WO2022195967A1 - Membrane de séparation et procédé pour fabriquer une membrane de séparation - Google Patents

Membrane de séparation et procédé pour fabriquer une membrane de séparation Download PDF

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WO2022195967A1
WO2022195967A1 PCT/JP2021/043439 JP2021043439W WO2022195967A1 WO 2022195967 A1 WO2022195967 A1 WO 2022195967A1 JP 2021043439 W JP2021043439 W JP 2021043439W WO 2022195967 A1 WO2022195967 A1 WO 2022195967A1
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separation membrane
graphene
holes
hole
layer
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PCT/JP2021/043439
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English (en)
Japanese (ja)
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広貴 佐久間
靖彦 多田
誠之 廣岡
優史 丸山
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株式会社日立製作所
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Priority to AU2021434229A priority Critical patent/AU2021434229A1/en
Publication of WO2022195967A1 publication Critical patent/WO2022195967A1/fr

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    • 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
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • 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
    • B01D71/02—Inorganic material
    • 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
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • B01D71/14—Esters of organic acids
    • B01D71/16—Cellulose acetate
    • 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
    • B01D71/26—Polyalkenes
    • 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
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/36—Polytetrafluoroethene
    • 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
    • B01D71/50—Polycarbonates
    • 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
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • 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
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material

Definitions

  • the present disclosure relates to a separation membrane and a method for manufacturing a separation membrane.
  • RO membranes are used for seawater desalination, and most of the current commercially available RO membranes have a structure in which a thin aromatic polyamide selective layer is formed on a porous support layer.
  • RO membranes There is a high demand for new membrane materials to improve the performance (separation performance, water permeability, etc.) of RO membranes.
  • Patent Document 1 A method for producing a filter molded body having a layer of graphene as a filter material, in which a layer of a support 3 is formed on the surface of a layer of graphene 1 formed on initial substrates 2 and 9 for graphene. a step of forming water passage holes in the layer of the support 3; a step of removing the initial substrates 2 and 9 for graphene; and a step of heating and holding at a low temperature in the air for a predetermined time to form water passage holes.”
  • Patent Literature 1 describes a separation film composed of a resist layer and graphene (FIG. 1(6)).
  • FOG. 1(6) graphene
  • the separation membrane of the present disclosure includes a support having water permeability, a matrix layer supported by the support and having first pores, and a graphene material supported by the matrix layer and containing at least one of graphene and graphene oxide. and a graphene layer having a second hole overlapping the first hole.
  • FIG. 2 is a cross-sectional view of the separation membrane of this embodiment
  • 1 is a perspective view of a separation membrane of this embodiment
  • FIG. 4 is a top view of the separation membrane of the present embodiment
  • FIG. 4 is a flow chart showing a method for manufacturing a separation membrane according to this embodiment.
  • FIG. 1 is a cross-sectional view of the separation membrane 10 of this embodiment.
  • the separation membrane 10 can be used, for example, to remove solutes such as ions and predetermined molecules from a solution containing the solutes.
  • the separation membrane 10 can be used to remove a dispersion from a slurry containing the dispersion.
  • the separation membrane 10 can stand on its own and is easy to handle. Although the separation membrane 10 has a rectangular shape (FIG. 2) in the illustrated example, the shape of the separation membrane 10 is not limited to the illustrated example. Separation membrane 10 includes support 11 , matrix layer 12 , and graphene layer 13 . Separation membrane 10 may contain arbitrary layers other than these.
  • the support 11 supports the matrix layer 12 and the graphene layer 13 and has water permeability.
  • the separation membrane 10 can be made self-supporting, and the strength of the separation membrane 10 can be improved, for example, the durability to high pressure can be improved.
  • the specific configuration of the support 11 is not particularly limited, it is preferably made of, for example, a water-permeable porous material. By using a porous material, water can pass through the support 11 and the strength of the support 11 can be improved, so that the strength of the separation membrane 10 as a whole can be improved.
  • the openings formed by the porous material may extend only in one direction along the thickness direction (water flow direction) of the support 11, or may extend in a zigzag pattern inside the support 11. .
  • the pressure loss of the support 11 is small when water is passed through it. For this reason, it is preferable to increase the porosity of the porous body within a range in which the strength of the support 11 can be maintained.
  • the diameter of the opening (not shown) of the support 11 is preferably 1 ⁇ m or more and 100 ⁇ m or less.
  • the aperture diameter can be measured using a scanning electron microscope (SEM) or the like.
  • the porosity is, for example, 40% or more and 80% or less. The porosity can be measured by the Archimedes method or the like.
  • the material of the support 11 is not particularly limited. polymer materials such as polypropylene, polyethylene, polysulfone, polyethersulfone, polytetrafluoroethylene (PTFE), cellulose acetate, polyvinylidene fluoride (PVDF), polyacrylonitrile; Ceramic materials such as silica, alumina, titania, zirconia, At least one of the Among these, the support 11 preferably contains at least one selected from the group consisting of polyethylene, polypropylene, polycarbonate, polytetrafluoroethylene, polyethersulfone, polysulfone, and cellulose acetate. By containing at least one of these, the separation membrane 10 can be made lighter and the strength of the separation membrane 10 can be improved.
  • polymer materials such as polypropylene, polyethylene, polysulfone, polyethersulfone, polytetrafluoroethylene (PTFE), cellulose acetate, polyvinylidene fluoride (PVDF), polyacrylon
  • the shape of the support 11 is also not particularly limited, and can be, for example, mesh-like, woven fabric-like, or non-woven fabric-like.
  • the support 11 may be appropriately coated at least on the side where the matrix layer 12 is arranged.
  • the coating material to be used is not particularly limited, at least one of polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP) and the like can be used.
  • the coating material may be obtained by cross-linking different coating materials.
  • the matrix layer 12 has first holes 14 .
  • defects an example of openings whose size is not controlled
  • defects that originally existed in the graphene layer 13
  • the first holes 14 can suppress permeation of the separation membrane 10 through the defects.
  • the separation performance of the separation membrane 10 can be secured.
  • a substance having a size corresponding to the opening diameter of the first hole 14 can be flowed.
  • the opening density of the matrix layer 12, that is, the number of the first holes 14 per unit area on the plane perpendicular to the water flow direction is not particularly limited.
  • the aperture density of the matrix layer 12 is a factor that affects the maximum aperture density of the graphene layer 13 .
  • the opening density is a factor that affects the water permeability of the separation membrane 10 , and the higher the opening density , the more preferable. Water permeability can be improved by making it 0.1 ⁇ 10 3 pieces/ ⁇ m 2 or more. On the other hand, by setting the density to 10 ⁇ 10 3 pieces/ ⁇ m 2 or less, the function of the matrix layer 12 as a mask can be easily exhibited, although the details will be described later.
  • the aperture density can be determined, for example, based on the number of first holes 14 measured using a scanning electron microscope (SEM).
  • the opening diameter of the first hole 14 is not particularly limited, and may be appropriately set according to the size of the target permeable matter.
  • the opening diameter of the first hole 14 is preferably 5 nm or more and 20 nm or less. By setting the thickness within this range, the effect of blocking defects and the like existing in the graphene layer 13 can be increased. Moreover, the opening density can be improved, and the water permeability can be improved. Furthermore, the precision at the time of patterning (described later) can be improved.
  • the opening diameter of the first hole 14 can be measured using, for example, a scanning electron microscope (SEM).
  • FIG. 2 is a perspective view of the separation membrane 10 of this embodiment.
  • FIG. 3 is a top view of the separation membrane 10 of this embodiment.
  • the first holes 14 are arranged in a scattered manner, but the specific form thereof is not particularly limited.
  • the first holes 14 can be a first hole group 141 in which the first holes 14 are linearly arranged continuously at equal intervals, and a plurality of first hole groups 141 can be arranged in parallel at equal intervals.
  • a 60° staggered arrangement in which the angle ⁇ formed by the three adjacent first holes 14 is 60°
  • a 45° staggered arrangement in which the angle ⁇ formed by the three adjacent first holes 14 is 45° (not shown). etc. are also mentioned.
  • the angle ⁇ formed here is an angle formed by two line segments L connecting the centers P of three adjacent first holes 14, and is the smallest angle.
  • the arrangement pattern of the first holes 14 is preferably the 60° staggered arrangement shown in FIGS. 2 and 3 from the viewpoint of increasing the opening density.
  • the opening diameter of the first holes 14 can be set to, for example, 5 nm or more and 20 nm or less, and the distance between adjacent first holes 14 (center-to-center distance, length of one line segment) is It can be, for example, 2 to 4 times (for example, 10 nm to 80 nm) the opening diameter of the first hole 14 .
  • the matrix layer 12 supports the entire graphene layer 13 other than the first holes 14 . Accordingly, even if unintended defects or the like are present in the graphene layer 13 , the size of the permeated matter can be controlled by the second holes 15 of the matrix layer 12 .
  • the thickness (film thickness) of the matrix layer 12 is not particularly limited.
  • the thickness is preferably 5 nm or more and 50 nm or less.
  • the first holes 14 can be easily formed, and the second holes 15 of the graphene layer 13 can be easily formed.
  • the thickness is set to 50 nm or less, the pressure loss of the matrix layer 12 can be reduced.
  • a constituent material of the matrix layer 12 is not particularly limited.
  • a positive or negative photoresist material Block copolymer polymers, specifically polystyrene (PS)-polymethyl methacrylate (PMMA) copolymer, polysilsesquioxane methacrylate (PMAPOSS)-polymethyl methacrylate copolymer, etc.
  • Ceramic materials such as mesoporous silica and porous alumina, At least one such as
  • the matrix layer 12 preferably contains at least one selected from the group consisting of block copolymer polymer, mesoporous silica, and porous alumina.
  • the matrix layer 12 capable of supporting the graphene layer 13 can be formed.
  • the matrix layer 12 contains a block copolymer polymer.
  • the graphene layer 13 is supported by the matrix layer 12 and contains a graphene material containing at least one of graphene and graphene oxide, and has second holes 15 .
  • the graphene layer 13 usually contains graphene oxide.
  • the graphene layer 13 includes one or more unit layers composed of graphene material sheets, and the second holes 15 are formed so as to penetrate the unit layers. By doing so, separation can be performed by the separation membrane 10 even when the number of unit layers is one, and when the number of unit layers is plural, the opening diameter of the second hole 15 is irrespective of the interlayer distance between adjacent unit layers. Control can control the size of the permeate.
  • the second hole 15 is formed overlapping the first hole 14 .
  • “Overlapping” refers to a state in which the first hole 14 and the second hole 15 are in communication with each other and permeate such as solutes and dispersions can flow.
  • the degree of overlap it is not necessary that the second hole 15 completely overlaps the first hole 14 (that is, the opening diameter of the second hole 15 is smaller than the opening diameter of the first hole 14 as shown in FIG. 1, for example). However, it is sufficient that the second hole 15 overlaps at least a part of the first hole 14 .
  • the second holes 15 of the graphene layer 13 are formed using the matrix layer 12 as a mask. Therefore, the opening diameter of the second hole 15 and the opening diameter of the first hole 14 are usually substantially the same (or may be completely the same).
  • the opening density of the second holes 15 in the graphene layer 13, that is, the number of the second holes 15 per unit area on the plane perpendicular to the water flow direction is not particularly limited.
  • the opening density of the graphene layer 13 is a factor that affects the water permeability of the separation membrane 10 , and is preferably as high as possible. is preferred. Water permeability can be improved by making it 0.1 ⁇ 10 3 pieces/ ⁇ m 2 or more. On the other hand, by setting the number to 10 ⁇ 10 3 pieces/ ⁇ m 2 or less, the function of the graphene layer 13 to have high strength, for example, can be easily exhibited.
  • the aperture density can be determined based on the number of second holes 15 measured using, for example, an atomic force microscope (AFM), transmission electron microscope (TEM), scanning electron microscope (SEM), or the like.
  • the opening diameter of the second hole 15 is not particularly limited, and may be appropriately set according to the size of the target permeable matter. For example, if relatively large molecules such as macromolecules are to be removed from the aqueous solution, the thickness is, for example, 2 nm or more and 100 nm or less. preferably.
  • the opening diameter of the second hole 15 can be measured by the same method as for the first hole 14 using, for example, an atomic force microscope (AFM), a transmission electron microscope (TEM), a scanning electron microscope (SEM), or the like.
  • AFM atomic force microscope
  • TEM transmission electron microscope
  • SEM scanning electron microscope
  • the opening diameters of the first hole 14 and the second hole 15 are is preferably controlled. 0.02 ⁇ dM ⁇ dG ⁇ 1.0 ⁇ dM Formula (1)
  • the second holes 15 can be easily formed and the strength of the graphene layer 13 can be improved.
  • the second holes 15 in the graphene layer 13 are formed using the matrix layer 12 as a mask. Therefore, the maximum value of the opening diameter dG of the second holes 15 usually matches the opening diameter dM of the matrix layer 12, which is a mask. On the other hand, the minimum value is about 0.5 nm, which is about 0.02 to 0.1 times dM, assuming a structure in which one six-point ring of graphene or graphene oxide is removed. Therefore, by controlling the opening diameters of the first hole 14 and the second hole 15 so as to satisfy the above (1), the second hole 15 can be easily formed.
  • the graphene material forming the graphene layer 13 usually contains graphene oxide, and the first functional groups forming the inner walls 151 (including openings) of the second holes 15 are usually hydroxyl groups and carboxyl groups contained in the graphene oxide. , an oxygen-containing functional group such as an epoxy group.
  • the first functional group is preferably molecularly modified with a second functional group capable of bonding to the first functional group.
  • the graphene material is oxidized when the second holes 15 are formed, and these oxygen-containing functional groups are likely to be generated on the inner walls of the second holes 15, although the details will be described later.
  • a substance that passes through the second hole 15 can be selected according to the type of the second functional group, or the size of the substance passing through the second hole 15 can be selected according to the size of the second functional group. can be controlled.
  • the second functional group is not particularly limited as long as it can react with and bond with the first functional group.
  • the second functional group includes, for example, a reactive functional group capable of bonding with the first functional group, and a functional functional group capable of bonding with the first functional group and exhibiting functions such as opening diameter control.
  • At least one group such as an alkoxysilyl group, a chlorosilyl group, an amino group, a carboxyl group, and a hydroxyl group can be used as the reactive functional group.
  • Examples of functional functional groups include alkyl groups (methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, etc.), functional groups derived from polyethylene glycol (PEG), acrylic groups, methacrylic groups, At least one of functional groups including acrylamide groups, fluoroalkyl groups, zwitterions (phosphorylcholine, sulfobetaine, carboxybetaine, etc.), derivatives thereof, and the like.
  • the second functional group is an alkyl group, a functional group derived from polyethylene glycol, an acrylic group, a methacrylic group, an acrylamide group, a fluoroalkyl group, a functional group containing a zwitterion, and a group consisting of derivatives thereof. It is preferable to include at least one selected from. By containing at least one of these, the second functional group can be bonded toward the center of the second hole 15 to exhibit various functions.
  • FIG. 4 is a flow chart showing the method for manufacturing the separation membrane 10 (FIG. 1) of this embodiment.
  • the method for manufacturing the separation membrane 10 includes a graphene layer forming step S1, a first arranging step S2, a first hole forming step S3, a second hole forming step S4, a modifying step S5, a second arranging step S6, usually in that order.
  • the graphene layer forming step S1 is a step of forming the graphene layer 13 containing a graphene material containing at least one of graphene and graphene oxide on the substrate.
  • the graphene layer forming step S1 may not be performed, and if not performed, for example, an arbitrary graphene layer 13 may be separately purchased and prepared.
  • any substrate can be used as long as the graphene layer 13 can be formed and the graphene layer 13 can be separated from the substrate.
  • Examples thereof include metal foil such as copper foil.
  • the metal foil may be appropriately formed on another substrate such as a silicon substrate or a sapphire substrate.
  • the graphene layer 13 can be formed on the substrate by chemical vapor deposition (CVD), for example.
  • the graphene layer 13 is preferably a single-layer graphene having only one unit layer composed of a graphene material sheet, but may be a multi-layer graphene having a plurality of unit layers. When single-layer graphene is used, single-crystal graphene having a large crystal size and few crystal grain boundaries is preferable from the viewpoint of film strength.
  • the first arranging step S2 is, for example, a step of arranging the matrix layer 12 on the surface of the graphene layer 13 formed in the graphene layer forming step S1 using a matrix material.
  • the matrix material is, for example, a positive or negative photoresist material; block copolymer polymer, At least one of ceramic materials such as mesoporous silica and porous alumina can be used.
  • a block copolymer polymer is one molecule formed by connecting a plurality of types of polymers with covalent bonds.
  • the matrix material preferably contains a block copolymer polymer.
  • a block copolymer polymer By containing a block copolymer polymer, one polymer can be removed by microphase separation to form the second pores 15, and the remaining polymer can form the matrix layer 12 composed of the other polymer.
  • the block copolymer polymer includes at least one of, for example, a copolymer of polystyrene (PS) and polymethyl methacrylate (PMMA), a copolymer of polysilsesquioxane methacrylate (PMAPOSS) and PMMA, and the like. mentioned.
  • the method of arranging the matrix material on the graphene layer 13 is not particularly limited.
  • it can be formed by applying a solution or slurry containing the matrix material and drying or solidifying it.
  • the first hole forming step S3 is a step of forming the first holes 14 in the matrix layer 12 arranged in the graphene layer 13 .
  • a method for forming the first hole 14 is not particularly limited, and can be performed, for example, as follows.
  • the first holes 14 can be formed by exposing the photoresist material to ultraviolet light, X-rays, electron beams, or the like after forming a film, and then treating the film with a developer. .
  • the aperture diameter and aperture density can be controlled by changing at least one of the molecular weights of one polymer and the other polymer, or the ratio of the molecular weights. For example, by increasing the molecular weight of the polymer corresponding to the first polymer, the opening diameter of the first hole 14 can be increased.
  • a ceramic material for example, in the case of mesoporous silica, after forming a film using a solution containing a SiO 2 precursor such as tetraethoxysilane (TEOS) and a surfactant such as cetyltrimethylammonium bromide, a predetermined It should be heated at temperature. After that, the first hole 14 can be formed by removing the surfactant by washing. In addition, the opening diameter and opening density of the first holes 14 can be controlled by changing at least one of the type of surfactant and processing conditions (temperature, solvent, etc.).
  • TEOS tetraethoxysilane
  • a surfactant such as cetyltrimethylammonium bromide
  • the second hole forming step S4 is a step of forming the second holes 15 in the graphene layer 13 along the first holes 14 after the first hole forming step S3.
  • a specific method is not particularly limited as long as the formation of the second holes 15 can be performed, for example, on the graphene layer 13 exposed on the matrix layer 12 side from the first holes 14 .
  • at least one method such as a dry process such as oxygen plasma treatment or UV ozone treatment, or a wet process such as immersion in an aqueous solution of potassium permanganate, can be performed. can.
  • the modification step S5 is a step of molecularly modifying the first functional group forming the inner wall 151 of the second hole 15 with a second functional group capable of binding to the first functional group.
  • the inner wall 151 can be molecularly modified with the second functional group, and at least one of the opening diameter of the second pore 15 and the substance selectivity of the separation membrane 10 can be controlled.
  • the second functional group is a long-chain alkyl group, a bulky functional group, or the like
  • the opening diameter of the second hole 15 can be made smaller than the opening diameter when formed in the second hole forming step S4.
  • Chemical modification can be performed, for example, by immersing the separation membrane 10 in a solution of a compound having a second functional group. At this time, deaeration treatment, heat treatment, and addition of a catalyst may be performed as necessary.
  • modification step S5 is preferably performed, it does not have to be performed. Furthermore, the modification step S5 may be performed during the formation of the second holes 15 or at any time after the formation.
  • the integral body of the matrix layer 12 and the graphene layer 13 in which the first holes 14 and the second holes 15 are respectively formed is placed on the surface of the support 11 having water permeability so that the matrix layer 12 side is in contact.
  • a specific arrangement method is not particularly limited, but for example, the matrix layer 12 and the support 11 can be arranged by pressing them against each other. At this time, a vacuum laminating device or the like may be used for pressure bonding.
  • the separation membrane 10 can be obtained by immersing it in a copper etching solution such as an aqueous solution of ferric chloride to remove the metal foil such as copper foil, washing with water, and drying. Note that the separation membrane 10 is obtained by etching and washing a metal foil such as a copper foil before being pressure-bonded to the support 11, and for example, by scooping up the integrated matrix layer 12 and the graphene layer 13 with the support 11 in water. can also
  • Example 1 The separation membrane 10 shown in FIG. 1 was produced according to the flow chart shown in FIG. 4 (however, the modification step S5 was not performed).
  • a polysulfone membrane was prepared as the support 11, and a block copolymer of polystyrene (number average molecular weight: 46,100) and polymethyl methacrylate (number average molecular weight: 21,000) was prepared as the matrix material.
  • a graphene layer 13 composed of monolayer graphene was formed on the copper foil by the CVD method (graphene layer forming step S1).
  • a block copolymer material was applied and solidified on the graphene layer 13 to form a matrix layer 12 (first arrangement step S2).
  • the whole was heated in vacuum (at 230° C. for more than 1 hour) to induce microphase separation in the matrix material to form a structure with upstanding cylindrical domains of polymethyl methacrylate.
  • the polystyrene region was insolubilized by ultraviolet irradiation in nitrogen for 1 minute, and the polymethyl methacrylate was removed by immersing in acetic acid for 2 minutes to form the first holes 14 in the matrix layer 12 ( First hole forming step S3).
  • the entire surface was treated with oxygen plasma, the oxygen plasma was brought into contact with the graphene layer 13 through the first holes 14, and the second holes 15 were formed along the first holes 14 (second hole forming step S4). Furthermore, the graphene in the graphene layer 13 was partially oxidized by the oxygen plasma treatment. The oxygen plasma treatment time was adjusted so that the opening diameter of the second holes 15 was 1 nm or less.
  • the separation membrane 10 of Example 1 was obtained by immersing it in an aqueous iron chloride solution to remove the copper foil, washing it with water, and pressing it against the support 11 (second placement step S6).
  • Example 2 In the same manner as in Example 1, except that the modification step S5 was performed between the second hole formation step S4 and the second placement step S6 during the separation membrane 10 preparation, A separation membrane 10 of Example 2 was produced.
  • the modification step S5 was performed by immersing the whole including the copper foil after the UV ozone treatment in methoxydimethyloctylsilane at room temperature for 24 hours.
  • a hydroxyl group (first functional group) bonded to the inner wall 151 of the second hole 15 is molecularly modified with an alkylsilane group (second functional group).
  • Comparative Example 2 A separation membrane of Comparative Example 2 was produced in the same manner as in Example 1, except that the support 11 was not provided.
  • ⁇ Performance evaluation> A fluorescent dye aqueous solution (2 ⁇ 10 ⁇ 5 mol/L porphyrin derivative (5,10,15,20-tetrakis(4- Sulfophenyl) porphyrin; TPPS) aqueous solution) was passed through and the dye-blocking ability and water permeation rate were evaluated.
  • a cross-flow type filtration device was used for the evaluation. This filtration device has a support (not shown) that supports the separation membrane, and the test was performed with each separation membrane supported by the support.
  • the separation membrane using graphene according to the present disclosure has been described in detail by way of embodiments and examples, the gist of the present disclosure is not limited to this, and includes various modifications.
  • the above-described embodiments have been described in detail for easy understanding of the present disclosure, and are not necessarily limited to those having all the described configurations.
  • part of the configuration of one embodiment can be replaced with the configuration of another embodiment, and the configuration of another embodiment can be added to the configuration of one embodiment.

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  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une membrane de séparation ayant une excellente durabilité. Afin de résoudre ce problème, une membrane de séparation 10 comprend : un corps de support 11 qui a une perméabilité à l'eau ; une couche de matrice 12 qui est supportée sur le corps de support 11 et comporte des premiers trous 14 ; et une couche de graphène 13 qui est supportée sur la couche de matrice 12, comprend un matériau de graphène comprenant au moins l'un parmi le graphène et l'oxyde de graphène, et a des seconds trous 15 qui se chevauchent avec les premiers trous 14. La densité des ouvertures des premiers trous 14 et des seconds trous 15 est individuellement de 0.1×103trous/μm2 ou plus et de 10×103trous/μm2 ou moins.
PCT/JP2021/043439 2021-03-17 2021-11-26 Membrane de séparation et procédé pour fabriquer une membrane de séparation WO2022195967A1 (fr)

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JP2021043953A JP2022143451A (ja) 2021-03-17 2021-03-17 分離膜及び分離膜の製造方法
JP2021-043953 2021-03-17

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015521103A (ja) * 2012-05-16 2015-07-27 ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア 低抵抗微細加工フィルタ
JP2017515668A (ja) * 2014-05-08 2017-06-15 ロッキード・マーチン・コーポレーション 積層された二次元材料およびそれが組み込まれた構造物を作製するための方法
WO2020122151A1 (fr) * 2018-12-11 2020-06-18 東レ株式会社 Système de production d'énergie
JP2020203285A (ja) * 2016-05-20 2020-12-24 日東電工株式会社 選択透過性酸化グラフェン膜

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015521103A (ja) * 2012-05-16 2015-07-27 ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア 低抵抗微細加工フィルタ
JP2017515668A (ja) * 2014-05-08 2017-06-15 ロッキード・マーチン・コーポレーション 積層された二次元材料およびそれが組み込まれた構造物を作製するための方法
JP2020203285A (ja) * 2016-05-20 2020-12-24 日東電工株式会社 選択透過性酸化グラフェン膜
WO2020122151A1 (fr) * 2018-12-11 2020-06-18 東レ株式会社 Système de production d'énergie

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