WO2020050617A1 - Membrane d'ultrafiltration de polyéthylène téréphtalate et son procédé de production - Google Patents

Membrane d'ultrafiltration de polyéthylène téréphtalate et son procédé de production Download PDF

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WO2020050617A1
WO2020050617A1 PCT/KR2019/011389 KR2019011389W WO2020050617A1 WO 2020050617 A1 WO2020050617 A1 WO 2020050617A1 KR 2019011389 W KR2019011389 W KR 2019011389W WO 2020050617 A1 WO2020050617 A1 WO 2020050617A1
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polyethylene terephthalate
ultrafiltration membrane
polymer solution
membrane
solvent
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PCT/KR2019/011389
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English (en)
Korean (ko)
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임재원
홍성표
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도레이첨단소재 주식회사
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    • 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
    • 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
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • 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
    • B01D61/14—Ultrafiltration; Microfiltration
    • 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
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B01D69/1071—Woven, non-woven or net mesh
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1213—Laminated layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/48—Polyesters
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/08—Specific temperatures applied
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/12—Specific ratios of components used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/219—Specific solvent system
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/219—Specific solvent system
    • B01D2323/22—Specific non-solvents or non-solvent system
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/025—Finger pores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/0283—Pore size
    • B01D2325/02833—Pore size more than 10 and up to 100 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/20—Specific permeability or cut-off range
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/34—Molecular weight or degree of polymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes

Definitions

  • the present invention relates to a polyethylene terephthalate ultrafiltration membrane and a method for manufacturing the same, and more specifically, the membrane material itself exhibits hydrophilicity, thus having excellent stain resistance to hydrophobic organic materials, and having mechanical structure while having a favorable pore structure for water permeation. And a polyethylene terephthalate ultrafiltration membrane having excellent water permeability and a method for manufacturing the same.
  • the conventional ultrafiltration membrane for water treatment used a method of incorporating a hydrophilic additive into a polymer solution when preparing a separator, or surface modification of the prepared separator or coating the surface of the separator with a hydrophilic material.
  • the hydrophilic additive has a high affinity with water, so it can be dissolved in water.
  • the hydrophilic additive dissolves and disappears in water during the operation of the ultrafiltration membrane, thereby improving the water permeability or anti-fouling effect induced by the use of the additive.
  • the separation membrane is contaminated by adsorption of organic substances, and thus, the permeation performance of the membrane is remarkably reduced, which may shorten the life of the separation membrane.
  • the present invention has been devised in view of the above points, and the membrane material itself exhibits more hydrophilicity, thus having excellent stain resistance to hydrophobic organic materials, and having excellent pore structure with excellent water permeability, and excellent mechanical strength and water permeability. It is an object to provide a polyethylene terephthalate ultrafiltration membrane and a method for manufacturing the same.
  • the present invention has another object to provide a reverse osmosis membrane comprising the polyethylene terephthalate ultrafiltration membrane according to the invention.
  • the present invention comprises the steps of (1) mixing a polymer solution composition containing polyethylene terephthalate and a solvent to prepare a polymer solution having a predetermined temperature, and (2) treating the polymer solution on a substrate. It provides a method for producing a polyethylene terephthalate ultrafiltration membrane comprising the step of induction and the step (3) of the polymer solution treated on the substrate to precipitate in a non-solvent set to 35 ⁇ 100 °C lower than the temperature of the polymer solution.
  • the solvent is dimethylacetamide (Dimethylacetamide), N-methyl-2-pyrrolidone (N-Methyl-2-pyrrolidone), N-octyl-pyrrolidone (N-octyl pyrrolidone) ), N-phenyl-pyrrolidone (N-methyl pyrrolidone), Dimethylformamide, Dimethyl sulfoxide, Trifluoroacetic acid, 1,1,2,2-tetrachloro Ethylene (1,1,2,2-Tetrachloroethylene), m-cresol, 2-chlorophenol, butyrolactone, ⁇ -butyrolactone, Diglycolamine (diglycolamine), tetrahydrofuran (Tetrahydrofuran), methyl ethyl ketone (Methyl ethyl ketone), sulfolane (sulfolane), and derivatives thereof.
  • Dimethylacetamide Dimethylacetamide
  • the polyethylene terephthalate and the solvent may be mixed in a weight ratio of 1: 9 to 4: 6.
  • the temperature of the polymer solution may be 60 ⁇ 100 °C.
  • the temperature of the non-solvent may be set to be 35 to 75 ° C lower than the temperature of the polymer solution.
  • the non-solvent may include at least one selected from water, alcohols and glycols.
  • the polymer solution composition further includes any one selected from polyethylene glycol, polyvinylpyrrolidone, silica (SiO 2 ), and titanium dioxide. can do.
  • the present invention has a pore structure including a first region having a finger-shaped pore structure formed on an upper portion based on a cross-section of a membrane and a large pore formed below the first region and communicating with the finger-shaped pore structure.
  • a polyethylene terephthalate ultrafiltration membrane having a second region and having an average pore size of 20 to 55 nm on the upper surface of the first region is provided.
  • the thickness of the ultrafiltration membrane may be 120 ⁇ 200 ⁇ m.
  • the first region and the second region may be included in a thickness ratio of 1: 0.5 to 1: 2.
  • the ultrafiltration membrane has the following conditions (a) and (25) for pure water at a temperature of 25 ° C. and a pressure of 1 kgf / cm 2 containing 1,000 ppm of polyethylene oxide having a weight average molecular weight of 100,000. b) can be satisfied.
  • the present invention provides a reverse osmosis membrane comprising a polyethylene terephthalate ultrafiltration membrane and a hydrophilic selective layer formed on the polyethylene terephthalate ultrafiltration membrane according to the present invention.
  • the term "removal rate” refers to the concentration of the high molecular weight substance contained in the filtered water compared to the concentration of the high molecular weight substance contained in the raw water when the raw water containing the high molecular weight substance is filtered through a separator. It is expressed as a percentage.
  • the high molecular weight material may be, for example, polyethylene oxide (PEO), but is not limited thereto.
  • the polyethylene terephthalate ultrafiltration membrane according to the present invention exhibits more hydrophilicity as the membrane material itself, and thus has excellent fouling resistance to hydrophobic organic materials, and has excellent pore structure for permeation of water, and at the same time expresses excellent water permeability and extends the life of the membrane. Increasing the membrane replacement cycle and reducing membrane cleaning costs.
  • 1A is a cross-sectional SEM image of a polyethylene terephthalate ultrafiltration membrane according to an embodiment of the present invention.
  • 1B is an SEM image of a top surface of a first region of a polyethylene terephthalate ultrafiltration membrane according to an embodiment of the present invention.
  • Figure 2a is a cross-sectional SEM image of the polyethylene terephthalate ultrafiltration membrane of Comparative Example 1.
  • 2B is an SEM image of the top surface of the first region of the polyethylene terephthalate ultrafiltration membrane of Comparative Example 1.
  • hydrophobic polymers such as polysulfone (PSf) and polyisulfone (PES), but these hydrophobic polymers have a low affinity with water and thus water permeability is significantly lower when manufactured as a separation membrane.
  • hydrophobic organic materials which occupy most of the suspended matter in the water, are easily adsorbed on the surface of the separator to cause membrane contamination and consequently to degrade the permeation performance of the membrane.
  • the ultrafiltration membrane according to the present invention can increase or decrease the water permeability of the separation membrane using polyethylene terephthalate, which is a more hydrophilic polymer, while preventing or minimizing membrane contamination by hydrophobic organic materials.
  • a pore structure in which water is easily permeated is formed by a temperature difference between a polymer solution containing polyethylene terephthalate and a non-solvent during membrane production, thereby further improving the water permeability of the separator.
  • a polymer solution composition containing polyethylene terephthalate (PET) and a solvent is mixed to prepare a polymer solution having a predetermined temperature.
  • PET polyethylene terephthalate
  • the polyethylene terephthalate may be amorphous, and accordingly, the polyethylene terephthalate may be dissolved with a conventional solvent used to dissolve polymers in the art.
  • the solvent contained in the polymer solution may be used without limitation as long as it is a solvent capable of dissolving polyethylene terephthalate, but dimethylacetamide, N-methyl-2-pyrrolidone, N-octyl pyrrolidone, N-phenyl pyrrolidone, dimethylformamide, dimethyl sulfoxide, trifluoroacetic acid ), 1,1,2,2-tetrachloroethylene (1,1,2,2-Tetrachloroethylene), m-cresol, 2-chlorophenol, butyrolactone , ⁇ -butyrolactone, ⁇ -butyrolactone, diglycolamine, tetrahydrofuran, methyl ethyl ketone, sulfolane and derivatives thereof, More preferably, it may include dimethylformamide.
  • the polyethylene terephthalate and the solvent may be mixed in a weight ratio of 1: 9 to 4: 6, and if the weight ratio is less than 1: 9, the content of the polyethylene terephthalate is low to form a desired thickness during membrane formation. It may be difficult or unintended pores may be generated on the surface of the separator, and thus, membrane formation in a flat form may be difficult, and when it exceeds 4: 6, the polyethylene terephthalate content is excessively high to form a pore structure of a desired form in the manufacture of the separator. It may be difficult or the viscosity of the polymer solution may be excessively increased, making it difficult to prepare a separator having a desired thickness.
  • the polymer solution may be prepared by mixing the polymer solution composition at 60 to 100 ° C, and the prepared polymer solution may be the same as the temperature set when mixing the polymer solution composition. If the polymer solution composition is mixed at less than 60 ° C., the polymer solution may solidify, making it difficult to form a separator. When mixing at a temperature exceeding 100 ° C., the viscosity of the polymer solution is excessively low, making it difficult to form a separator. You can.
  • step (2) the polymer solution is treated on a substrate.
  • the method of treating the polymer solution on the substrate can be used without limitation as long as it is a conventional method of treating a polymer solution used in forming a polymer separation membrane for water treatment in the art, for example dipping, spraying, drop casting. (drop casting), self-assembly, spin coating, doctor blade, bar coating, slot die coating, microgravure coating, coma coating ( coma coating), printing (printing), casting (casting method) any one method selected, preferably may be a casting method.
  • the substrate may be used without limitation as long as it is a material commonly used in the art that can process a polymer solution, and for example, the substrate may be a glass substrate.
  • the polymer solution is processed on a glass substrate and then described later.
  • the ultrafiltration membrane can be used by separating the ultrafiltration membrane attached to the glass substrate.
  • the substrate may be a porous support, in which case the substrate serves as a support member of the ultrafiltration membrane without separate separation after manufacturing the polyethylene terephthalate ultrafiltration membrane.
  • the porous support is not particularly limited as long as it usually serves as a support for the separation membrane for water treatment, but may be preferably a fabric.
  • the fabric refers to a fabric, a knitted fabric, or a non-woven fabric, and the fabric has a directionality as it is woven with warp and weft, and a knitted fabric may have a specific directionality depending on the knitting method, but in a broad sense, in either direction Can have a directionality of
  • the nonwoven fabric has no vertical and horizontal directionality, unlike the fabric or knitted fabric.
  • the fabric is a fabric
  • physical properties such as porosity, pore size, strength, and permeability of a desired porous support can be controlled by adjusting the type of fibers forming the warp yarns, the fineness, the density of the warp yarns, and the tissues of the fabric.
  • the fabric when the fabric is knitted, it is possible to control the properties of porosity, pore size, strength, permeability, etc. of the desired porous support by controlling the type, fineness, tissue, gauge, cut, etc. of fibers included in the knitted fabric. .
  • the type, fineness, fiber length, basis weight, density, etc. of fibers included in the non-woven fabric can be adjusted to control physical properties such as porosity, pore size, strength, and permeability of the desired porous support. .
  • the material of the porous support can usually serve as a porous support for the separation membrane for water treatment, and can be used without limitation as long as it is used for the porous support of the separation membrane for water treatment.
  • synthetic fibers selected from the group consisting of polyester, polypropylene, nylon, and polyethylene or natural fibers including cellulose may be used.
  • the physical properties of the membrane may be adjusted according to the porosity and hydrophilicity of the porous support.
  • the porous support may have an air permeability of 2 cc / cm 2 ⁇ sec or more, preferably an air permeability of 2 to 20 cc / cm 2 ⁇ sec, and an average pore size of the porous support is 1 It may be from 600 to 600 ⁇ m, preferably 5 to 300 ⁇ m. When the air permeability and the pore size of the average pore are satisfied, smooth inflow of water and water permeability can be improved.
  • the thickness of the porous support may be 20 ⁇ 150 ⁇ m, if less than 20 ⁇ m, the strength of the entire film may be lowered, if it exceeds 150 ⁇ m, it may cause the flow rate decreases.
  • the polymer solution composition may further include an additive for helping to form pores in the membrane or improving the hydrophilicity of the membrane in the induction phase transition step (3) described below, wherein the additive does not react with polyethylene terephthalate, and the polymer It is not particularly limited as long as it is well mixed with the solvent contained in the solution composition, but is preferably selected from polyethylene glycol, polyvinylpyrrolidone, silica (SiO 2 ), and titanium dioxide. It can be either.
  • the additive may be included in 0.01 to 3% by weight based on the weight of the polymer solution composition.
  • step (3) an induction phase transfer step is performed in which the polymer solution treated on the substrate is precipitated in a non-solvent at a predetermined temperature.
  • the non-solvent may be in phase with the solvent contained in the polymer solution composition to form pores in the polyethylene terephthalate ultrafiltration membrane, and the non-solvent may include at least one selected from water, alcohols, and glycols.
  • the pore structure in the polyethylene terephthalate ultrafiltration membrane prepared by the temperature difference between the non-solvent and the polymer solution composition, and the non-solvent to form a pore structure in which water permeation in the polyethylene terephthalate ultrafiltration membrane is advantageous.
  • the temperature of the polymer solution may be set to be 35 to 100 ° C lower than the temperature of the polymer solution. If the temperature difference between the non-solvent and the polymer solution is less than 35 ° C., the rate of pore formation is lowered and the pore size of the produced separator becomes smaller than the desired level, and the permeate flow rate of the separator may decrease, exceeding 100 ° C. In this case, it may be difficult to achieve the object of the present invention, such as a decrease in the removal rate of the separation membrane by increasing the pore formation rate excessively, so that the size of the pores of the separation membrane produced is larger than a desired level.
  • the temperature of the non-solvent may be set to be 35 to 75 ° C lower than the temperature of the polymer solution, and thus the pore size of the separator to be prepared is more easily formed to a desired level, and the permeate flow rate of the separator and And / or the removal rate can be further improved.
  • the temperature of the non-solvent may be set to be 35 to 60 ° C. lower than the temperature of the polymer solution, and thus the separation membrane produced may exhibit a removal rate of 90% or more and have an excellent permeation flow rate.
  • the temperature of the non-solvent may be 0 to 70 ° C, more preferably 5 to 30 ° C. If the temperature of the non-solvent is less than 0 ° C, it may be difficult for the non-solvent to solidify to perform a phase transition, and if it exceeds 70 ° C, the cross-sectional structure of the separator to be produced changes to a sponge structure and the permeate flow rate decreases or the separator It may shrink or deform by heat.
  • the thickness of the polyethylene terephthalate ultrafiltration membrane prepared according to the method of the present invention may be 120 to 200 ⁇ m, and if the thickness is less than 120 ⁇ m, the pressure resistance and / or contamination resistance of the membrane may be reduced and exceed 200 ⁇ m. In this case, the water permeability of the membrane may be lowered.
  • the polyethylene terephthalate ultrafiltration membrane has pores including a first region having a finger-shaped pore structure formed on an upper portion based on a cross-section of the membrane, and a large pore formed below the first region and communicating with the finger-type pore structure. It includes a second region having a structure.
  • the water permeability and mechanical strength of the membrane may be determined according to the thickness ratio of the first region and the second region, and preferably, the first region and the second region are polyethylene terephthalate at a thickness ratio of 1: 0.5 to 1: 2. It can be included in the ultrafiltration membrane. If the thickness ratio is less than 1: 0.5, the water permeability of the membrane may be lowered, and when it exceeds 1: 2, the mechanical strength of the membrane may be lowered, resulting in a decrease in pressure resistance and / or contamination resistance of the membrane.
  • pores having a predetermined average pore size are formed on the upper surface of the first region, and the average pore size of the upper surface of the first region is 20 to 55 nm, preferably Preferably, it may be 20 to 45 nm, more preferably 20 to 33 nm, and if the average pore size of the upper surface of the first region is less than 20 nm, the permeate flow rate of the separation membrane may be reduced and exceed 55 nm. If it does, it may be difficult to achieve the object of the present invention, such as the removal rate of the separation membrane is lowered.
  • the ultrafiltration membrane may exhibit a removal rate of 80% or more, and at the same time, an excellent permeate flow rate, and the average pore size of the upper surface of the first region 20 In the case of ⁇ 33 nm, the ultrafiltration membrane may exhibit a removal rate of 90% or more, and at the same time, have an excellent permeate flow rate.
  • the ultrafiltration membrane according to an embodiment of the present invention may satisfy the following conditions (a) and (b) for pure water at a temperature of 25 ° C and a pressure of 1 kgf / cm 2 , and an ultrafiltration membrane composed of a conventional hydrophobic polymer material It is possible to express more remarkably excellent water permeability.
  • the polyethylene terephthalate ultrafiltration membrane according to the present invention can be used as a polymer support layer of a reverse osmosis membrane.
  • the reverse osmosis membrane of the present invention includes a polyethylene terephthalate ultrafiltration membrane and a hydrophilic selective layer formed on the polyethylene terephthalate ultrafiltration membrane according to the present invention.
  • the reverse osmosis membrane may further include a porous support under the polyethylene terephthalate ultrafiltration membrane.
  • the hydrophilic selective layer may be used without limitation as long as it can be used as a selective layer of a reverse osmosis membrane in the art, but is preferably a polyamide-based polymer compound, a polypiperazine-based polymer compound, a polyphenylene diamine-based polymer compound, It may include at least one selected from polychlorophenylene diamine-based polymer compounds and polybenzidine-based polymer compounds, and more preferably polyamide-based polymer compounds.
  • the method for forming the hydrophilic selective layer may be different depending on the type of material included in the selected hydrophilic selective layer, but the method may be based on a conventional method for forming a selective layer according to the type of material.
  • a method of forming a hydrophilic selective layer made of a polyamide-based polymer compound among materials that may be included in the hydrophilic selective layer will be described below.
  • the polyethylene terephthalate ultrafiltration membrane is immersed in an aqueous solution containing a polyfunctional amine, and then contacted with an organic solution containing a polyfunctional acid halide compound for hydrophilicity.
  • a selective layer can be formed.
  • the polyfunctional amine is a material having 2 to 3 amine functional groups per monomer, and may be a primary amine or a polyamine containing a secondary amine.
  • aromatic primary diamine is used as metaphenylenediamine, paraphenylenediamine, orthophenyldiamine, and substituents
  • cycloaliphatic primary diamine such as aliphatic primary diamine and cyclohexenediamine is another example.
  • Cycloaliphatic secondary amines such as piperazine, aromatic secondary amines, and the like.
  • metaphenylenediamine among the multifunctional amines wherein the concentration is preferably an aqueous solution form containing 0.5 to 10% by weight of metaphenylenediamine, and more preferably metaphenylenediamine 1 To 4% by weight, more preferably 1.5 to 2.5% by weight may be included, through which there is an advantage that can express an improved permeate flow rate.
  • the polyfunctional amine-containing aqueous solution may be immersed on the polymer support layer for 0.1 to 10 minutes, more preferably 0.5 to 1 minute.
  • a substance that reacts with the polyfunctional amine used in forming the hydrophilic selective layer is a polyfunctional acid halogen compound, preferably a polyfunctional acyl halide, more preferably trimethoyl chloride, isophthaloyl chloride, 5-methoxy At least one selected from -1,3-isophthaloyl chloride and terephthaloyl chloride can be used.
  • a polyfunctional acid halogen compound preferably a polyfunctional acyl halide, more preferably trimethoyl chloride, isophthaloyl chloride, 5-methoxy At least one selected from -1,3-isophthaloyl chloride and terephthaloyl chloride can be used.
  • the polyfunctional acyl halide can be dissolved in an aliphatic hydrocarbon solvent at 0.01 to 2% by weight, wherein the aliphatic hydrocarbon solvent is a mixture of n-alkanes having 5 to 12 carbon atoms and structural isomers of saturated or unsaturated hydrocarbons having 8 carbon atoms, or Cyclic hydrocarbons having 5 to 7 carbon atoms can be used.
  • the polyfunctional acyl halide-containing solution may be dissolved in an aliphatic hydrocarbon solvent at 0.01 to 2% by weight, more preferably 0.05 to 0.3% by weight of the polyfunctional acyl halide.
  • the polyfunctional acid-halogen compound may be immersed in the membrane treated with the polyfunctional amine-containing aqueous solution for 0.1 to 10 minutes, more preferably 0.5 to 1 minute.
  • the thickness of the hydrophilic selective layer may be 0.1 to 1 ⁇ m, and if the thickness is less than 0.1 ⁇ m, the salt removal ability may be reduced, and if it exceeds 1 ⁇ m, the permeate flow rate of the reverse osmosis membrane may be reduced.
  • Polyethylene terephthalate (PET) and dimethylformamide (DMF) were mixed at a weight ratio of 1.57: 8.43, followed by stirring at 65 ° C for 2 hours or more to prepare a polymer solution at a temperature of 65 ° C.
  • the polymer solution was cast at a rate of 15 m / min to a thickness of 150 ⁇ m on a glass plate at 60 ° C.
  • the polymer solution cast in a coagulation tank containing 25 ° C. pure water was immersed to coagulate.
  • the residual solvent component contained in the separation membrane prepared in the water washing tank was extracted to prepare an ultrafiltration membrane.
  • An ultrafiltration membrane was prepared in the same manner as in Example 1, using a polymer solution at 80 ° C and a non-solvent at 25 ° C.
  • An ultrafiltration membrane was prepared in the same manner as in Example 1, using a polymer solution at 95 ° C and a non-solvent at 25 ° C.
  • An ultrafiltration membrane was prepared in the same manner as in Example 1, using a polymer solution at 110 ° C and a non-solvent at 25 ° C.
  • Example 2 The same procedure as in Example 2 was carried out, but instead of DMF, dimethylacetamide (DMAc) was used as a solvent to prepare an ultrafiltration membrane.
  • DMF dimethylacetamide
  • Example 2 The same procedure as in Example 2 was carried out, but N-methyl-2-pyrrolidone (nmP) was used instead of DMF as a solvent to prepare an ultrafiltration membrane.
  • nmP N-methyl-2-pyrrolidone
  • Example 2 The same procedure as in Example 2 was performed, but an ultrafiltration membrane was prepared using o-chlorophenol (OCP) instead of DMF as a solvent.
  • OCP o-chlorophenol
  • An ultrafiltration membrane was prepared using a polymer solution prepared by mixing polyethylene terephthalate (PET) and dimethylformamide (DMF) at a weight ratio of 0.5: 9.5.
  • PET polyethylene terephthalate
  • DMF dimethylformamide
  • PET polyethylene terephthalate
  • DMF dimethylformamide
  • An ultrafiltration membrane was prepared in the same manner as in Example 1, using a polymer solution at 50 ° C and a non-solvent at 25 ° C.
  • An ultrafiltration membrane was prepared in the same manner as in Example 1, using a polymer solution at 58 ° C and a non-solvent at 25 ° C.
  • An ultrafiltration membrane was prepared in the same manner as in Example 1, using a polymer solution at 130 ° C and a non-solvent at 25 ° C.
  • FIG. 1A is a cross-sectional SEM image of the ultrafiltration membrane prepared in Example 1.
  • a pore structure including a first region having a finger-type pore structure formed on an upper portion based on a cross-section of a membrane and a large pore formed below the first region and communicating with the finger-type pore structure It can be confirmed that it has.
  • the thickness ratio of the first region and the second region is 1: 1.27.
  • Figure 1b is an SEM image of the top surface of the ultrafiltration membrane prepared in Example 1. Referring to FIG. 1B, it can be seen that the average pore size of the upper surface of the first region is 30 nm.
  • FIG. 2A is a cross-sectional SEM image of the ultrafiltration membrane prepared in Comparative Example 1. Referring to Figure 2a, it can be seen that the overall sponge structure is formed based on the cross-section of the membrane, it can be confirmed that the pore structure of the finger shape is not formed.
  • Figure 2b is an SEM image of the top surface of the ultrafiltration membrane prepared in Comparative Example 1.
  • permeate flow rate and removal rate were measured at a pressure of 25 ° C. and 1 kgf / cm 2 using an UF flat membrane evaluator (Millipore® UF Stirred Cell ⁇ XF UF 07601>).
  • Example 1 in which the temperature difference between the polymer solution and the non-solvent is 40 ° C can be confirmed that the permeate flow rate was significantly increased than Comparative Example 2 in which the temperature difference was 33 ° C.
  • Comparative Example 3 in which the temperature difference was 105 ° C it was confirmed that the PEO removal rate was decreased by 20.3% compared to Example 4 in which the temperature difference was 85 ° C.
  • Examples 1 to 3 have a permeate flow rate of 2000 GFD or more and at the same time secure a PEO removal rate of 80% or more, and in particular, Examples 1 and 2 can secure a PEO removal rate of 90% or more.

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  • Chemical Kinetics & Catalysis (AREA)
  • Water Supply & Treatment (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

La présente invention concerne une membrane d'ultrafiltration de polyéthylène téréphtalate et son procédé de production et, plus particulièrement, une membrane d'ultrafiltration de polyéthylène téréphtalate et son procédé de production, la membrane d'ultrafiltration de polyéthylène téréphtalate présentant elle-même une hydrophilicité, ayant ainsi une excellente résistance à l'encrassement par des substances organiques hydrophobes, et ayant une structure de pores avec une perméation d'eau favorable, outre une excellente résistance mécanique et une excellente perméabilité à l'eau.
PCT/KR2019/011389 2018-09-05 2019-09-04 Membrane d'ultrafiltration de polyéthylène téréphtalate et son procédé de production WO2020050617A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
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EP3939694A1 (fr) * 2020-07-17 2022-01-19 Leibniz-Institut für Oberflächenmodifizierung e.V. Membrane en pet et production d'une telle membrane par inversion de phase

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KR950016849A (ko) * 1993-12-31 1995-07-20 박홍기 항균성 한외여과막의 제조방법
KR101381890B1 (ko) * 2012-12-27 2014-04-07 광주과학기술원 나노복합체 초박형 분리막 및 이의 제조방법
KR20140073300A (ko) * 2012-12-06 2014-06-16 삼성전자주식회사 분리막, 및 상기 분리막을 포함하는 수처리 장치
KR101448859B1 (ko) * 2012-12-04 2014-10-13 한국과학기술원 수처리용 멤브레인, 및 이의 제조 방법
KR101781473B1 (ko) * 2016-02-17 2017-09-26 주식회사 마이크로필터 정삼투막 제조방법

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KR101418063B1 (ko) 2012-10-29 2014-07-09 롯데케미칼 주식회사 정밀여과막 또는 한외여과막 제조용 고분자 첨가제 및 이의 제조 방법

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KR950016849A (ko) * 1993-12-31 1995-07-20 박홍기 항균성 한외여과막의 제조방법
KR101448859B1 (ko) * 2012-12-04 2014-10-13 한국과학기술원 수처리용 멤브레인, 및 이의 제조 방법
KR20140073300A (ko) * 2012-12-06 2014-06-16 삼성전자주식회사 분리막, 및 상기 분리막을 포함하는 수처리 장치
KR101381890B1 (ko) * 2012-12-27 2014-04-07 광주과학기술원 나노복합체 초박형 분리막 및 이의 제조방법
KR101781473B1 (ko) * 2016-02-17 2017-09-26 주식회사 마이크로필터 정삼투막 제조방법

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3939694A1 (fr) * 2020-07-17 2022-01-19 Leibniz-Institut für Oberflächenmodifizierung e.V. Membrane en pet et production d'une telle membrane par inversion de phase

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