membrane distillation unit.
  • the concentration unit includes a mechanism that cools and recovers low-concentration water using raw water having a temperature lower than the temperature of the supply water supplied to the concentration unit. Alkali metal separation and recovery method.
  • a nanofiltration membrane unit that obtains nanofiltration membrane permeated water and nanofiltration membrane concentrated water by permeating and separating raw water containing alkali metal using a nanofiltration membrane, and permeating and separating the nanofiltration membrane permeated water.
  • An alkali metal separation and recovery apparatus comprising: a concentration unit for obtaining concentrated unit concentrated water; and a recovery unit for recovering at least a part of the alkali metal contained in the concentrated unit concentrated water.
  • the present invention makes it possible to efficiently recover alkali metals such as lithium and potassium from raw 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.
  • FIG. 2 is a schematic flow diagram showing an embodiment of the alkali metal separation and recovery method for refluxing the concentrated unit waste water to the supply water according to the present invention.
  • FIG. 3 is a schematic flow diagram showing one embodiment of an alkali metal separation and recovery method for refluxing concentrated unit waste water to pretreated water according to the present invention.
  • FIG. 4 is a schematic flow diagram showing one embodiment of the alkali metal separation and recovery method according to the present invention, in which the concentration unit is a heat utilization type concentration unit.
  • 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, then processed by a pretreatment unit 4 by a supply pump 3, and the pretreated supply water is a booster pump 5.
  • the nanofiltration membrane unit 6 Is sent to the nanofiltration membrane unit 6 to obtain nanofiltration membrane permeated water and nanofiltration membrane concentrated water 7 from which alkali metal is permeated and separated.
  • the permeated water of the nanofiltration membrane unit 6 is sent to the concentrating unit 9 by the booster pump 8 to obtain the concentrating unit waste water 10 in which the alkali metal has a low concentration and the concentrated unit concentrated water 11 in which the alkali metal is concentrated.
  • the concentrated unit concentrated water 11 is sent to the recovery unit 12 to recover the alkali metal 13 (embodiments (1) and (2)).
  • the size of the alkali metal on the supply water side is smaller than other alkaline earth metals, so that it is not blocked by the nanofiltration membrane.
  • the alkali metal concentration in the permeate does not exceed the alkali metal concentration in the raw water, so by concentrating the permeate of the nanofiltration membrane with a concentration unit, Alkali metal can be efficiently recovered in the post-processing recovery unit (effect of the 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 from the viewpoint of separation and recovery efficiency, the lithium ion concentration of the feed water after dilution is preferably in the range of 0.5 ppm to 10,000 ppm, more preferably 5 ppm to 5000 ppm.
  • An aqueous solution having a range of 50 ppm to 2000 ppm is preferably used as the raw water.
  • the purification inhibitor when a desired purified alkali metal salt such as lithium carbonate or potassium chloride is separated and recovered by post-treatment, the purification inhibitor may be an alkaline earth metal salt or sulfate that easily produces a hardly soluble salt, Examples of such organic substances include magnesium salts and / or sulfates.
  • the magnesium ion concentration in the alkali metal salt aqueous solution to be supplied water is 1000 times or less than the lithium ion concentration. The efficiency is preferably 500 times or less, more preferably 100 times or less, 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. Until then, it is preferable to perform the removal treatment by the nanofiltration membrane unit. 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.
  • 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 when 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 were permeated at an operating pressure of 0.5 MPa, respectively.
  • Is 90% or more, and a nanofiltration membrane having a difference between glucose removal rate and isopropyl alcohol removal rate of 30% or more is used, regardless of the total salt concentration, alkali metal salts, especially lithium salts and purification inhibitors Is particularly preferred since the separation of 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. In order to make the nanofiltration membrane units 6 different, it is easy to make the nanofiltration membranes different. In order to efficiently permeate the alkali metal and block other solutes in the present invention, 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. In particular, since 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 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 increases, but not a small amount of alkali metal ions permeate through the nanofiltration membrane.
  • the ratio of the concentration of polyvalent ions such as 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.
  • 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.
  • 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.
  • 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 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.
  • 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, among them, 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-C3 linear or cyclic saturated or unsaturated aliphatic group, H, OH, COOH, SO 3 H, COF, COCl, COBr, COI To be elected.
  • 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 pressure of the feed water of each stage in addition to making the nanofiltration membranes of the front stage and the rear stage different from each other, it is also preferable to increase the pressure of 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 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.
  • the reverse osmosis membrane method refers to a reverse osmosis membrane having an alkali metal removal rate of 95% or more.
  • the concentration unit 16 when using a concentration unit such as a distillation method or a membrane distillation method that uses thermal energy as a driving force for separation, as shown in FIG. 4, the concentration unit 16 at any point before entering the concentration unit 16 from raw water. It is also a preferred embodiment to take a method in which the supplied water is preheated by, for example, the heating unit 17 and the low-concentration water generated by concentration is recovered with cooling water.
  • the direct contact method which is one of the membrane distillation methods, is a method in which only water permeates from the high-temperature water to the cooling water through the membrane, and the high-temperature water is concentrated, which is very preferable for application of the present invention. .
  • the position of the heating unit 17 is not particularly limited as long as it is after the nanofiltration membrane unit 6 is removed from the raw water, but there is a pretreatment or the like before the supply to the concentration unit 16.
  • the performance may be affected if the pretreatment involves filtration or chemical reaction.
  • the temperature is high before the supply to the nanofiltration membrane unit, the water permeability and separation performance of the nanofiltration membrane may change significantly, and the concentrated water of the nanofiltration membrane will become high-temperature drainage. Because it leads to energy loss, design attention is required.
  • the heat generated by the pump is large, the temperature can be raised by the pump.
  • the purified alkali metal salt is recovered.
  • 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 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 residual liquid after the alkali metal is recovered by the recovery unit can be drained or can be refluxed to the supply water depending on the alkali metal content.
  • the nanofiltration membrane unit concentrated water has pressure energy, it is preferable to apply an energy recovery unit because it saves energy.
  • nanofiltration membrane unit concentrated water is generally drained because it contains a large amount of alkali metal production inhibitor, but the concentration of alkali metal ions to be recovered is less than the other components, but the concentration of raw water exceeds the concentration. Therefore, it can be reused as feed water after the concentration of the production inhibitor is reduced by ion exchange or adsorption.
  • 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.
  • turbidity treatment such as sand filtration, microfiltration membrane, ultrafiltration membrane
  • turbidity treatment such as sand filtration, microfiltration membrane, ultrafiltration membrane
  • a bactericidal agent 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 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 preferable.
  • 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 alkali metal concentration in the nanofiltration membrane concentrated water is reduced by reducing the alkali metal concentration in the raw water. And the loss of alkali metal can be reduced.
  • alkaline earth metals have a high rejection rate in the nanofiltration membrane unit, so the concentration gradually increases, and depending on the operating conditions, it becomes a scale and precipitates on the surface of the nanofiltration membrane, reducing the performance of the nanofiltration membrane. Since the nanofiltration membrane is damaged, it has an advantage that it is difficult to precipitate the scale, which is preferable.
  • Concentration unit wastewater is water that has already been pretreated and may not require the same pretreatment process. In this case, by returning the concentrated unit waste water to the pretreatment water, the burden on the pretreatment process can be reduced, and energy saving and cost reduction can be achieved.
  • the present invention relates to a device 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 concentrates, separates by adding dilution water to raw water containing alkali metals, Alkali metals can be efficiently separated and recovered from water containing various solutes that are difficult to recover.

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Abstract

La présente invention concerne un procédé de séparation et de récupération d'un métal alcalin, qui comprend : une étape pour obtenir de l'eau ayant subi une perméation à travers une membrane de nanofiltration et de l'eau concentrée par une membrane de nanofiltration, pour ce faire, de l'eau brute contenant un métal alcalin est soumise à une séparation par perméation à l'aide d'une membrane de nanofiltration; une étape pour obtenir de l'eau concentrée dans une unité de concentration, pour ce faire, l'eau ayant subi une perméation à travers une membrane de nanofiltration est soumise à une séparation par perméation à l'aide d'une unité de concentration; et une unité de récupération d'au moins une partie du métal alcalin contenu dans l'eau concentrée dans l'unité de concentration.
PCT/JP2012/066798 2011-07-04 2012-06-29 Procédé de séparation et de récupération d'un métal alcalin, et appareil de séparation et de récupération d'un métal alcalin WO2013005694A1 (fr)

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CN108392986A (zh) * 2018-05-11 2018-08-14 梁小朝 一种四甲基碳酸铵的提纯装置
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CN111573950A (zh) * 2020-05-29 2020-08-25 盛隆资源再生（无锡）有限公司 一种含有机溶剂废水的回收处理方法
CN112777616A (zh) * 2021-01-30 2021-05-11 四川思达能环保科技有限公司 氢氧化锂重溶液除杂工艺
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CN112777616A (zh) * 2021-01-30 2021-05-11 四川思达能环保科技有限公司 氢氧化锂重溶液除杂工艺

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