WO2022130741A1 - 分離膜複合体、分離装置、分離方法および分離膜複合体の製造方法 - Google Patents

分離膜複合体、分離装置、分離方法および分離膜複合体の製造方法 Download PDF

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Publication number
WO2022130741A1
WO2022130741A1 PCT/JP2021/036740 JP2021036740W WO2022130741A1 WO 2022130741 A1 WO2022130741 A1 WO 2022130741A1 JP 2021036740 W JP2021036740 W JP 2021036740W WO 2022130741 A1 WO2022130741 A1 WO 2022130741A1
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Prior art keywords
separation membrane
separation
coating film
dense
support
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Ceased
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PCT/JP2021/036740
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English (en)
French (fr)
Japanese (ja)
Inventor
憲一 野田
航 小林
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NGK Insulators Ltd
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NGK Insulators Ltd
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Filing date
Publication date
Application filed by NGK Insulators Ltd filed Critical NGK Insulators Ltd
Priority to DE112021005859.2T priority Critical patent/DE112021005859T5/de
Priority to JP2022569726A priority patent/JP7614228B2/ja
Priority to CN202180061877.XA priority patent/CN116437998A/zh
Publication of WO2022130741A1 publication Critical patent/WO2022130741A1/ja
Priority to US18/317,193 priority patent/US20230277989A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B01D63/066—Tubular membrane modules with a porous block having membrane coated passages
    • 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
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0051—Inorganic membrane manufacture by controlled crystallisation, e,.g. hydrothermal growth
    • 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
    • B01D69/02—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
    • B01D69/108—Inorganic support material
    • 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
    • B01D71/02—Inorganic material
    • B01D71/028—Molecular sieves
    • B01D71/0281—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/40—Clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/04—Specific sealing means
    • B01D2313/042—Adhesives or glues
    • 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
    • B01D2323/081—Heating
    • 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
    • B01D2325/022—Asymmetric membranes
    • B01D2325/0233—Asymmetric membranes with clearly distinguishable layers
    • 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
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • 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
    • B01D67/0083—Thermal after-treatment

Definitions

  • the present invention relates to a zeolite membrane composite and a technique for separating a mixed substance using the zeolite membrane composite.
  • a porous support and a pair of dense glasses covering both end faces of the porous support are provided as a separation membrane composite suitable for separating liquid and gas.
  • a separation membrane composite suitable for separating liquid and gas.
  • those comprising a seal and a zeolite membrane formed on a porous support.
  • a glass seal covering the end face of the porous support covers the end surface of the porous support and is in contact with the glass seal to form a zeolite membrane.
  • a through hole (that is, a cell) of a columnar porous support that is, a monolithic porous support
  • a monolithic separation membrane composite in which a zeolite membrane is formed on the inner surface, as a method of repairing a cell having a defect, a method of closing both ends of the cell having a defect with a polymer compound such as a synthetic resin, or a method of closing both ends of the cell with a defect with a polymer compound such as a synthetic resin, A method has been proposed in which the polymer compound is poured into a cell having a defect and cured. In this way, by filling the defective cell itself without directly repairing the defect, the time required for repairing the defect of the separation membrane composite is shortened.
  • both the separation membrane and the dense portion are covered at the boundary portion between the separation membrane and the dense portion formed on the porous support.
  • a technique for suppressing defects at the boundary portion by providing a film-shaped coating zeolite is disclosed.
  • the present invention is directed to a separation membrane complex, and an object thereof is to improve the separation performance of the separation membrane complex and to easily produce the separation membrane complex.
  • the separation membrane composite has a support having a porous portion and a dense portion that are continuously arranged, and the support is provided on the porous portion of the support and the end portion is described above.
  • a separation membrane that comes into contact with the dense portion and a coating film formed of a layered inorganic compound that covers the boundary portion between the dense portion and the separation membrane are provided.
  • the separation performance of the separation membrane composite can be improved.
  • the separation membrane composite can be easily produced.
  • the layered inorganic compound is a clay mineral or a layered metal oxide.
  • the layered inorganic compound is a clay mineral.
  • the layered inorganic compound is smectite.
  • the average thickness of the coating film is 0.002 ⁇ m or more.
  • the separation membrane is a zeolite membrane.
  • the present invention is also directed to a separator.
  • the separation device includes the above-mentioned separation membrane complex and a supply unit for supplying a mixed substance containing a plurality of types of gases or liquids to the separation membrane complex.
  • the separation membrane complex separates from the mixed substance by permeating the highly permeable substance in the mixed substance.
  • the present invention is also directed to a separation method.
  • the separation method comprises a) the step of preparing the above-mentioned separation membrane composite, and b) supplying a mixed substance containing a plurality of types of gases or liquids to the separation membrane composite.
  • the present invention comprises a step of separating a highly permeable substance in the mixed substance from the mixed substance by permeating the separation membrane complex.
  • the mixture is hydrogen, helium, nitrogen, oxygen, water, water vapor, carbon monoxide, carbon dioxide, nitrogen oxides, ammonia, sulfur oxides, hydrogen sulfide, sulfur fluoride, mercury, alcine, hydrogen cyanide, etc. It contains one or more substances among carbonyl sulfide, hydrogens of C1 to C8, organic acids, alcohols, mercaptans, esters, ethers, ketones and aldehydes.
  • the present invention is directed to a method for producing a separation membrane composite.
  • the method for producing a separation membrane composite includes a) a step of continuously arranging a dense portion of a support in a porous portion, and b) on the porous portion of the support.
  • the step of forming the separation film and c) the boundary is formed by forming a coating film formed of a layered inorganic compound on the boundary portion between the separation film and the dense portion where the end portion is in contact with the dense portion. It comprises a step of covering a portion.
  • the layered inorganic compound is a clay mineral or a layered metal oxide.
  • the layered inorganic compound is a clay mineral.
  • the layered inorganic compound is smectite.
  • the average thickness of the coating film is 0.002 ⁇ m or more.
  • the separation membrane is a zeolite membrane.
  • the method for producing the separation membrane composite further comprises a step of heat-treating the support, the separation membrane and the coating film at a temperature of 200 ° C. or higher after the step c).
  • FIG. 3 is an enlarged cross-sectional view showing an end portion of another separation membrane composite.
  • FIG. 3 is an enlarged cross-sectional view showing an end portion of another separation membrane composite.
  • FIG. 3 is an enlarged cross-sectional view showing an end portion of another separation membrane composite.
  • FIG. 3 is an enlarged cross-sectional view showing an end portion of another separation membrane composite.
  • FIG. 3 is an enlarged cross-sectional view showing an end portion of another separation membrane composite.
  • FIG. 3 is an enlarged cross-sectional view showing an end portion of another separation membrane composite.
  • FIG. 3 is an enlarged cross-sectional view showing an end portion of another separation membrane composite.
  • FIG. 3 is an enlarged cross-sectional view showing an end portion of another separation membrane composite.
  • FIG. 1 is a cross-sectional view of the separation membrane complex 1 according to the embodiment of the present invention.
  • FIG. 2 is an enlarged cross-sectional view showing a part of an end portion of the separation membrane complex 1 in the longitudinal direction (that is, the left-right direction in FIG. 1).
  • FIG. 3 is an enlarged cross-sectional view showing a part of the central portion of the separation membrane complex 1 in the longitudinal direction.
  • the separation membrane complex 1 includes a support 11, a separation membrane 12, and a coating membrane 13.
  • the support 11 includes a porous portion 41 which is a columnar main body portion, and a dense portion 42 which covers the surfaces of both ends of the porous portion 41 in the longitudinal direction (that is, the left-right direction in FIG. 1).
  • the separation membrane 12 is drawn with a thick line.
  • the illustration of the coating film 13 shown in FIG. 2 is omitted.
  • parallel diagonal lines are provided on the porous portion 41, the dense portion 42, and the separation membrane 12, and the coating film 13 is shown by a thick line.
  • the thicknesses of the dense portion 42, the separation film 12, and the coating film 13 are drawn thicker than they actually are.
  • the thickness of the separation membrane 12 is drawn thicker than it actually is.
  • the porous portion 41 of the support 11 is an integrally molded, substantially columnar member.
  • the porous portion 41 is provided with a plurality of through holes 111 extending in the longitudinal direction. That is, the porous portion 41 is a so-called monolith-type member.
  • the outer shape of the porous portion 41 is, for example, substantially cylindrical.
  • the porous portion 41 is a porous member having pores through which gas and liquid can permeate.
  • the cross section perpendicular to the longitudinal direction of each through hole 111 ie, cell
  • the diameter of the through hole 111 is larger than the actual diameter, and the number of the through hole 111 is smaller than the actual number.
  • the length of the porous portion 41 (that is, the length in the left-right direction in FIG. 1) is, for example, 10 cm to 200 cm.
  • the outer diameter of the porous portion 41 is, for example, 0.5 cm to 30 cm.
  • the distance between the central axes of the adjacent through holes 111 is, for example, 0.3 mm to 10 mm.
  • the surface roughness (Ra) of the porous portion 41 is, for example, 0.1 ⁇ m to 5.0 ⁇ m, preferably 0.2 ⁇ m to 2.0 ⁇ m.
  • the shape of the porous portion 41 may be, for example, a honeycomb shape, a flat plate shape, a tubular shape, a cylindrical shape, a columnar shape, a polygonal columnar shape, or the like. When the shape of the porous portion 41 is tubular or cylindrical, the thickness of the porous portion 41 is, for example, 0.1 mm to 10 mm.
  • the porous portion 41 As the material of the porous portion 41 , various substances (for example, ceramic or metal) can be adopted as long as they have chemical stability in the step of forming the separation film 12 on the surface.
  • the porous portion 41 is formed of a ceramic sintered body.
  • the ceramic sintered body selected as the material of the porous portion 41 include alumina, silica, mullite, zirconia, titania, ittria, silicon nitride, silicon carbide and the like.
  • the porous portion 41 contains at least one of alumina, silica and mullite.
  • the porous portion 41 may contain an inorganic binder.
  • the inorganic binder at least one of titania, mullite, easily sinterable alumina, silica, glass frit, clay mineral, and easily sinterable cordierite can be used.
  • the average pore diameter of the porous portion 41 is, for example, 0.01 ⁇ m to 70 ⁇ m, preferably 0.05 ⁇ m to 25 ⁇ m.
  • the average pore diameter of the porous portion 41 in the vicinity of the surface on which the separation membrane 12 is formed is 0.01 ⁇ m to 1 ⁇ m, preferably 0.05 ⁇ m to 0.5 ⁇ m.
  • the average pore size can be measured by, for example, a mercury porosimeter, a palm porosimeter or a nanopalm porosimeter.
  • D5 is, for example, 0.01 ⁇ m to 50 ⁇ m
  • D50 is, for example, 0.05 ⁇ m to 70 ⁇ m
  • D95 is, for example, 0.1 ⁇ m to 2000 ⁇ m. be.
  • the porosity of the porous portion 41 in the vicinity of the surface on which the separation membrane 12 is formed is, for example, 20% to 60%.
  • the porous portion 41 has, for example, a multilayer structure in which a plurality of layers having different average pore diameters are laminated in the thickness direction.
  • the average pore diameter and sintered particle size in the surface layer including the surface on which the separation film 12 is formed are smaller than the average pore diameter and sintered particle size in the layers other than the surface layer.
  • the average pore diameter of the surface layer of the porous portion 41 is, for example, 0.01 ⁇ m to 1 ⁇ m, preferably 0.05 ⁇ m to 0.5 ⁇ m.
  • the above-mentioned materials can be used as the material for each layer.
  • the materials of the plurality of layers forming the multilayer structure may be the same or different.
  • the dense portion 42 is a film-like or thin plate-like member fixed to both ends of the porous portion 41 in the longitudinal direction.
  • the dense portion 42 covers the longitudinal end surface of the porous portion 41, the outer surface in the vicinity of the end face, and the inner surface in the vicinity of the end surface of each through hole 111 at each end portion in the longitudinal direction of the porous portion 41. And seal.
  • the dense portion 42 is, for example, a non-porous member having substantially no pores.
  • the dense portion 42 preferably has high strength, high heat resistance and chemical resistance.
  • the dense portion 42 is formed of, for example, glass, ceramic, metal, resin, or the like.
  • the dense portion 42 is made of glass.
  • the dense portion 42 is, for example, a glass film formed by firing on the surface of the porous portion 41.
  • the average thickness of the dense portion 42 is, for example, 1 ⁇ m to 1000 ⁇ m.
  • the dense portion 42 is formed by, for example, attaching a glass frit to the surface of the porous portion 41 and firing it together with the porous portion 41.
  • the formation of the dense portion 42 may be performed in parallel with the formation of the separation membrane 12, and may be performed before or after the formation of the separation membrane 12.
  • the material and shape of the dense portion 42 may be changed as appropriate.
  • the dense portion 42 may be a porous member having pores having an average pore diameter smaller than that of the surface layer of the porous portion 41.
  • the dense portion 42 is a sealing portion that is continuously arranged in the porous portion 41 and substantially prevents the inflow and outflow of gas and liquid into the porous portion 41.
  • the portion of the dense portion 42 that covers the end face of the porous portion 41 in the longitudinal direction is provided with a plurality of openings that overlap with the plurality of through holes 111 of the porous portion 41. Therefore, both ends of each through hole 111 in the longitudinal direction are not covered with the dense portion 42, and gas and liquid can flow in and out of the through hole 111 from both ends.
  • the separation membrane 12 is a substantially cylindrical thin film provided on the inner surface of the through hole 111 of the porous portion 41 over substantially the entire surface of the inner surface.
  • the longitudinal end of the separation membrane 12 comes into contact with the dense portion 42 covering the longitudinal end of the inner surface on the inner surface of the through hole 111. That is, the separation membrane 12 covers substantially the entire region of the inner surface of the through hole 111 that is not covered by the dense portion 42.
  • the longitudinal edge of the separation membrane 12 and the longitudinal edge of the dense portion 42 are in contact with each other, and the longitudinal end of the separation membrane 12 and the longitudinal edge of the compact portion 42 are in contact with each other.
  • the end portion in the direction hardly overlaps with the radial end of the through hole 111 (that is, the vertical direction in FIG. 2).
  • the separation membrane 12 is a dense porous membrane having fine pores.
  • the separation membrane 12 can separate a specific substance from a mixed substance in which a plurality of types of substances are mixed.
  • the average pore diameter of the separation membrane 12 is larger than the average pore diameter of the dense portion 42 when the dense portion 42 is a porous member.
  • the dense portion 42 is denser than the separation membrane 12.
  • the dense portion 42 is a porous member, if the dense portion 42 attempts to separate the specific substance from the mixed substance, the permeation rate of the specific substance is 1 in the case where the separation is performed by the separation membrane 12. It is / 10 or less (preferably 1/100 or less).
  • the dense portion 42 is a non-porous member that is sufficiently denser than the separation membrane 12 and does not substantially allow the specific substance to permeate.
  • the separation membrane 12 is a zeolite membrane.
  • the zeolite membrane does not include, at least, a film in which zeolite is formed in the form of a film on the surface of the porous portion 41 of the support 11, and the zeolite particles are simply dispersed in the organic film.
  • the zeolite membrane can be used as a separation membrane for separating a specific substance from the mixed substance.
  • other substances are less likely to permeate than the specific substance.
  • the permeation amount of the other substance in the zeolite membrane is smaller than the permeation amount of the specific substance.
  • the zeolite membrane may contain two or more types of zeolite having different structures and compositions.
  • the thickness of the separation membrane 12 is, for example, 0.05 ⁇ m to 30 ⁇ m, preferably 0.1 ⁇ m to 20 ⁇ m, and more preferably 0.5 ⁇ m to 10 ⁇ m. Thickening the separation membrane 12 improves the separation performance. When the separation membrane 12 is thinned, the permeation rate increases.
  • the surface roughness (Ra) of the separation membrane 12 is, for example, 5 ⁇ m or less, preferably 2 ⁇ m or less, more preferably 1 ⁇ m or less, and further preferably 0.5 ⁇ m or less.
  • the pore diameter of the zeolite crystals contained in the separation membrane 12 (hereinafter, also simply referred to as “pore diameter of the separation membrane 12”) is 0.2 nm or more and 0.8 nm or less, more preferably 0.3 nm or more and It is 0.7 nm or less, more preferably 0.3 nm or more and 0.5 nm or less. If the pore diameter of the separation membrane 12 is less than 0.2 nm, the amount of the substance that permeates the separation membrane 12 may be small, and if the pore diameter of the separation membrane 12 is larger than 0.8 nm, the substance due to the separation membrane 12 May be inadequate in selectivity.
  • the pore diameter of the separation membrane 12 is the diameter of the pores in a direction substantially perpendicular to the maximum diameter of the pores of the zeolite crystals constituting the separation membrane 12 (that is, the major diameter which is the maximum value of the oxygen atom distance) (that is, the diameter of the pores). Short diameter).
  • the pore diameter of the separation membrane 12 is smaller than the average pore diameter on the surface of the porous portion 41 of the support 11 on which the separation membrane 12 is arranged.
  • the minor axis of the n-membered ring pores is defined as the pore diameter of the separation membrane 12.
  • the minor axis of the n-membered ring pore having the largest minor diameter is defined as the pore diameter of the separation membrane 12.
  • the n-membered ring is a portion in which the number of oxygen atoms constituting the skeleton forming the pores is n, and each oxygen atom is bonded to a T atom described later to form a cyclic structure.
  • the n-membered ring refers to a ring having a through hole (channel), and does not include a ring having no through hole.
  • the n-membered ring pores are pores formed by the n-membered ring.
  • the maximum number of membered rings of the zeolite contained in the above-mentioned separation membrane 12 is preferably 8 or less (for example, 6 or 8).
  • the pore diameter of the separation membrane 12 which is a zeolite membrane is uniquely determined by the skeleton structure of the zeolite, and is described in "Database of Zeolite Structures" [online] of the International Zeolite Society, Internet ⁇ URL: http: // www. iza-structure. It can be obtained from the values disclosed in org / databases />.
  • the type of zeolite constituting the separation membrane 12 is not particularly limited, but is, for example, AEI type, AEN type, AFN type, AFV type, AFX type, BEA type, CHA type, DDR type, ERI type, ETL type, FAU type.
  • X type, Y type GIS type, IHW type, LEV type, LTA type, LTJ type, MEL type, MFI type, MOR type, PAU type, RHO type, SOD type, SAT type and the like.
  • the zeolite is an 8-membered ring zeolite, for example, AEI type, AFN type, AFV type, AFX type, CHA type, DDR type, ERI type, ETL type, GIS type, IHW type, LEV type, LTA type, LTJ Zeolites of type, RHO type, SAT type and the like.
  • the zeolite constituting the separation membrane 12 has T atoms (that is, atoms located at the center of the oxygen tetrahedron (TO 4 ) constituting the zeolite), for example, silicon (Si), aluminum (Al), phosphorus (P). Including at least one of.
  • T atoms that is, atoms located at the center of the oxygen tetrahedron (TO 4 ) constituting the zeolite
  • the T atom is only Si or a zeolite composed of Si and Al
  • the T atom is an AlPO type zeolite composed of Al and P
  • the T atom is composed of Si, Al and P.
  • SAPO type zeolite SAPO type zeolite, MAPSO type zeolite whose T atom is composed of magnesium (Mg), Si, Al and P, ZnASPSO type zeolite whose T atom is composed of zinc (Zn), Si, Al and P, etc. are used. be able to. A part of the T atom may be replaced with another element.
  • the separation membrane 12 contains, for example, Si.
  • the separation membrane 12 may contain, for example, any two or more of Si, Al, and P.
  • the separation membrane 12 may contain an alkali metal.
  • the alkali metal is, for example, sodium (Na) or potassium (K).
  • the Si / Al ratio in the separation membrane 12 is, for example, 1 or more and 100,000 or less.
  • the Si / Al ratio is the molar ratio of the Si element to the Al element contained in the separation membrane 12.
  • the Si / Al ratio is preferably 5 or more, more preferably 20 or more, still more preferably 100 or more, and the higher the ratio, the more preferable.
  • the Si / Al ratio in the separation membrane 12 can be adjusted by adjusting the mixing ratio of the Si source and the Al source in the raw material solution described later.
  • the separation membrane 12 may include a membrane other than the zeolite membrane in addition to the zeolite membrane.
  • the separation membrane 12 may be a membrane other than the zeolite membrane.
  • the coating film 13 is a thin-film member that covers the boundary portion 45 between the dense portion 42 and the separation membrane 12 in each through hole 111 over substantially the entire area.
  • the boundary portion 45 between the dense portion 42 and the separation membrane 12 is a substantially circumferential region where the longitudinal edge of the dense portion 42 and the separation membrane 12 are in contact with each other.
  • the substantially circumferential region that is, the contact portion in which the longitudinal edge of the dense portion 42 and the separation membrane 12 are in contact with each other is directly covered with the separation membrane 12.
  • the boundary portion is a substantially circumferential region where the surface extending from the contact portion in the direction perpendicular to the surface of the porous portion 41 (that is, the normal direction of the surface of the porous portion 41) and the surface of the separation membrane 12 intersect. It is set to 45.
  • the coating film 13 is a member including a substantially cylindrical portion provided on the boundary portion 45 between the dense portion 42 and the separation film 12 over the entire circumference of the inner surface of the through hole 111.
  • the coating film 13 may extend from the boundary portion 45 on both sides in the longitudinal direction. Further, the covering film 13 may continuously spread in the longitudinal direction from the longitudinal end portion of the separation membrane 12 to the dense portion 42, and may cover the longitudinal end portion of the dense portion 42.
  • the coating film 13 extends from the boundary portion 45 toward the separation film 12 in the longitudinal direction by 1 mm to 50 mm. Further, the coating film 13 covers substantially the entire surface of the dense portion 42 on the inner surface of the through hole 111. In the example shown in FIG. 2, the covering film 13 extends from the boundary portion 45 to the longitudinal end surface of the support 11 (that is, the longitudinal end surface of the dense portion 42), but on the end surface. It does not have to be extended to. Alternatively, the edge of the covering film 13 on the dense portion 42 side may be located between the longitudinal end surface of the support 11 and the boundary portion 45.
  • FIG. 4A is an SEM (Scanning Electron Microscope) image showing a cross section of the separation membrane composite 1 in the vicinity of the coating film 13.
  • FIG. 4B is an enlarged SEM image showing the coating film 13 of FIG. 4A.
  • the coating film 13 is a thin film member having a layered microstructure formed of a layered inorganic compound.
  • the layered inorganic compound is an inorganic compound having a layered structure.
  • SEM or TEM Transmission Electron Microscope
  • the layered structure is a structure in which atoms are strongly bonded by covalent bonds or ionic bonds and closely arranged, and are stacked substantially in parallel in the thickness direction by a weak bond force such as van der Waals force, or the said structure.
  • the sheet structure is a highly flat structure in which sheets are stacked in the thickness direction and bonded via ions or molecules.
  • a large number of sheet structures are laminated in layers in the vertical direction in the drawing.
  • the thickness of each sheet structure is, for example, 0.3 nm to 10 nm.
  • the layered inorganic compound forming the coating film 13 for example, clay minerals, layered metal oxides, layered double hydroxides, layered phosphates, layered carbons and the like can be used.
  • the clay mineral for example, pyrophyllite, mica, smectite, vermiculite, chlorite, kaolinite, halloysite, talc, and other layered silicates can be used.
  • the layered metal oxide for example, layered titanate, layered niobate, layered manganese oxide, layered perovskite and the like can be used.
  • layered phosphate for example, ⁇ -type zirconium phosphate, ⁇ -type zirconium phosphate, ⁇ -type titanium phosphate, ⁇ -type titanium phosphate, aluminum triphosphate and the like can be used.
  • layered carbon for example, graphite, graphene, graphene oxide and the like can be used.
  • the layered inorganic compound forming the coating film 13 is preferably a clay mineral or a layered metal oxide, and more preferably a clay mineral. More preferably, the layered inorganic compound forming the coating film 13 is smectite. As the smectite, montmorillonite, byderite, nontronite, saponite, hectorite, stepnsite, saponite and the like can be used.
  • the coating film 13 does not substantially permeate gas and liquid, and even if it permeates, the amount of permeation is small.
  • the coating film 13 is a porous member, if the coating film 13 attempts to separate the specific substance from the mixed substance, the permeation rate of the specific substance is determined by the separation membrane 12. The following (preferably 1/10 or less, more preferably 1/100 or less).
  • the coating film 13 is a non-porous member that is sufficiently denser than the separation membrane 12 and is substantially impermeable to the particular substance.
  • the coating film 13 preferably has high strength, high heat resistance and chemical resistance. Either the coating film 13 or the dense portion 42 may be more dense, and may have the same degree of denseness.
  • the average thickness of the coating film 13 is, for example, 0.002 ⁇ m or more, preferably 0.01 ⁇ m or more. By setting the average thickness to 0.002 ⁇ m, the denseness of the coating film 13 is improved, and the permeation of gas, liquid, or the like through the coating film 13 is preferably suppressed. Further, when the average thickness is 0.01 ⁇ m or more, the denseness of the coating film 13 is further improved.
  • the upper limit of the average thickness of the coating film 13 is not particularly limited, but is, for example, 10 ⁇ m or less, preferably 5 ⁇ m or less. By setting the average thickness to 10 ⁇ m or less, it is possible to prevent defects such as cracks from occurring in the coating film 13. Further, by setting the average thickness to 5 ⁇ m or less, the occurrence of defects is further suppressed.
  • the average thickness of the coating film 13 can be obtained by observing the cross section with SEM or TEM.
  • FIG. 5 is a diagram showing the separating device 2.
  • FIG. 6 is a diagram showing a flow of separation of mixed substances by the separation device 2.
  • a mixed substance containing a plurality of types of fluids that is, gas or liquid
  • a highly permeable substance in the mixed substance is permeated through the separation membrane complex 1.
  • Separation in the separation device 2 may be performed for the purpose of extracting a highly permeable substance (hereinafter, also referred to as “highly permeable substance”) from the mixed substance, and may be performed for the purpose of extracting a substance having low permeability (hereinafter, “highly permeable substance”). It may be carried out for the purpose of concentrating (also referred to as "lowly permeable substance”).
  • the mixed substance (that is, a mixed fluid) may be a mixed gas containing a plurality of types of gases, a mixed liquid containing a plurality of types of liquids, and a gas-liquid two-phase containing both a gas and a liquid. It may be a fluid.
  • the mixed substances include, for example, hydrogen (H 2 ), helium (He), nitrogen (N 2 ), oxygen (O 2 ), water (H 2 O), water vapor (H 2 O), carbon monoxide (CO), and the like.
  • Carbon dioxide (CO 2 ) nitrogen oxides, ammonia (NH 3 ), sulfur oxides, hydrogen sulfide (H 2 S), sulfur fluoride, mercury (Hg), arsine (AsH 3 ), hydrogen cyanide (HCN), sulfide
  • the above-mentioned highly permeable substance is, for example, one or more of H 2 , He, N 2 , O 2 , H 2 O, CO 2 , NH 3 and H 2 S.
  • Nitrogen oxides are compounds of nitrogen and oxygen.
  • the above-mentioned nitrogen oxides include, for example, nitric oxide (NO), nitrogen dioxide (NO 2 ), nitrous oxide (also referred to as dinitrogen monoxide) (N 2 O), and dinitrogen trioxide (N 2 O 3 ). ), Nitric oxide (N 2 O 4 ), Nitric oxide (N 2 O 5 ) and other gases called NO X.
  • Sulfur oxides are compounds of sulfur and oxygen.
  • the above-mentioned sulfur oxide is, for example, a gas called SO X (sox) such as sulfur dioxide (SO 2 ) and sulfur trioxide (SO 3 ).
  • Sulfur fluoride is a compound of fluorine and sulfur.
  • the hydrocarbons of C1 to C8 are hydrocarbons having 1 or more carbon atoms and 8 or less carbon atoms.
  • the hydrocarbons C3 to C8 may be any of a linear compound, a side chain compound and a cyclic compound.
  • the hydrocarbons of C2 to C8 are saturated hydrocarbons (that is, those in which double bonds and triple bonds are not present in the molecule) and unsaturated hydrocarbons (that is, double bonds and / or triple bonds are molecules). It may be either of those present in it).
  • Hydrocarbons of C1 to C4 are, for example, methane (CH 4 ), ethane (C 2 H 6 ), ethylene (C 2 H 4 ), propane (C 3 H 8 ), propylene (C 3 H 6 ), normal butane.
  • the above-mentioned organic acid is a carboxylic acid, a sulfonic acid or the like.
  • Carboxylic acids include, for example, formic acid (CH 2 O 2 ), acetic acid (C 2 H 4 O 2 ), oxalic acid (C 2 H 2 O 4 ), acrylic acid (C 3 H 4 O 2 ) or benzoic acid (C). 6 H 5 COOH) and the like.
  • the sulfonic acid is, for example, ethane sulfonic acid (C 2 H 6 O 3 S) or the like.
  • the organic acid may be a chain compound or a cyclic compound.
  • the above-mentioned alcohols include, for example, methanol (CH 3 OH), ethanol (C 2 H 5 OH), isopropanol (2-propanol) (CH 3 CH (OH) CH 3 ), ethylene glycol (CH 2 (OH) CH 2 ). (OH)) or butanol (C 4 H 9 OH) or the like.
  • Mercaptans are organic compounds having hydrogenated sulfur (SH) at the end, and are substances also called thiols or thioalcohols.
  • the above-mentioned mercaptans are, for example, methyl mercaptan (CH 3 SH), ethyl mercaptan (C 2 H 5 SH), 1-propanethiol (C 3 H 7 SH) and the like.
  • ester is, for example, formate ester or acetic acid ester.
  • ether is, for example, dimethyl ether ((CH 3 ) 2 O), methyl ethyl ether (C 2 H 5 OCH 3 ) or diethyl ether ((C 2 H 5 ) 2 O).
  • ketone is, for example, acetone ((CH 3 ) 2 CO), methyl ethyl ketone (C 2 H 5 COCH 3 ) or diethyl ketone ((C 2 H 5 ) 2 CO).
  • aldehydes are, for example, acetaldehyde (CH 3 CHO), propionaldehyde (C 2 H 5 CHO) or butyraldehyde (butyraldehyde) (C 3 H 7 CHO) and the like.
  • the mixed substance separated by the separating device 2 will be described as being a mixed gas containing a plurality of types of gases.
  • the separation device 2 includes a separation membrane complex 1, an outer cylinder 22, two sealing members 23, a supply unit 26, a first collection unit 27, and a second collection unit 28.
  • the separation membrane complex 1 and the sealing member 23 are housed in the outer cylinder 22.
  • the supply unit 26, the first collection unit 27, and the second collection unit 28 are arranged outside the outer cylinder 22 and connected to the outer cylinder 22.
  • the shape of the outer cylinder 22 is not particularly limited, but is, for example, a substantially cylindrical tubular member.
  • the outer cylinder 22 is made of, for example, stainless steel or carbon steel.
  • the longitudinal direction of the outer cylinder 22 is substantially parallel to the longitudinal direction of the separation membrane complex 1.
  • a supply port 221 is provided at one end of the outer cylinder 22 in the longitudinal direction (that is, the left end in FIG. 5), and a first discharge port 222 is provided at the other end.
  • a second discharge port 223 is provided on the side surface of the outer cylinder 22.
  • a supply unit 26 is connected to the supply port 221.
  • the first collection unit 27 is connected to the first discharge port 222.
  • the second collection unit 28 is connected to the second discharge port 223.
  • the internal space of the outer cylinder 22 is a closed space isolated from the space around the outer cylinder 22.
  • the two sealing members 23 are arranged over the entire circumference between the outer surface of the separation membrane complex 1 and the inner surface of the outer cylinder 22 in the vicinity of both ends in the longitudinal direction of the separation membrane complex 1.
  • Each sealing member 23 is a substantially annular member made of a material that is impermeable to gas and liquid.
  • the seal member 23 is, for example, an O-ring made of a flexible resin.
  • the sealing member 23 is in close contact with the outer surface of the separation membrane complex 1 and the inner surface of the outer cylinder 22 over the entire circumference. In the example shown in FIG. 5, the sealing member 23 adheres to a portion on the outer surface of the support 11 of the separation membrane complex 1 where the porous portion 41 is covered by the dense portion 42.
  • a coating film 13 may be formed at a portion of the dense portion 42 where the seal member 23 is arranged.
  • the seal member 23 and the dense portion 42 may be in close contact with each other via the coating film 13.
  • the space between the sealing member 23 and the outer surface of the separation membrane complex 1 and the space between the sealing member 23 and the inner surface of the outer cylinder 22 are sealed, and the passage of gas and liquid is almost or completely impossible. Is.
  • the supply unit 26 supplies the mixed gas to the internal space of the outer cylinder 22 via the supply port 221.
  • the supply unit 26 includes, for example, a pressure feeding mechanism such as a blower or a pump that pumps the mixed gas toward the outer cylinder 22.
  • the pressure feeding mechanism includes, for example, a temperature control unit and a pressure control unit that adjust the temperature and pressure of the mixed gas supplied to the outer cylinder 22, respectively.
  • the first recovery unit 27 and the second recovery unit 28 include, for example, a storage container for storing the gas derived from the outer cylinder 22, or a blower or a pump for transferring the gas.
  • the separation membrane complex 1 is prepared (FIG. 6: step S11). Specifically, the separation membrane complex 1 is prepared by being attached to the inside of the outer cylinder 22. Subsequently, the supply unit 26 supplies a mixed gas containing a plurality of types of gases having different permeability to the separation membrane 12 to the inside of the outer cylinder 22 as shown by an arrow 251.
  • the main components of the mixed gas are CO 2 and CH 4 .
  • the mixed gas may contain a gas other than CO 2 and CH 4 .
  • the pressure of the mixed gas supplied from the supply unit 26 to the inside of the outer cylinder 22 (that is, the pressure on the supply side) is, for example, 0.1 MPaG to 20.0 MPaG.
  • the temperature of the mixed gas supplied from the supply unit 26 is, for example, 10 ° C to 250 ° C.
  • the mixed gas supplied from the supply unit 26 to the outer cylinder 22 is introduced into each through hole 111 of the support 11 from the left end in the drawing of the separation membrane complex 1.
  • the mixed gas from the supply unit 26 is supplied to the separation membrane complex 1 in the outer cylinder 22.
  • the highly permeable substance for example, CO 2
  • CO 2 which is a highly permeable gas in the mixed gas, forms a separation membrane 12 provided on the inner surface of each through hole 111 and a porous portion 41 of the support 11. It is transmitted and derived from the outer surface of the support 11. As a result, the highly permeable substance is separated from the mixed gas (step S12).
  • the gas derived from the outer surface of the support 11 (hereinafter referred to as “permeate”) is guided to the second recovery unit 28 via the second discharge port 223 as shown by the arrow 253. It is collected by the second collection unit 28.
  • the pressure of the gas recovered by the second recovery unit 28 (that is, the pressure on the permeation side) is, for example, 0.0 MPaG.
  • the permeable substance may contain a low permeable substance (for example, CH 4 ) which is a gas having low permeability in the mixed gas.
  • the gas excluding the substance that has permeated through the separation membrane 12 and the support 11 has each through hole 111 of the support 11 from the left side to the right side in the drawing.
  • the gas is collected by the first collection unit 27 via the first discharge port 222.
  • the pressure of the gas recovered by the first recovery unit 27 is, for example, substantially the same as the introduction pressure.
  • the impermeable substance may include a highly permeable substance that has not penetrated the separation membrane 12 in addition to the above-mentioned low permeable substance.
  • the impermeable substance recovered by the first recovery unit 27 may be circulated to the supply unit 26 and supplied again into the outer cylinder 22, for example.
  • step S21 a raw material containing an aggregate material for the porous portion 41, a pore-forming agent, a binder, and the like is prepared and mixed. Subsequently, water is added to the raw material and kneaded by a kneader to prepare clay. Next, the clay is molded by an extrusion molding machine or the like, and a molded body having a plurality of through holes 111 (see FIG. 1) is obtained.
  • the molded product may be molded by a molding method other than extrusion molding.
  • step S21 is a step of continuously forming and arranging the dense portion 42 of the support 11 in the porous portion 41.
  • the temperature (that is, the firing temperature) of the outermost layer of the molded product during the firing process is, for example, 1000 ° C to 1500 ° C, and 1250 ° C in the present embodiment.
  • the firing time is, for example, 1 hour to 100 hours.
  • the conditions for the firing process of the molded product may be changed as appropriate.
  • the porous portion 41 is formed by firing without attaching the glass frit or the like to the molded body, and then the glass frit or the like is attached to the porous portion 41 and fired again.
  • a continuous dense portion 42 may be formed in the porous portion 41.
  • a raw material solution of a seed crystal is prepared by dissolving or dispersing a raw material such as a Si source and a structure-defining agent (Structure-Directing Agent, hereinafter also referred to as “SDA”) in a solvent. .. Subsequently, hydrothermal synthesis of the raw material solution is performed, and the obtained crystals are washed and dried to obtain a zeolite (for example, DDR type zeolite) powder.
  • the zeolite powder may be used as a seed crystal as it is, or a seed crystal may be obtained by processing the powder by pulverization or the like.
  • the seed crystal is attached onto the inner surface of the through hole 111 of the support 11 (step S23). Specifically, the seed crystal is attached to the portion of the inner surface of each through hole 111 where the porous portion 41 is exposed.
  • the adhesion of the seed crystal to the support 11 is performed, for example, by immersing the porous support 11 in a dispersion liquid in which the seed crystal is dispersed in a solvent (for example, water or an alcohol such as ethanol). .. Immersion of the support 11 in the dispersion liquid may be repeated a plurality of times. Further, the seed crystal may be attached to the support 11 by another method different from the above.
  • the support 11 to which the seed crystal is attached is immersed in the raw material solution.
  • the raw material solution is prepared, for example, by dissolving a Si source, SDA, or the like in a solvent.
  • the composition of the raw material solution is, for example, 1.0SiO 2 : 0.015SDA: 0.12 (CH 2 ) 2 (NH 2 ) 2 .
  • Alcohol such as water or ethanol may be used as the solvent of the raw material solution.
  • the molar ratio of SDA to the water contained in the raw material solution is preferably 0.01 or less.
  • the molar ratio of SDA to water contained in the raw material solution is preferably 0.00001 or more.
  • the SDA contained in the raw material solution is, for example, an organic substance.
  • As the SDA for example, 1-adamantanamine can be used.
  • a DDR-type separation membrane 12 is formed on the porous portion 41 of the support 11 (step S24).
  • the longitudinal end of the separation membrane 12 is in contact with the longitudinal end of the compact 42, as described above.
  • the temperature during hydrothermal synthesis is preferably 120 to 200 ° C, for example 130 ° C.
  • the hydrothermal synthesis time is preferably 5 to 100 hours, for example, 15 hours.
  • the support 11 and the separation membrane 12 are washed with pure water. After washing, the support 11 and the separation membrane 12 are dried at, for example, 80 ° C. After the support 11 and the separation membrane 12 are dried, the separation membrane 12 is heat-treated to substantially completely burn off the SDA in the separation membrane 12 and penetrate the fine pores in the separation membrane 12 (step S25). ).
  • step S21 the formation of the dense portion 42 in step S21 may be performed after steps S22 to S25 (that is, the formation of the separation membrane 12 on the porous portion 41). .. Further, step S25 may be omitted depending on the usage mode of SDA.
  • steps S21 to S25 are completed, a coating film 13 formed of a layered inorganic compound is formed on the boundary portion 45 between the separation film 12 and the dense portion 42. As a result, the boundary portion 45 is covered with the coating film 13 (step S26).
  • the material of the coating film 13 (hereinafter, also referred to as “coating film material”) is dispersed in a solvent to prepare a dispersion liquid.
  • the coating film material is a powder of a layered inorganic compound (for example, a clay mineral such as smectite).
  • solvent molecules enter the layers of the layered inorganic compound, and the layered inorganic compound is separated into flakes.
  • the size of each slice in the plane direction (that is, the direction perpendicular to the thickness direction) is, for example, several tens of nm to several tens of ⁇ m.
  • the type of solvent is appropriately determined according to the type of material of the coating film 13.
  • the material of the coating film 13 When smectite is used as the material of the coating film 13, pure water or the like can be used as the solvent.
  • the content of the coating film material in the dispersion liquid is appropriately determined depending on the type of the coating film material, the thickness of the coating film 13 to be formed, and the like. The content is, for example, 0.1% by mass to 10% by mass.
  • the dispersion liquid is applied to the support 11 on which the separation film 12 is formed on the inner side surface of the through hole 111.
  • the dispersion liquid is applied to the entire region where the coating film 13 is to be formed (that is, the region including the boundary portion 45) on the inner surface of the through hole 111, and is not applied to other regions.
  • the dispersion liquid is applied, for example, by inserting the longitudinal end portion of the support 11 into the dispersion liquid stored in the container and immersing it (so-called dip coating).
  • the dispersion liquid may be applied by various methods other than dip coating.
  • the dispersion liquid may be sprayed on the support 11 and the separation membrane 12, or the dispersion liquid may be applied by a coater such as a brush.
  • the support 11 and the separation membrane 12 coated with the dispersion liquid are dried.
  • the drying is, for example, natural drying or ventilation drying in a temperature environment of 20 ° C to 100 ° C.
  • a coating film 13 that covers the boundary portion 45 between the separation membrane 12 and the dense portion 42 is formed, and the above-mentioned separation membrane composite 1 is obtained.
  • the separation membrane complex 1 (that is, the support 11, the separation membrane 12 and the coating membrane 13) may be heat-treated at a temperature of 200 ° C. or higher after step S26 (that is, the separation membrane complex 1 and the coating film 13) may be heat-treated (that is, the support film 11 and the coating film 13).
  • Step S27 This improves the adhesion of the coating film 13 to the separation film 12 and the dense portion 42.
  • the denseness of the coating film 13 is also improved.
  • the heating temperature during the heat treatment is, for example, 200 ° C. or higher and 1000 ° C. or lower, preferably 250 ° C. or higher and 800 ° C. or lower, and more preferably 300 ° C. or higher and 600 ° C.
  • the heating time during the heat treatment is, for example, 1 hour to 100 hours.
  • the heat treatment is performed, for example, by accommodating the separation membrane complex 1 in a dryer, an electric furnace, or the like and heating it.
  • the heat treatment may be performed by various other methods.
  • the atmosphere at the time of heat treatment for example, air, oxygen, an inert gas and the like can be used.
  • the separation membrane complex 1 of Examples 1 to 3 in Table 1 is a separation membrane complex including the above-mentioned coating film 13.
  • the separation membrane complex of Comparative Example 1 is a separation membrane complex that does not include a coating film 13 (that is, the boundary portion 45 between the separation membrane 12 and the dense portion 42 is exposed).
  • the permeance rate (that is, permeance) of CO 2 and CH 4 in the separation membrane composite 1 is such that in the above-mentioned separation device 2, the mixed gas of CO 2 and CH 4 is supplied from the supply unit 26 to the separation membrane composite in the outer cylinder 22. I supplied it to 1 and asked for it.
  • the unit of permeation rate is [nmol / ( m2 ⁇ s ⁇ Pa)].
  • the content of CO 2 in the mixed gas is 50% by volume, and the content of CH 4 is 50% by volume.
  • the pressure of the mixed gas supplied from the supply unit 26 to the separation membrane composite 1 (that is, the pressure on the supply side) is 0.3 MPaG.
  • the pressure of the permeated gas that has permeated the separation membrane complex 1 (that is, the permeation side pressure) is 0 MPaG.
  • the permeation rates of CO 2 and CH 4 were determined by measuring the permeated gas with a mass flow meter (MFM) and a gas chromatograph. Then, the CO 2 permeation rate was divided by the CH 4 permeation rate to obtain the ratio of the CO 2 permeation rate to the CH 4 permeation rate (that is, the permeation rate ratio CO 2 / CH 4 ).
  • the transmission rate ratio coefficient in Table 1 is the ratio of the transmission rate ratio CO 2 / CH 4 of Examples 1 to 3 with the transmission rate ratio CO 2 / CH 4 of Comparative Example 1 as a reference (that is, 1.0). It is shown.
  • the permeation rate ratio coefficient is a value obtained by dividing the permeation rate ratio CO 2 / CH 4 of Examples 1 to 3 by the permeation rate ratio CO 2 / CH 4 of Comparative Example 1.
  • the separation membrane complex of Comparative Example 1 was produced by the production method shown in steps S21 to 25 described above.
  • the porous portion 41 of the support 11 is a monolith-type porous alumina base material.
  • the dense portion 42 is a thin film made of glass.
  • the separation membrane 12 is a DDR type zeolite membrane.
  • the hydrothermal synthesis temperature and the hydrothermal synthesis time in step S24 are 130 ° C. and 15 hours, respectively.
  • step SDA was removed by heating at 450 ° C. for 50 hours.
  • the separation membrane complex 1 of Example 1 was produced by performing the above-mentioned steps S26 to S27 with respect to the separation membrane complex of Comparative Example 1.
  • the dispersion liquid in step S26 was prepared by using a clay mineral "Smecton-SA" (manufactured by Kunimine Kogyo Co., Ltd.) as a coating film material and dispersing the coating film material in pure water.
  • Smecton-SA is a synthetic smectite containing saponite as a main component.
  • the content of the coating film material in the dispersion was 1% by mass.
  • the heating temperature and heating time during the heat treatment in step S27 were set to 200 ° C. and 20 hours, respectively.
  • the permeation rate ratio coefficient was 1.6, and the separation performance of the separation membrane complex 1 was improved as compared with Comparative Example 1 having no coating film 13.
  • the improvement in separation performance was that defects such as cracks at the boundary portion 45 between the separation membrane 12 and the dense portion 42 were covered (that is, repaired) by the coating film 13, and leakage of CH 4 from the defects was suppressed. according to.
  • the thickness of the coating film 13 was 0.8 ⁇ m.
  • Example 2 is the same as Example 1 except that the coating film material is changed to the clay mineral "Smecton-SWN" (manufactured by Kunimine Industries, Ltd.).
  • Smecton-SWN is a synthetic smectite containing hectorite as a main component.
  • the permeation rate ratio coefficient was 1.6, and the separation performance of the separation membrane complex 1 was improved as compared with Comparative Example 1 having no coating film 13.
  • the thickness of the coating film 13 was 2.0 ⁇ m.
  • Example 3 is the same as Example 1 except that the coating film material is changed to the clay mineral "Kunipia-F" (manufactured by Kunimine Industries, Ltd.).
  • Kunipia-F is a purified bentonite containing montmorillonite as a main component.
  • the permeation rate ratio coefficient was 1.3, and the separation performance of the separation membrane complex 1 was improved as compared with Comparative Example 1 having no coating film 13.
  • the thickness of the coating film 13 was 0.5 ⁇ m.
  • the permeation rate ratio coefficient was measured in the same manner as above, and as a result, the permeation rate ratio coefficient did not change. From this, it can be seen that the coating film 13 in the separation membrane complex 1 of Examples 1 to 3 has high heat resistance.
  • the separation membrane complex 1 includes a support 11, a separation membrane 12, and a coating membrane 13.
  • the support 11 has a porous portion 41 and a dense portion 42 which are continuously arranged.
  • the separation membrane 12 is provided on the porous portion 41 of the support 11.
  • the end portion of the separation membrane 12 comes into contact with the compact portion 42.
  • the coating film 13 is formed of a layered inorganic compound.
  • the coating film 13 covers the boundary portion 45 between the dense portion 42 and the separation membrane 12.
  • defects such as cracks at the boundary portion 45 between the separation membrane 12 and the dense portion 42 are covered (that is, repaired) by the coating membrane 13, so that the above-mentioned low-permeability substance is removed from the defects. It is possible to prevent leakage and inclusion in the permeate.
  • the separation performance of the separation membrane complex 1 can be improved. Further, by using the layered inorganic compound as the coating film material, it is possible to easily form a dense coating film 13 as compared with the case where the coating film is formed by zeolite. As a result, the separation membrane complex 1 can be easily produced.
  • the layered inorganic compound is preferably a clay mineral or a layered metal oxide. As a result, the heat resistance of the coating film 13 can be increased.
  • the layered inorganic compound is more preferably a clay mineral. This makes it possible to further facilitate the formation of the coating film 13. Further, since clay minerals are easily available and relatively inexpensive, the production cost of the separation membrane complex 1 can be reduced.
  • the layered inorganic compound is smectite (Examples 1 and 2).
  • the denseness of the coating film 13 can be further improved and the separation performance of the separation membrane composite 1 can be further improved as compared with the case where the layered inorganic compound is bentonite (Example 3). ..
  • the average thickness of the coating film 13 is preferably 0.002 ⁇ m or more.
  • the denseness of the coating film 13 can be improved, and the permeation of gas, liquid, or the like through the coating film 13 can be suitably suppressed.
  • the separation performance of the separation membrane complex 1 can be suitably improved.
  • the separation membrane 12 is preferably a zeolite membrane.
  • the separation membrane 12 is preferably a zeolite membrane.
  • the separation device 2 includes the separation membrane complex 1 and a supply unit 26 that supplies a mixed substance containing a plurality of types of gases or liquids to the separation membrane complex 1.
  • the separation membrane complex 1 separates from the mixed substance by permeating the highly permeable substance (that is, the highly permeable substance) in the mixed substance.
  • the highly permeable substance can be separated from the mixed substance at a high permeation rate ratio.
  • step S11 the step of preparing the separation membrane complex 1 (step S11) and a mixed substance containing a plurality of types of gases or liquids are supplied to the separation membrane complex 1, and the permeability in the mixed substance is increased.
  • step S12 of separating a high substance (that is, a highly permeable substance) from the mixed substance by permeating the separation membrane composite 1 is provided. This makes it possible to separate the highly permeable substance from the mixed substance at a high permeation rate ratio.
  • the mixed substances are hydrogen, helium, nitrogen, oxygen, water, steam, carbon monoxide, carbon dioxide, nitrogen oxides, ammonia, sulfur oxides, hydrogen sulfide, sulfur fluoride, mercury, alcine, and hydrogen cyanide.
  • the method for producing the separation membrane composite 1 described above includes a step of continuously arranging the dense portion 42 of the support 11 on the porous portion 41 (step S21) and a separation membrane 12 on the porous portion 41 of the support 11.
  • step S21 By forming a coating film 13 formed of a layered inorganic compound on the boundary portion 45 between the separation film 12 whose end contacts the dense portion 42 and the dense portion 42 (step S24).
  • step S26 A step (step S26) of covering the boundary portion 45 is provided.
  • the method for producing the separation membrane complex 1 further includes a step (step S27) of heat-treating the support 11, the separation membrane 12, and the coating film 13 at a temperature of 200 ° C. or higher after step S26. Is preferable. As a result, the adhesion between the separation film 12 and the dense portion 42 and the coating film 13 can be improved. In addition, the denseness of the coating film 13 can be improved.
  • the average thickness of the coating film 13 does not necessarily have to be 0.002 ⁇ m or more, and does not have to be 10 ⁇ m or less. That is, the average thickness of the coating film 13 may be less than 0.002 ⁇ m or thicker than 10 ⁇ m.
  • the longitudinal end portion of the separation membrane 12 and the longitudinal end portion of the dense portion 42 are in the radial direction of the through hole 111 (that is, the figure). Although they hardly overlap in the vertical direction in 2), these ends may overlap.
  • the longitudinal end of the dense portion 42 is in direct contact with the inner surface of the through hole 111 of the porous portion 41, and the longitudinal end of the separation membrane 12 is , May be provided on the dense portion 42.
  • the longitudinal end portion of the separation membrane 12 is indirectly in contact with the inner surface of the through hole 111 of the porous portion 41 with the dense portion 42 interposed therebetween.
  • the boundary portion 45 between the separation membrane 12 and the dense portion 42 extends a substantially circumferential region in contact between the edge of the dense portion 42 and the separation membrane 12 in a direction perpendicular to the surface of the porous portion 41. It refers to a substantially circumferential portion where the surface of the separation membrane 12 and the surface of the separation membrane 12 intersect.
  • the coating film 13 covers the boundary portion 45 over substantially the entire area and extends from the boundary portion 45 on both sides in the longitudinal direction. Thereby, the separation performance of the separation membrane complex 1 can be improved in the same manner as described above. Moreover, the dense coating film 13 can be easily formed.
  • the longitudinal end of the separation membrane 12 is in direct contact with the inner surface of the through hole 111 of the porous portion 41, and the longitudinal end of the dense portion 42 is , May be provided on the separation membrane 12.
  • the longitudinal end of the dense portion 42 is indirectly in contact with the inner surface of the through hole 111 of the porous portion 41 with the separation membrane 12 interposed therebetween.
  • the boundary portion 45 between the separation membrane 12 and the dense portion 42 refers to a substantially circumferential portion where the edge of the dense portion 42 and the separation membrane 12 are in contact with each other in the radial direction of the through hole 111.
  • the coating film 13 covers the boundary portion 45 over substantially the entire area and extends from the boundary portion 45 on both sides in the longitudinal direction. Thereby, the separation performance of the separation membrane complex 1 can be improved in the same manner as described above. Moreover, the dense coating film 13 can be easily formed.
  • the dense portion 42 may be fixed to the end face in the longitudinal direction of the porous portion 41.
  • the cross-sectional shape of the porous portion 41 and the cross-sectional shape of the dense portion 42 may be substantially the same or different.
  • the separation membrane 12 is provided on the porous portion 41 and extends on the dense portion 42. That is, the separation membrane 12 covers the boundary between the porous portion 41 and the dense portion 42.
  • the boundary portion 45 between the separation membrane 12 and the dense portion 42 refers to a substantially circumferential portion where the edge of the dense portion 42 and the separation membrane 12 are in contact with each other in the radial direction of the through hole 111.
  • the coating film 13 covers the boundary portion 45 over substantially the entire area and extends from the boundary portion 45 on both sides in the longitudinal direction. Thereby, the separation performance of the separation membrane complex 1 can be improved in the same manner as described above. Moreover, the dense coating film 13 can be easily formed. In the example shown in FIG. 10, the covering film 13 covers the inner side surface of the through hole 421 of the dense portion 42 over substantially the entire surface.
  • the method for producing the separation membrane complex 1 is not limited to the above example, and may be changed in various ways.
  • the step of heat-treating the separation film 12 and the coating film 13 at a temperature of 200 ° C. or higher may be omitted.
  • the separation membrane complex 1 may further include a functional membrane or a protective membrane laminated on the separation membrane 12 in addition to the support 11, the separation membrane 12 and the coating membrane 13.
  • a functional film or a protective film may be an inorganic film such as a zeolite film, a silica film or a carbon film, or an organic film such as a polyimide film or a silicone film.
  • the separation membrane 12 may be a membrane other than the zeolite membrane (for example, the above-mentioned inorganic membrane or organic membrane).
  • the separation device 2 and the separation method described above substances other than the substances exemplified in the above description may be separated from the mixed substance. Further, the structure of the separating device 2 is not limited to the above example, and may be changed in various ways.
  • the separation membrane composite of the present invention can be used as, for example, a gas separation membrane, and further, can be used in various fields as a separation membrane, an adsorption membrane, and the like of various substances other than gas.

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PCT/JP2021/036740 2020-12-17 2021-10-05 分離膜複合体、分離装置、分離方法および分離膜複合体の製造方法 Ceased WO2022130741A1 (ja)

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JP2022569726A JP7614228B2 (ja) 2020-12-17 2021-10-05 分離膜複合体、分離装置、分離方法および分離膜複合体の製造方法
CN202180061877.XA CN116437998A (zh) 2020-12-17 2021-10-05 分离膜复合体、分离装置、分离方法及分离膜复合体的制造方法
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