WO2016158580A1 - Ddr型ゼオライト種結晶及びddr型ゼオライト膜の製造方法 - Google Patents
Ddr型ゼオライト種結晶及びddr型ゼオライト膜の製造方法 Download PDFInfo
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- WO2016158580A1 WO2016158580A1 PCT/JP2016/059044 JP2016059044W WO2016158580A1 WO 2016158580 A1 WO2016158580 A1 WO 2016158580A1 JP 2016059044 W JP2016059044 W JP 2016059044W WO 2016158580 A1 WO2016158580 A1 WO 2016158580A1
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- type zeolite
- seed crystal
- ddr type
- ddr
- zeolite membrane
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- 239000013078 crystal Substances 0.000 title claims abstract description 99
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 67
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000010457 zeolite Substances 0.000 title claims abstract description 67
- 239000012528 membrane Substances 0.000 title claims description 52
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 238000000034 method Methods 0.000 title description 16
- 239000002245 particle Substances 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 239000002344 surface layer Substances 0.000 description 19
- 239000010410 layer Substances 0.000 description 17
- 239000011148 porous material Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 238000000926 separation method Methods 0.000 description 14
- 241000282341 Mustela putorius furo Species 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 8
- 230000035699 permeability Effects 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000002296 dynamic light scattering Methods 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000012935 Averaging Methods 0.000 description 2
- HXQQNYSFSLBXQJ-UHFFFAOYSA-N COC1=C(NC(CO)C(O)=O)CC(O)(CO)CC1=NCC(O)=O Chemical compound COC1=C(NC(CO)C(O)=O)CC(O)(CO)CC1=NCC(O)=O HXQQNYSFSLBXQJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000971 Silver steel Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920006268 silicone film Polymers 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- 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
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0046—Inorganic membrane manufacture by slurry techniques, e.g. die or slip-casting
-
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
-
- 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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
Definitions
- the present invention relates to a method for producing a DDR type zeolite seed crystal and a DDR type zeolite membrane.
- a technique of forming a DDR type zeolite membrane on the surface of a support using a DDR type zeolite seed crystal (hereinafter referred to as “seed crystal”) is known (for example, see Patent Documents 1 and 2).
- seed crystal a DDR type zeolite seed crystal
- a DDR type zeolite membrane is formed by crystal growth of a seed crystal coated on the surface of the support in the form of a film.
- the separability of the DDR type zeolite membrane improves as the density increases, and the permeability of the DDR type zeolite membrane tends to improve as the film thickness decreases.
- the film thickness becomes thick, so it is not easy to achieve both separation and permeability.
- the present invention has been made in view of the above situation, and an object thereof is to provide a DDR type zeolite seed crystal and a method for producing a DDR type zeolite membrane that can improve the separation and permeability of the DDR type zeolite membrane. To do.
- the DDR type zeolite seed crystal according to the present invention has an average particle diameter of 0.2 ⁇ m or less and an average aspect ratio of 1.3 or less.
- a DDR type zeolite seed crystal and a method for producing a DDR type zeolite membrane that can improve the separability and permeability of the DDR type zeolite membrane.
- the average particle diameter of the DDR type zeolite seed crystal (hereinafter referred to as “seed crystal”) according to the present embodiment is 0.2 ⁇ m or less. By setting the average particle diameter to 0.2 ⁇ m or less, the gap between the seed crystals applied to the surface of the support can be reduced.
- the average particle size of the seed crystal is preferably 0.05 ⁇ m or more.
- the average particle size of the seed crystal is the median value of the particle size on a volume basis, and can be measured by a dynamic light scattering method.
- the particle size distribution of a suspension obtained by dropping a dispersion of seed crystals in water into water so as to have a measurable concentration and then dispersing with ultrasonic waves is the dynamic light scattering particle size.
- the median diameter (D50) obtained from the measured particle size distribution is the average particle diameter of the seed crystal.
- the average aspect ratio of the seed crystal is 1.3 or less. By setting the average aspect ratio of the seed crystals to 1.3 or less, the density of the applied seed crystals can be improved.
- the lower limit of the average aspect ratio of the seed crystal is 1.0.
- the aspect ratio of the seed crystal is a value obtained by dividing the maximum ferret diameter by the minimum ferret diameter (maximum ferret diameter / minimum ferret diameter).
- the maximum ferret diameter is the maximum distance between two parallel straight lines sandwiching the seed crystal on the FE-SEM (field emission scanning electron microscope) image of the seed crystal.
- the minimum ferret diameter is the minimum distance between two parallel straight lines sandwiching the seed crystal in the FE-SEM image of the seed crystal.
- the maximum ferret diameter and the minimum ferret diameter can be measured using an in-lens FE-SEM.
- the average aspect ratio of the seed crystal is a value obtained by arithmetically averaging the aspect ratios of 20 seed crystals arbitrarily selected on the FE-SEM image.
- 20 seed crystals are arbitrarily selected from a plurality of FE-SEM images. do it.
- the crystallinity index of the seed crystal is preferably 60 or more.
- the crystallinity index is a representative value indicating the abundance ratio of DDR type zeolite crystals and amorphous. Since the remaining amorphous can be reduced by setting the crystallinity index of the seed crystal to 60 or more, the film formability of the DDR type zeolite membrane can be improved.
- the crystallinity index means that the diffraction intensity of the diffraction peak due to the (024) plane obtained by XRD (powder X-ray diffraction) measurement is A, and the distance between the peaks of the (024) plane and the (116) plane. This is the value of (AC) / (BC), where B is the minimum value of the diffraction intensity at C and C is the minimum value of the diffraction intensity between the peaks of the (024) plane and the (202) plane.
- nucleus containing DDR type zeolite (hereinafter referred to as “nucleus”) is prepared.
- the core is preferably a DDR type zeolite crystal or a mixture of a DDR type zeolite crystal and amorphous silica.
- the average particle diameter of the nuclei can be 0.100 to 0.200 ⁇ m.
- the average particle diameter of the nucleus can be measured by a dynamic light scattering method.
- the method for producing the nucleus is not particularly limited.
- a raw material solution (raw material sol) containing a nucleus, silica, and 1-adamantanamine as a structure directing agent is prepared.
- the raw material solution may contain water, ethylenediamine and the like.
- concentration of the nucleus in a raw material solution can be 0.4 mass% or more, and it is preferable that it is 0.5 mass% or more.
- seed crystals are generated by heating the raw material solution at 110 to 150 ° C. for 4 hours or longer (hydrothermal synthesis). At this time, the aspect ratio of the seed crystal can be reduced as the heating temperature is lowered, and the aspect ratio of the seed crystal can be reduced as the heating time is increased.
- the heating time of the raw material solution is preferably 24 hours or longer.
- the seed crystal is dispersed in a dispersion medium (water, alcohols, etc.) and the dispersion adjusted to pH 7.5 or higher is washed by a shaking method or an ultrasonic method.
- a dispersion medium water, alcohols, etc.
- a seed crystal having an average particle size of 0.2 ⁇ m or less and an aspect ratio of 1.3 or less is produced.
- FIG. 1 is a cross-sectional view showing the configuration of the separation membrane structure 10.
- the separation membrane structure 10 includes a support 20 and a DDR type zeolite membrane 30.
- the support 20 supports the DDR type zeolite membrane 30.
- the support 20 has chemical stability such that the DDR type zeolite membrane 30 can be formed into a film shape (crystallization, coating, or precipitation) on the surface.
- the support 20 may have any shape that can supply the mixed fluid to be separated to the DDR type zeolite membrane 30. Examples of the shape of the support 20 include a honeycomb shape, a monolith shape, a flat plate shape, a tubular shape, a cylindrical shape, a columnar shape, and a prismatic shape.
- the support 20 has a base body 21, an intermediate layer 22, and a surface layer 23.
- the base 21 is made of a porous material.
- a porous material for example, a ceramic sintered body, metal, organic polymer, glass, or carbon can be used.
- the ceramic sintered body include alumina, silica, mullite, zirconia, titania, yttria, silicon nitride, and silicon carbide.
- the metal include aluminum, iron, bronze, silver, and stainless steel.
- the organic polymer include polyethylene, polypropylene, polytetrafluoroethylene, polysulfone, and polyimide.
- the substrate 21 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 substrate 21 can be set to 5 ⁇ m to 25 ⁇ m, for example.
- the average pore diameter of the substrate 21 can be measured with a mercury porosimeter.
- the porosity of the substrate 21 can be set to 25% to 50%, for example.
- the average particle diameter of the porous material constituting the substrate 21 can be set to 5 ⁇ m to 100 ⁇ m, for example.
- the average particle diameter of the substrate 21 is a value obtained by arithmetically averaging the maximum diameters of 30 measurement target particles measured by cross-sectional microstructure observation using a SEM (scanning electron microscope).
- the intermediate layer 22 is formed on the base 21.
- the intermediate layer 22 can be made of the porous material that can be used for the substrate 21.
- the average pore diameter of the intermediate layer 22 may be smaller than the average pore diameter of the substrate 21, and may be, for example, 0.005 ⁇ m to 2 ⁇ m.
- the average pore diameter of the intermediate layer 22 can be measured with a palm porometer.
- the porosity of the intermediate layer 22 can be set to 20% to 60%, for example.
- the thickness of the intermediate layer 22 can be set to 30 ⁇ m to 300 ⁇ m, for example.
- the surface layer 23 is formed on the intermediate layer 22.
- the surface layer 23 can be composed of the porous material that can be used for the base 21.
- the average pore diameter of the surface layer 23 may be smaller than the average pore diameter of the intermediate layer 22, and may be, for example, 0.001 ⁇ m to 0.5 ⁇ m.
- the average pore diameter of the surface layer 23 can be measured with a palm porometer.
- the porosity of the surface layer 23 can be set to 20% to 60%, for example.
- the thickness of the surface layer 23 can be set to 1 ⁇ m to 50 ⁇ m, for example.
- the DDR type zeolite membrane 30 is formed using the seed crystal described above. Therefore, the DDR type zeolite membrane 30 has good separability and permeability. A method for manufacturing the DDR type zeolite membrane 30 will be described later.
- the DDR type zeolite membrane 30 contains DDR type zeolite as a main component.
- the zeolite membrane 30 may contain an inorganic binder (such as silica or alumina), an organic binder (such as a polymer), and a silylating agent.
- the phrase “the composition X contains the substance Y as a main component” means that the substance Y occupies 60% by weight or more in the entire composition X.
- a molded body of the base 21 having a desired shape is formed by an extrusion molding method, a press molding method, a cast molding method, or the like.
- the molded body of the substrate 21 is fired (for example, 900 ° C. to 1450 ° C.) to form the substrate 21.
- an intermediate layer 22 formed by using a ceramic raw material having a desired particle size is formed on the surface of the base 21 to form a formed body of the intermediate layer 22.
- the molded body of the intermediate layer 22 is fired (for example, 900 ° C. to 1450 ° C.) to form the intermediate layer 22.
- the surface layer 23 is formed on the surface of the intermediate layer 22 by forming a slurry for the surface layer using a ceramic raw material having a desired particle diameter, thereby forming a formed body of the surface layer 23.
- the molded body of the surface layer 23 is fired (for example, 900 ° C. to 1450 ° C.) to form the surface layer 23.
- a slurry in which seed crystals are dispersed in alcohol is applied to the surface of the surface layer 23 by a flow-down method or a dip method.
- the average particle diameter of the seed crystal is 0.2 ⁇ m or less and the aspect ratio is 1.3 or less, the packing property (coverage) of the surface of the surface layer 23 by the seed crystal can be improved.
- the amount of seed crystals attached can be controlled by the content of seed crystals in the slurry, and the content of seed crystals is preferably 0.001% by mass to 0.5% by mass.
- the content rate of a seed crystal 0.001 mass% or more, it can suppress that it becomes difficult to produce
- the seed crystal content is more preferably 0.01% by mass to 0.4% by mass, and particularly preferably 0.05% by mass to 0.3% by mass.
- the support 20 is immersed in a pressure vessel containing a raw material solution containing a silica source, an alumina source, an alkali source and water.
- the raw material solution may contain an organic template.
- the pressure vessel is put into a dryer and heated at 100 to 200 ° C. for about 1 to 240 hours (hydrothermal synthesis) to grow a seed crystal into a film. Since the seed crystal packing property on the surface of the surface layer 23 is high, a dense DDR type zeolite membrane 30 is formed in a short time.
- the support 20 on which the DDR type zeolite membrane 30 is formed is washed and dried at 80 to 100 ° C.
- the organic template is burned and removed by placing the support 20 in an electric furnace and heating in the atmosphere (400 to 800 ° C., 1 to 200 hours). .
- the seed crystal according to the present embodiment has an average particle diameter of 0.2 ⁇ m or less and an aspect ratio of 1.3 or less. Therefore, compared with the case where the average particle diameter is larger than 0.2 ⁇ m (see FIG. 2A) and the aspect ratio is larger than 1.3 (see FIG. 2B), it depends on the seed crystal on the surface of the surface layer 23.
- the packing property can be improved (see FIG. 2C). As a result, since the dense DDR type zeolite membrane 30 can be formed in a short time, both separation and permeability can be improved by making the DDR type zeolite membrane 30 thin and dense.
- the support 20 has the base 21, the intermediate layer 22, and the surface layer 23.
- the support 20 may not have one or both of the intermediate layer 22 and the surface layer 23.
- the separation membrane structure 10 includes the support 20 and the DDR type zeolite membrane 30, but may further include a functional membrane or a protective membrane laminated on the DDR type zeolite membrane 30.
- a film an inorganic film such as a zeolite film, a carbon film, or a silica film, or an organic film such as a polyimide film or a silicone film can be used.
- aqueous solution containing 0.90% by mass of a DDR type zeolite crystal as a nucleus is put in another container, and 97.90 g of silica sol (Snowtex S, manufactured by Nissan Chemical Industries, Ltd.) containing 30% by mass of silica is added.
- silica sol containing nuclei was obtained by stirring.
- DDR type zeolite powder having an average particle size of 2.9 ⁇ m is pulverized by a beads mill (trade name: Star Mill) manufactured by Ashizawa Finetech Co., Ltd. And then centrifuged to remove coarse particles.
- the average particle diameter of the nuclei was as shown in Table 1.
- a raw material solution (raw material sol) was obtained by adding and stirring the silica sol containing the nucleus prepared previously in an airtight container containing ethylenediamine in which 1-adamantanamine was dissolved.
- concentration of nuclei in the raw material solution was as shown in Table 1.
- the seed crystal dispersion was dropped into ethanol and stirred to prepare a seeding slurry having a seed crystal concentration of 0.075% by mass.
- seeding slurry was poured into the cell of the support from above the vertically placed monolithic support (diameter 30 mm ⁇ length 160 mm, average pore diameter 0.10 ⁇ m).
- the seeding slurry applied to the cell wall surface was dried by flowing air at room temperature for 10 minutes at a wind speed of 2 to 7 m / sec.
- ethylenediamine manufactured by Wako Pure Chemical Industries, Ltd.
- 1-adamantanamine manufactured by Sigma Aldrich
- silica sol (Snowtex S, manufactured by Nissan Chemical Industries, Ltd.) containing 30% by mass of silica and 35.71 g of ion exchange water were placed in another container and stirred to prepare a silica dispersion. .
- an ethylenediamine solution in which 1-adamantanamine was dissolved was added to the silica dispersion and stirred, and then diluted with ion-exchanged water to prepare a film forming raw material solution.
- a support with a seed crystal attached was placed in a stainless steel pressure resistant vessel with a fluororesin inner cylinder.
- the raw material solution for film formation was put into a container and heated at 125 ° C. for 20 hours (hydrothermal synthesis) to form a DDR type zeolite film containing 1-adamantanamine on the cell wall surface of the support. .
- the support was taken out from the container, washed in water, and dried at 80 ° C. for 16 hours.
- the seed crystal dispersion liquid of each sample was dropped into about 20 ml of water so as to have a measurable concentration, and then dispersed by ultrasonic waves for 5 minutes or more to obtain a seed crystal suspension.
- the particle size distribution of the suspension was measured with a dynamic light scattering particle size distribution measuring device (trade name: Nanotrac, manufactured by Nikkiso Co., Ltd.).
- the average particle size of the seed crystal of each sample is as shown in Table 1.
- N 2 permeation amount of DDR type zeolite membrane In order to evaluate the denseness of the DDR type zeolite membrane of each sample, the N 2 permeation amount was measured. Specifically, 100 KPa of N 2 gas was introduced into the cell of the support, and the amount of N 2 gas permeated through the support was measured with a mass flow meter. The measurement results are as shown in Table 1.
- the separability and permeability of the DDR type zeolite membrane can be improved by using a seed crystal having an average particle size of 0.2 ⁇ m or less and an aspect ratio of 1.3 or less.
- Sample No. with a crystallinity index of 60 or more was used. 1-No. In No. 5, the N 2 permeation amount of the DDR type zeolite membrane could be further suppressed.
- the separability and permeability of the DDR type zeolite membrane can be improved, which is useful in the field of separation membranes.
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Abstract
Description
本実施形態に係るDDR型ゼオライト種結晶(以下、「種結晶」という。)の平均粒子径は、0.2μm以下である。平均粒子径を0.2μm以下とすることによって、支持体の表面に塗布される種結晶の隙間を小さくすることができる。
種結晶の製造方法の一例について説明する。
まず、DDR型ゼオライトを含む核(以下、「核」という。)を準備する。核は、DDR型ゼオライト結晶、又は、DDR型ゼオライト結晶とアモルファスシリカとの混合物であることが好ましい。核の平均粒子径は、0.100~0.200μmとすることができる。核の平均粒子径は、動的光散乱法によって測定することができる。核の製造方法は特に限定されない。
図1は、分離膜構造体10の構成を示す断面図である。分離膜構造体10は、支持体20とDDR型ゼオライト膜30を備える。
分離膜構造体10の製造方法について説明する。
本実施形態に係る種結晶は、平均粒子径が0.2μm以下であり、アスペクト比が1.3以下である。従って、平均粒子径が0.2μmより大きい場合(図2(a)参照)やアスペクト比が1.3より大きい場合(図2(b)参照)に比べて、表層23の表面の種結晶によるパッキング性を高めることができる(図2(c)参照)。その結果、短時間で緻密なDDR型ゼオライト膜30を形成できるため、DDR型ゼオライト膜30の薄膜化と緻密化によって分離性と透過性を共に向上させることができる。
上記実施形態において、支持体20は、基体21と中間層22と表層23を有することとしたが、中間層22と表層23の一方又は両方を有していなくてもよい。
まず、フッ素樹脂製の密閉容器に12.63gのエチレンジアミン(和光純薬工業社製)を入れた後、1.98gの1-アダマンタンアミン(シグマアルドリッチ社製)を加えて、超音波によって1-アダマンタンアミンを溶解した。
各サンプルの種結晶分散液を約20mlの水に測定可能な濃度となるよう滴下した後、超音波で5分以上分散させることによって種結晶の懸濁液を得た。
各サンプルの種結晶分散液から取り出して、種結晶のFE-SEM(ZEISS社製、商品名(型番):ULTRA55)画像を取得した。
各サンプルの種結晶分散液を120℃で1時間乾燥した後に、メノウ製マグネット乳鉢にて粉末状とした種結晶の(024)面に起因する回折ピークの回折強度(A)、(024)面と(116)面のピーク間における回折強度の最低値(B)、及び(024)面と(202)面のピーク間における回折強度の最低値(C)をX線回折装置(リガク社製、商品名(型番):RINT-2500)で測定した。
各サンプルのDDR型ゼオライト膜の緻密性を評価するためにN2透過量を測定した。具体的には、100KPaのN2ガスを支持体のセルに導入して、支持体を透過したN2ガスの透過量をマスフローメーターで測定した。測定結果は表1に示す通りであった。
20 支持体
21 基体
22 中間層
23 表層
30 分離膜
Claims (6)
- 平均粒子径が0.2μm以下であり、平均アスペクト比が1.3以下である、
DDR型ゼオライト種結晶。 - 結晶性指数が60以上である、
請求項1に記載のDDR型ゼオライト種結晶。 - 平均粒子径が0.2μm以下であり、平均アスペクト比が1.3以下のDDR型ゼオライト種結晶を含有するスラリーを支持体の表面に塗布する工程と、
前記DDR型ゼオライト種結晶を結晶成長させる工程と、
を備えるDDR型ゼオライト膜の製造方法。 - DDR型ゼオライト結晶を含む核を含有する原料溶液を24時間以上加熱することによって前記DDR型ゼオライト種結晶を形成する工程を備える
請求項3に記載のDDR型ゼオライト膜の製造方法。 - 前記原料溶液における前記核の濃度は0.5質量%以上である、
請求項4に記載のDDR型ゼオライト膜の製造方法。 - 前記原料溶液を110℃以上150℃以下で加熱する、
請求項4又は5に記載のDDR型ゼオライト膜の製造方法。
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WO2019142531A1 (ja) * | 2018-01-16 | 2019-07-25 | 日本碍子株式会社 | ゼオライト膜複合体、および、ゼオライト膜複合体の製造方法 |
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