WO2021186959A1 - ガス分離方法およびゼオライト膜 - Google Patents

ガス分離方法およびゼオライト膜 Download PDF

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Publication number
WO2021186959A1
WO2021186959A1 PCT/JP2021/004990 JP2021004990W WO2021186959A1 WO 2021186959 A1 WO2021186959 A1 WO 2021186959A1 JP 2021004990 W JP2021004990 W JP 2021004990W WO 2021186959 A1 WO2021186959 A1 WO 2021186959A1
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Prior art keywords
gas
zeolite membrane
highly permeable
mixed gas
zeolite
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PCT/JP2021/004990
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English (en)
French (fr)
Japanese (ja)
Inventor
清水　克也
真紀子 市川
谷島　健二
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NGK Insulators Ltd
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NGK Insulators Ltd
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Priority to JP2022508134A priority Critical patent/JP7376689B2/ja
Priority to BR112022018502-2A priority patent/BR112022018502B1/pt
Publication of WO2021186959A1 publication Critical patent/WO2021186959A1/ja
Priority to US17/931,918 priority patent/US12458949B2/en
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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
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • 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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • 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
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • 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
    • B01D69/1213—Laminated layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1218—Layers having the same chemical composition, but different properties, e.g. pore size, molecular weight or porosity
    • 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
    • B01D71/0215—Silicon carbide; Silicon nitride; Silicon oxycarbide
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • B01D2256/245—Methane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates to a gas separation method for separating a mixed gas and a zeolite membrane formed on a porous support.
  • Japanese Patent Application Laid-Open No. 2012-236123 proposes a system for separating and recovering carbon dioxide in exhaust gas by permeating it through a zeolite membrane.
  • International Publication No. 2016/052058 proposes a technique for separating an olefin compound from a fluid to be treated by using a zeolite membrane.
  • the trace components include final products, unreacted raw materials, intermediate products such as olefins, alcohols, esters or carboxylic acids. Is.
  • Document 1 proposes that the exhaust gas is guided to the pretreatment facility before the exhaust gas is supplied to the zeolite membrane, and the pretreatment facility removes the water content in the exhaust gas to reduce the water concentration. .. Further, in Document 2, a reduction treatment of acetylene compounds, a reduction treatment of sulfur compounds, or a reduction treatment of fine particle components is performed in the pretreatment section.
  • the pretreatment equipment since there are a wide variety of trace substances contained in exhaust gas and the like, if all of these trace substances are to be removed in the pretreatment equipment in order to suppress changes in the permeation performance of the zeolite membrane over time, the pretreatment equipment will be used. It can be large and complex.
  • the present invention is directed to a gas separation method for separating a mixed gas, and an object of the present invention is to easily suppress a decrease in permeation performance of a zeolite membrane over time.
  • the gas separation method includes a) a step of preparing a zeolite membrane composite comprising a porous support and a zeolite membrane formed on the support, and b) high permeability.
  • a mixed gas containing the gas and a trace gas having a concentration lower than that of the highly permeable gas is supplied to the zeolite membrane composite, and the highly permeable gas is permeated through the zeolite membrane composite to allow another gas. It is provided with a step of separating from the gas.
  • the trace gas contains an organic substance having a molar concentration of 1.0 mol% or more in the mixed gas.
  • the adsorption equilibrium constant of the organic substance with respect to the zeolite membrane is less than 150 times that of the highly permeable gas.
  • the highly permeable gas is hydrogen, nitrogen, oxygen or carbon dioxide.
  • the maximum number of membered rings of the zeolite crystal contained in the zeolite membrane is 8.
  • the gas separation method further comprises a step of removing from the mixed gas an organic substance having an adsorption equilibrium constant with respect to the zeolite membrane of 150 times or more that of the highly permeable gas before the step b). ..
  • the mixed gas further contains a low permeable gas having a lower permeability to the zeolite membrane than the highly permeable gas.
  • the concentration of the trace gas is lower than the concentration of the low-permeability gas.
  • the mixed gas is hydrogen, helium, nitrogen, oxygen, water, water vapor, carbon monoxide, carbon dioxide, nitrogen oxides, ammonia, sulfur oxides, hydrogen sulfide, sulfur fluoride, mercury, arsine, hydrogen cyanide, etc. It contains one or more substances among carbonyl sulfide, hydrogen sulfides of C1 to C8, organic acids, alcohols, mercaptans, esters, ethers, ketones and aldehydes.
  • the present invention is also directed to a zeolite membrane formed on a porous support.
  • the zeolite membrane according to one preferred embodiment of the present invention contains a highly permeable gas and an organic substance having an adsorption equilibrium constant of less than 150 times that of the highly permeable gas, and is a trace gas having a concentration lower than that of the highly permeable gas.
  • the permeation ratio P40 / P10 is 0. It is 85 or more and 1.00 or less.
  • the highly permeable gas is hydrogen, nitrogen, oxygen or carbon dioxide.
  • the mixed gas further contains a low permeable gas having a lower permeability to the zeolite membrane than the highly permeable gas.
  • the concentration of the trace gas is lower than the concentration of the low-permeability gas.
  • FIG. 1 is a diagram showing a schematic structure of a separation device 2 according to an embodiment of the present invention.
  • the separation device 2 is a device that supplies a mixed gas containing a plurality of types of gases to the zeolite membrane composite 1 and separates a highly permeable gas in the mixed gas from the mixed gas by permeating the zeolite membrane composite 1. Is.
  • the separation in the separation device 2 may be performed, for example, for the purpose of extracting a gas having high permeability from the mixed gas, or may be performed for the purpose of concentrating the gas having low permeability.
  • the mixed gas includes, 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 oxide, ammonia (NH 3 ), sulfur oxide, hydrogen sulfide (H 2 S), sulfur fluoride, mercury (Hg), arsine (AsH 3 ), hydrogen cyanide (HCN), hydrogen sulfide It contains one or more substances among carbonyl (COS), hydrogens of C1 to C8, organic acids, alcohols, mercaptans, esters, ethers, ketones and aldehydes.
  • 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 nitrous oxide) (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 (socks) 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 of C3 to C8 may be any of a linear compound, a side chain compound and a cyclic compound.
  • the hydrocarbons of C3 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 the ones 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 3 H 4 O 2). 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 alcohols mentioned above 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) and 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 acetate ester.
  • ethers include, 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 mentioned above are, for example, acetaldehyde (CH 3 CHO), propionaldehyde (C 2 H 5 CHO) or butyraldehyde (butyraldehyde) (C 3 H 7 CHO).
  • the separation device 2 includes a zeolite membrane complex 1, a sealing portion 21, an outer cylinder 22, two sealing members 23, a supply portion 26, a first recovery section 27, and a second recovery section 28. ..
  • the zeolite membrane composite 1, the sealing portion 21, and the sealing member 23 are housed in the internal space of 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. In FIG. 1, parallel diagonal lines in the cross sections of some configurations are omitted.
  • the outer cylinder 22 is 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 zeolite membrane composite 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. 1), 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 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 is, for example, a blower or a pump that pumps the mixed gas toward the outer cylinder 22.
  • the blower or pump includes a pressure adjusting unit that adjusts the pressure of the mixed gas supplied to the outer cylinder 22.
  • the first recovery unit 27 and the second recovery unit 28 are, 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 sealing portions 21 are attached to both ends of the support 11 in the longitudinal direction (that is, the left-right direction in FIG. 1), and cover both end faces in the longitudinal direction of the support 11 and outer surfaces in the vicinity of the end faces. It is a member to be sealed.
  • the sealing portion 21 prevents the inflow and outflow of gas from both end faces of the support 11.
  • the sealing portion 21 is, for example, a plate-shaped member formed of glass or resin. The material and shape of the sealing portion 21 may be changed as appropriate. Since the sealing portion 21 is provided with a plurality of openings that overlap with the plurality of through holes 111 (described later) of the support 11, both ends of each through hole 111 of the support 11 in the longitudinal direction are sealed portions. Not covered by 21. Therefore, gas and the like can flow in and out from both ends into the through hole 111.
  • the two sealing members 23 are arranged over the entire circumference between the outer surface of the zeolite membrane complex 1 and the inner surface of the outer cylinder 22 in the vicinity of both ends in the longitudinal direction of the zeolite membrane composite 1.
  • Each sealing member 23 is a substantially annular member formed of a material that does not allow gas to permeate.
  • 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 zeolite membrane composite 1 and the inner surface of the outer cylinder 22 over the entire circumference. In the example shown in FIG. 1, the sealing member 23 is in close contact with the outer surface of the sealing portion 21, and indirectly adheres to the outer surface of the zeolite membrane composite 1 via the sealing portion 21.
  • the space between the sealing member 23 and the outer surface of the zeolite membrane composite 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 is almost or completely impossible. ..
  • FIG. 2 is a cross-sectional view of the zeolite membrane complex 1.
  • FIG. 3 is an enlarged cross-sectional view showing a part of the zeolite membrane complex 1.
  • the zeolite membrane complex 1 includes a porous support 11 and a zeolite membrane 12 formed on the support 11.
  • the zeolite membrane 12 does not include, at least, one in which zeolite is formed in a film shape on the surface of the support 11, and one in which zeolite particles are simply dispersed in an organic membrane. Further, the zeolite membrane 12 may contain two or more types of zeolite having different structures and compositions.
  • the zeolite membrane 12 is drawn with a thick line.
  • the zeolite membrane 12 is shaded in parallel. Further, in FIG. 3, the thickness of the zeolite membrane 12 is drawn thicker than it actually is.
  • the support 11 is a porous member that can permeate gas.
  • the support 11 is a monolith type in which a plurality of through holes 111 extending in the longitudinal direction (that is, the left-right direction in FIG. 2) are provided on an integrally molded columnar body. It is a support.
  • the support 11 has a substantially columnar shape.
  • 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 zeolite membrane 12 is formed on the inner side surface of the through hole 111, and covers the inner side surface of the through hole 111 over substantially the entire surface.
  • the length of the support 11 (that is, the length in the vertical direction in FIG. 1) is, for example, 10 cm to 200 cm.
  • the outer diameter of the support 11 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 support 11 is, for example, 0.1 ⁇ m to 5.0 ⁇ m, preferably 0.2 ⁇ m to 2.0 ⁇ m.
  • the shape of the support 11 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 support 11 is tubular or cylindrical, the thickness of the support 11 is, for example, 0.1 mm to 10 mm.
  • the support 11 is formed of a ceramic sintered body.
  • the ceramic sintered body selected as the material of the support 11 include alumina, silica, mullite, zirconia, titania, yttria, silicon nitride, and silicon carbide.
  • the support 11 contains at least one of alumina, silica and mullite.
  • the support 11 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 support 11 is, for example, 0.01 ⁇ m to 70 ⁇ m, preferably 0.05 ⁇ m to 25 ⁇ m.
  • the average pore diameter of the support 11 in the vicinity of the surface on which the zeolite 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. ..
  • the porosity of the support 11 in the vicinity of the surface on which the zeolite membrane 12 is formed is, for example, 20% to 60%.
  • the support 11 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 zeolite membrane 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 support 11 is, for example, 0.01 ⁇ m to 1 ⁇ m, preferably 0.05 ⁇ m to 0.5 ⁇ m.
  • the above 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 zeolite membrane 12 is a porous membrane having pores.
  • the zeolite membrane 12 can be used as a separation membrane that separates a specific substance from a mixed gas in which a plurality of types of gases are mixed by utilizing a molecular sieving action.
  • other gases are less likely to permeate than the specific gas.
  • the permeation amount of the other gas in the zeolite membrane 12 is smaller than the permeation amount of the specific gas.
  • the thickness of the zeolite 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 zeolite membrane 12 improves the separation performance. When the zeolite membrane 12 is thinned, the permeation amount increases.
  • the surface roughness (Ra) of the zeolite 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 average pore diameter of the zeolite membrane 12 is preferably 0.2 nm or more and 0.8 nm or less, more preferably 0.3 nm or more and 0.5 nm or less, and further preferably 0.3 nm or more and 0. It is 4 nm or less.
  • the average pore diameter of the zeolite membrane 12 is smaller than the average pore diameter of the support 11 in the vicinity of the surface on which the zeolite membrane 12 is formed.
  • the arithmetic mean of the minor axis and the major axis of the n-membered ring pores is taken as the average pore diameter.
  • the arithmetic mean of the minor axis and the major axis of all the n-membered ring pores is taken as the average pore diameter of the zeolite.
  • 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 average pore size of the zeolite membrane is uniquely determined by the skeletal 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 / database />.
  • the type of zeolite constituting the zeolite membrane 12 is not particularly limited, but 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, LEV-type, LTA-type, MEL-type, MFI-type, MOR-type, PAU-type, RHO-type, SAT-type, SOD-type, and other zeolites may be used.
  • zeolites such as AEI type, AFN type, AFV type, AFX type, CHA type, DDR type, ERI type, ETL type, GIS type, LEV type, LTA type, PAU type, RHO type and SAT type.
  • the zeolite constituting the zeolite membrane 12 contains, for example, Al as a T atom.
  • the atom (T atom) located at the center of the oxygen tetrahedron (TO 4 ) constituting the zeolite is a zeolite composed of silicon (Si) and aluminum (Al), and the T atom is Al.
  • SAPO-type zeolite consisting of T atom consisting of Si, Al and P SAPO-type zeolite consisting of T atom consisting of Si, Al and P
  • ZnAPSO-type zeolite whose T atom is composed of zinc (Zn), Si, Al, and P can be used.
  • a part of the T atom may be replaced with another element.
  • Zeolite membrane 12 contains, for example, Si.
  • the zeolite membrane 12 may contain, for example, any two or more of Si, Al and P.
  • the zeolite membrane 12 may contain an alkali metal.
  • the alkali metal is, for example, sodium (Na) or potassium (K).
  • the Si / Al ratio in the zeolite membrane 12 is, for example, 1 or more and 100,000 or less.
  • 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 zeolite 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 zeolite membrane 12 is, for example, a DDR type zeolite.
  • the zeolite membrane 12 is a zeolite membrane composed of zeolite whose structural code is "DDR" as defined by the International Zeolite Society.
  • the intrinsic pore diameter of the zeolite constituting the zeolite membrane 12 is 0.36 nm ⁇ 0.44 nm, and the average pore diameter is 0.40 nm.
  • the permeation amount (permeence) of CO 2 of the zeolite membrane 12 at 20 ° C. to 400 ° C. is, for example, 100 nmol / m 2 ⁇ s ⁇ Pa or more.
  • the CO 2 permeation amount / CH 4 leakage amount ratio (permeence ratio) of the zeolite membrane 12 at 20 ° C. to 400 ° C. is, for example, 100 or more.
  • the permeence and the permeence ratio are those when the partial pressure difference of CO 2 between the supply side and the permeation side of the zeolite membrane 12 is 1.5 MPa.
  • a seed crystal used for producing the zeolite membrane 12 is prepared.
  • the seed crystal is obtained from, for example, a DDR-type zeolite powder produced by hydrothermal synthesis and obtained from the 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 porous support 11 is immersed in the solution in which the seed crystal is dispersed, and the seed crystal is attached to the support 11.
  • the seed crystal is attached to the support 11 by bringing the solution in which the seed crystal is dispersed into contact with the portion of the support 11 on which the zeolite membrane 12 is to be formed.
  • a seed crystal adhesion support is produced.
  • the seed crystal may be attached to the support 11 by another method.
  • the support 11 to which the seed crystal is attached is immersed in the raw material solution.
  • the raw material solution is prepared by dissolving, for example, a Si source and a structure defining agent (hereinafter, also referred to as “SDA”) in a solvent.
  • SDA structure defining agent
  • 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 SDA contained in the raw material solution is, for example, an organic substance.
  • As the SDA for example, 1-adamantanamine can be used.
  • the DDR-type zeolite membrane 12 is formed on the support 11 by growing the DDR-type zeolite around the seed crystal as a nucleus by hydrothermal synthesis.
  • the temperature during hydrothermal synthesis is preferably 120 to 200 ° C, for example 160 ° C.
  • the hydrothermal synthesis time is preferably 10 to 100 hours, for example 30 hours.
  • the support 11 and the zeolite membrane 12 are washed with pure water. After washing, the support 11 and the zeolite membrane 12 are dried at, for example, 80 ° C. After the support 11 and the zeolite membrane 12 are dried, the zeolite membrane 12 is heat-treated to substantially completely burn and remove the SDA in the zeolite membrane 12 to penetrate the fine pores in the zeolite membrane 12. As a result, the above-mentioned zeolite membrane complex 1 is obtained.
  • the flow of separation of the mixed gas by the separation device 2 will be described with reference to FIG.
  • the zeolite membrane complex 1 is prepared by preparing the above-mentioned separation device 2 (step S11).
  • the supply unit 26 supplies a mixed gas containing a plurality of types of gases having different permeability to the zeolite membrane 12 to the internal space of the outer cylinder 22.
  • the mixed gas includes a highly permeable gas and a trace gas.
  • the mixed gas may further contain a low permeable gas.
  • the trace gas is a component having a molar concentration (mol%) of less than 10 mol% in the mixed gas.
  • the trace gas may be one type of gas or two or more types of gas.
  • the molar concentration of each kind of trace gas in the mixed gas is less than 10 mol%, and the total molar concentration of the two or more kinds of trace gases in the mixed gas is 10 mol%. May be larger than.
  • the total molar concentration is, for example, 1 mol% to 30 mol%, preferably 1 mol% to 10 mol%.
  • the main components of the mixed gas are a highly permeable gas and a low permeable gas.
  • the highly permeable gas is one type of gas having the highest permeability to the zeolite membrane 12 among the main components of the mixed gas.
  • the low-permeability gas is a component obtained by removing the high-permeability gas from the main component of the mixed gas, and the permeability to the zeolite membrane 12 is lower than that of the high-permeability gas.
  • the low-permeability gas may be one kind of gas or two or more kinds of gases. In other words, the mixed gas may contain three or more kinds of gases as main components.
  • the molar concentration of the highly permeable gas in the mixed gas and the molar concentration of the low permeable gas are 10 mol% or more.
  • the molar concentration of the trace gas in the mixed gas is based on the molar concentration of the highly permeable gas in the mixed gas and the molar concentration of the low permeable gas (in the case of two or more types of gas, each type of low permeable gas). Is also low.
  • the total content of the highly permeable gas and the low permeable gas in the mixed gas (that is, the content of the main component) is, for example, 70 mol% to 99 mol%, preferably 90 mol% to 99 mol%.
  • the highly permeable gas is, for example, H 2 , N 2 , O 2 or CO 2 .
  • the low permeable gas contains, for example, one or more of N 2 , air and CH 4.
  • the highly permeable gas and the low permeable gas are CO 2 and CH 4 , respectively.
  • Trace gas contains organic matter.
  • organic substances an organic substance in which the adsorption equilibrium constant with respect to the zeolite membrane 12 is 150 times or more the adsorption equilibrium constant with respect to the zeolite membrane 12 of the highly permeable gas is referred to as "highly adsorptive gas”.
  • the organic substances whose adsorption equilibrium constant with respect to the zeolite membrane 12 is less than 150 times the adsorption equilibrium constant with respect to the zeolite membrane 12 of the highly permeable gas are referred to as "low adsorptive gas”.
  • the molar concentration of the highly adsorptive gas in the mixed gas is less than 1.0 mol%, preferably less than 0.05 mol%, and more preferably less than 0.025 mol%.
  • the molar concentration of the low-adsorption gas in the mixed gas is 1.0 mol% or more, preferably 1.2 mol% or more.
  • the adsorption equilibrium constant of the highly permeable gas to the zeolite membrane 12 is determined by performing an adsorption test of the highly permeable gas to the zeolite membrane 12 and creating a Langmuir plot from the adsorption isotherm which is the obtained measurement data. It can be calculated. Specifically, first, the same type of zeolite powder as the zeolite membrane 12 (for example, DDR type zeolite powder) is prepared. The Si / Al ratio of the zeolite powder is substantially the same as the Si / Al ratio of the zeolite membrane 12. In addition, a glass container for the adsorption test is prepared, and the weight of the empty glass container is measured.
  • a predetermined weight of zeolite powder is contained in the glass container. Then, as the zeolite powder is heated, the inside of the glass container is exhausted to create a vacuum atmosphere (that is, evacuated). As a result, the adsorbent is desorbed from the zeolite powder. After that, the weight of the glass container containing the zeolite powder is measured, and the weight of the zeolite powder is obtained by subtracting the weight of the empty glass container described above from the measured weight.
  • the following processing is performed in a state where the temperature of the portion of the glass container containing the zeolite powder is maintained at a predetermined temperature.
  • the predetermined temperature is the same temperature as the temperature at which the mixed gas is separated in the separation device 2, and is, for example, room temperature (25 ° C.).
  • a predetermined amount of highly permeable gas is introduced into the glass container having a vacuum atmosphere. In the glass container, a part of the highly permeable gas is adsorbed on the zeolite powder. As a result, the pressure inside the glass container is reduced.
  • the pressure inside the glass container becomes constant and the adsorption of the highly permeable gas to the zeolite powder is stable
  • the pressure P inside the glass container is measured, and the pressure drop due to the adsorption indicates that the highly permeable gas
  • the adsorption amount q is calculated. After that, in the same manner as described above, the introduction of the highly permeable gas into the glass container and the acquisition of the pressure P and the adsorption amount q are repeated.
  • the measured values of the pressure P and the adsorption amount q are plotted with the horizontal axis as P and the vertical axis as P / q.
  • the plotted points are linearly approximated by the least squares method or the like, and the slope a and the intercept b of the approximate straight line are obtained.
  • the adsorption equilibrium constant of the highly permeable gas is calculated by dividing the slope a by the intercept b.
  • the adsorption equilibrium constants of the high-adsorption gas and the low-adsorption gas are also calculated by the same method as described above.
  • the highly adsorptive gas may be one kind of organic substance or may contain a plurality of kinds of organic substances.
  • the molar concentration of the highly adsorptive gas in the mixed gas is the total molar concentration of the plurality of types of organic substances.
  • the highly adsorptive gas is, for example, an organic substance composed of carbon (C) and hydrogen (H), or an organic substance composed of carbon (C), hydrogen (H) and oxygen (O), and has a vapor pressure at 25 ° C. It is a gas of less than 250 kPa.
  • the highly adsorptive gas for example, vinyl acetate or ethanol is used.
  • the low-adsorption gas may be one kind of organic substance or may contain a plurality of kinds of organic substances.
  • the molar concentration of the low-adsorption gas in the mixed gas is the total molar concentration of the plurality of types of organic substances.
  • the low-adsorption gas is, for example, an organic substance composed of carbon (C) and hydrogen (H), or an organic substance composed of carbon (C), hydrogen (H) and oxygen (O), and has a vapor pressure at 25 ° C. It is a gas of 250 kPa or more.
  • the low adsorption gas for example, ethylene or propylene is used.
  • the trace gas may contain an inorganic gas.
  • the trace gas may not substantially contain the highly adsorptive gas. In this case, the concentration of the highly adsorptive gas in the mixed gas is substantially 0 mol%.
  • the highly adsorptive gas is removed from the mixed gas before the mixed gas is supplied to the separation device 2 (step S12).
  • the molar concentration of the highly adsorptive gas in the mixed gas is reduced.
  • the removal of the highly adsorptive gas in step S12 is performed, for example, by passing the mixed gas through a liquid having a high absorbency of the highly adsorptive gas and allowing the liquid to absorb the highly adsorptive gas.
  • the removal of the highly adsorptive gas may be performed by passing the mixed gas through an adsorbent having a high adsorptivity of the highly adsorptive gas and adsorbing the highly adsorptive gas to the adsorbent.
  • step S12 In the treatment for removing the highly adsorptive gas in step S12, it is sufficient that the molar concentration of the highly adsorbent gas in the mixed gas can be reduced, and it is not always necessary to remove the entire amount of the highly adsorbent gas in the mixed gas. No.
  • step S12 preferably, the low permeable gas is not intentionally removed from the mixed gas.
  • the process intended to remove the low permeable gas from the mixed gas is not performed in step S12.
  • the pretreatment for separating the highly permeable gas in step S13 which will be described later, is simplified by selectively removing the highly adsorptive gas from the trace gases contained in the mixed gas. Can be done.
  • the low adsorption gas may also be removed.
  • the mixed gas after the removal of the highly adsorptive gas is performed is supplied from the supply unit 26 into the outer cylinder 22.
  • the pressure (that is, the introduction pressure) of the mixed gas supplied from the supply unit 26 to the internal space of the outer cylinder 22 is, for example, 0.1 MPa to 20.0 MPa.
  • the temperature at which the mixed gas is separated is, for example, 10 ° C to 200 ° 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 zeolite membrane composite 1 as shown by an arrow 251.
  • the highly permeable gas (for example, CO 2 ) in the mixed gas is derived from the outer surface of the support 11 through the zeolite membrane 12 provided on the inner surface of each through hole 111 and the support 11. NS.
  • the highly permeable gas is separated from other gases such as the low permeable gas (for example, CH 4) in the mixed gas (step S13).
  • the gas derived from the outer surface of the support 11 (hereinafter, referred to as “permeated gas”) is recovered by the second recovery unit 28 via the second discharge port 223 as shown by the arrow 253.
  • the pressure (that is, permeation pressure) of the gas recovered by the second recovery unit 28 via the second discharge port 223 is, for example, about 1 atm (0.101 MPa).
  • the gas excluding the gas that has permeated through the zeolite membrane 12 and the support 11 has the through holes 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 via the first discharge port 222 is, for example, substantially the same as the introduction pressure.
  • the non-permeated gas may include a highly permeable gas that has not permeated the zeolite membrane 12 in addition to the above-mentioned low permeable gas and trace gas.
  • the molar concentration of the organic matter of the trace gas in the mixed gas of the highly adsorptive gas is low. Therefore, it is suppressed that the organic substance of the trace gas is adsorbed on the pores of the zeolite membrane 12. As a result, it is possible to prevent the highly adsorptive gas adsorbed on the zeolite membrane 12 from inhibiting the permeation of the highly permeable gas through the zeolite membrane 12. As a result, it is possible to suppress a decrease in the permeation performance of the highly permeable gas due to the zeolite membrane 12 over time.
  • the permeation ratio (P40 / P10) in the table is such that in the separation device 2 described above, a mixed gas containing a highly permeable gas (for example, CO 2 ) is supplied to the zeolite membrane composite 1 to obtain the zeolite membrane composite 1. It was determined based on the permeation amount of the permeated gas.
  • a mixed gas containing a highly permeable gas for example, CO 2
  • the permeation amount ratio (P40 / P10) is obtained by dividing the permeation amount 40 minutes after the start of supply of the mixed gas by the permeation amount 10 minutes after the start of supply of the mixed gas.
  • the pressure of the mixed gas supplied from the supply unit 26 was 0.4 MPa, and the pressure (that is, permeation pressure) of the gas recovered by the recovery unit 28 was about 1 atm (0.101 MPa).
  • the zeolite membrane 12 of the zeolite membrane composite 1 is a DDR type.
  • Examples 1 to 6 and Comparative Examples 1 to 4 the highly permeable gas and the low permeable gas contained in the mixed gas were CO 2 and CH 4 , respectively, and the types of organic substances in the trace gas were changed. Further, in Examples 1 to 6 and Comparative Examples 1 to 4, the molar concentration of the highly permeable gas in the mixed gas was 50 mol%, and the molar concentration of the organic substance was 1.0 mol% to 1.5 mol%. Changed in range. The molar concentration of the low-permeability gas in the mixed gas is 100 mol% minus the molar concentration of the high-permeability gas and the organic substance.
  • the organic substances in the trace gas are ethylene, propylene, and 1-butene, respectively.
  • the adsorption equilibrium constant of ethylene with respect to the zeolite membrane 12 (hereinafter, also simply referred to as “adsorption equilibrium constant”) is 9 times the adsorption equilibrium constant of the highly permeable gas.
  • the adsorption equilibrium constants of propylene and 1-butene are 52 times and 134 times the adsorption equilibrium constants of highly permeable gas, respectively. Therefore, these organic substances in the trace gas are low adsorptive gases.
  • the molar concentration of the organic substance in the mixed gas is 1.5 mol%.
  • the permeation ratio (P40 / P10) was 0.98 to 1.00.
  • the organic substances in the trace gas are ethanol and vinyl acetate, respectively.
  • the adsorption equilibrium constant of ethanol is 474 times the adsorption equilibrium constant of highly permeable gas.
  • the adsorption equilibrium constant of vinyl acetate is 406 times the adsorption equilibrium constant of highly permeable gas. Therefore, these organic substances in the trace gas are highly adsorptive gases.
  • the molar concentration of the organic substance in the mixed gas is 1.5 mol% as in Examples 1 to 3.
  • the permeation ratio (P40 / P10) was as low as 0.09 to 0.32.
  • Examples 4 to 6 and Comparative Examples 3 to 4 are the same as those of Examples 1 to 3 and Comparative Examples 1 and 2 except that the molar concentration of the organic substance in the mixed gas was changed to 1.0 mol%.
  • the permeation ratio (P40 / P10) was as high as 0.99 to 1.00, and in Comparative Examples 3 to 4, the permeation ratio (P40 / P10) was 0.12 to 0. It was as low as 41.
  • the gas separation method for separating the mixed gas includes the step of preparing the zeolite membrane composite 1 (step S11), supplying the mixed gas to the zeolite membrane composite 1, and supplying the highly permeable gas to the zeolite.
  • a step (step S13) of separating from another gas by allowing the membrane composite 1 to permeate is provided.
  • the zeolite membrane complex 1 includes a porous support 11 and a zeolite membrane 12 formed on the support 11.
  • the mixed gas includes a highly permeable gas and a trace gas having a lower concentration than the highly permeable gas.
  • the trace gas contains an organic substance having a molar concentration of 1.0 mol% or more in the mixed gas.
  • the adsorption equilibrium constant of the organic substance with respect to the zeolite membrane 12 is less than 150 times that of the highly permeable gas.
  • the concentration of organic substances that is, low-adsorption gas
  • the concentration of organic substances that is, low-adsorption gas
  • the concentration of organic substances whose adsorption equilibrium constant with respect to the zeolite membrane 12 is less than 150 times that of the highly permeable gas is 1.0 mol.
  • the trace gas contains an organic substance having a relatively high adsorptivity to the zeolite membrane 12
  • the presence of the above-mentioned low adsorptive gas inhibits the adsorption of the organic substance to the zeolite membrane 12. Will be done.
  • the organic matter contained in the trace gas is not limited to one type, and a plurality of types of organic matter may be contained in the trace gas.
  • the adsorption equilibrium constant with respect to the zeolite membrane 12 is less than 150 times that of the highly permeable gas for the organic substance components having a molar concentration of 1.0 mol% or more in the mixed gas.
  • the adsorption equilibrium constant with respect to the zeolite membrane 12 is not particularly limited for the organic component having a molar concentration of less than 1.0 mol% in the mixed gas.
  • the trace gas contains three kinds of organic substances, the molar concentration of the first organic substance (that is, the first organic substance component) in the mixed gas is 1.0 mol% or more, and the molar concentration in the mixed gas of the second organic substance is 1.0 mol% or more.
  • the concentration is 1.0 mol% or more and the molar concentration of the third organic substance in the mixed gas is less than 1.0 mol%
  • the adsorption equilibrium constant of each of the first organic substance and the second organic substance is that of the highly permeable gas. It is less than 150 times, and the adsorption equilibrium constant of the third organic substance is not particularly limited.
  • the concentration of the organic substance that is, the highly adsorptive gas whose adsorption equilibrium constant with respect to the zeolite membrane 12 is 150 times or more that of the highly permeable gas is less than 0.05 mol%. It is preferable to have.
  • concentration of the highly adsorptive gas By lowering the concentration of the highly adsorptive gas in this way, it is further suppressed that the organic matter in the trace gas is adsorbed on the pores of the zeolite membrane 12, and the permeation of the zeolite membrane 12 of the highly permeable gas is the adsorbed organic matter. It is possible to further suppress the inhibition by. As a result, the deterioration of the permeation performance due to the zeolite membrane 12 with time can be further suppressed.
  • the highly permeable gas is preferably H 2 , N 2 , O 2 or CO 2.
  • H 2 , N 2 , O 2 or CO 2 can be efficiently separated while suppressing a decrease in permeation performance over time.
  • the maximum number of membered rings of the zeolite crystal contained in the zeolite membrane 12 is preferably 8. Thereby, in the zeolite membrane complex 1, selective permeation of a gas having a relatively small molecular diameter can be suitably realized.
  • the gas separation method removes an organic substance (that is, a highly adsorptive gas) having an adsorption equilibrium constant with respect to the zeolite membrane 12 of 150 times or more that of the highly permeable gas from the mixed gas before step S13. It is preferable to further include the step of performing (step S12). Thereby, the molar concentration of the highly adsorptive gas in the mixed gas can be easily lowered (preferably less than 0.05 mol%). As a result, the deterioration of the permeation performance of the zeolite membrane 12 with time can be easily suppressed. Further, in step S12, the removal step of step S12 can be simplified by selectively removing the high-adsorption gas without intentionally removing the low-adsorption gas. As a result, the deterioration of the permeation performance of the zeolite membrane 12 with time can be more easily suppressed.
  • an organic substance that is, a highly adsorptive gas having an adsorption equilibrium constant with respect to the zeolite membrane
  • the mixed gas further contains a low-permeability gas having a lower permeability to the zeolite membrane 12 than the high-permeability gas, and in the mixed gas, the concentration of the trace gas is lower than the concentration of the low-permeability gas. Is preferable. Thereby, a high permeance ratio can be realized in the separation of the highly permeable gas from the low permeable gas.
  • the gas separation methods described above include hydrogen, helium, nitrogen, oxygen, water, water vapor, carbon monoxide, carbon dioxide, nitrogen oxides, ammonia, sulfur oxides, hydrogen sulfide, sulfur fluoride, mercury, alcine, hydrogen cyanide, and sulfide. It is particularly suitable for separating mixed gases containing one or more substances among carbonyl, hydrogens of C1 to C8, organic acids, alcohols, mercaptans, esters, ethers, ketones and aldehydes.
  • the mixed gas when the mixed gas is supplied to the zeolite membrane 12 formed on the porous support 11, the molar concentration of the organic substance in the mixed gas is 1.0 mol% or more and 6.0 mol% or less. In this state, the permeation ratio (P40 / P10) of the zeolite membrane 12 is 0.85 or more and 1.00 or less. Thereby, similarly to the above, the deterioration of the permeation performance of the zeolite membrane 12 with time can be easily suppressed.
  • the mixed gas contains a highly permeable gas and a trace gas having a concentration lower than that of the highly permeable gas. Further, the trace gas contains an organic substance having an adsorption equilibrium constant of less than 150 times that of the highly permeable gas.
  • the zeolite membrane 12 is particularly suitable for separating mixed gases when the highly permeable gas is H 2 , N 2 , O 2 or CO 2.
  • the zeolite membrane 12 is suitable for separating the highly permeable gas from the low permeable gas when the mixed gas further contains a low permeable gas having a higher concentration than the trace gas.
  • the gas separation method described above can be changed in various ways.
  • the step of removing the highly adsorptive gas from the mixed gas may be omitted.
  • the mixed gas does not necessarily have to contain a low-permeability gas as long as it contains a highly permeable gas and a trace gas.
  • the highly permeable gas does not necessarily have to be H 2 , N 2 , O 2 or CO 2 , and may be a gas other than these gases.
  • the maximum number of membered rings of the zeolite membrane 12 may be smaller than 8 or larger than 8.
  • the zeolite membrane composite 1 may further include a functional membrane or a protective membrane laminated on the zeolite membrane 12.
  • 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.
  • a substance that easily adsorbs CO 2 may be added to the functional film or the protective film laminated on the zeolite membrane 12.
  • the gas separation method of the present invention can be used in various fields in which gas separation is performed.

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