WO2015146354A1 - モノリス型分離膜構造体及びモノリス型分離膜構造体の製造方法 - Google Patents
モノリス型分離膜構造体及びモノリス型分離膜構造体の製造方法 Download PDFInfo
- Publication number
- WO2015146354A1 WO2015146354A1 PCT/JP2015/054012 JP2015054012W WO2015146354A1 WO 2015146354 A1 WO2015146354 A1 WO 2015146354A1 JP 2015054012 W JP2015054012 W JP 2015054012W WO 2015146354 A1 WO2015146354 A1 WO 2015146354A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- separation membrane
- layer
- intermediate layer
- less
- membrane structure
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 124
- 238000000926 separation method Methods 0.000 title claims abstract description 121
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 230000003746 surface roughness Effects 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims description 152
- 239000002344 surface layer Substances 0.000 claims description 61
- 239000000463 material Substances 0.000 claims description 46
- 239000011148 porous material Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 35
- 239000002002 slurry Substances 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 27
- 239000011230 binding agent Substances 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 10
- 239000004927 clay Substances 0.000 claims description 5
- 230000000149 penetrating effect Effects 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 229910021536 Zeolite Inorganic materials 0.000 description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 12
- 239000010457 zeolite Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 238000010304 firing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910018503 SF6 Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 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 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
- 238000001125 extrusion Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 2
- 229960000909 sulfur hexafluoride Drugs 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 210000003771 C cell Anatomy 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012192 staining solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Images
Classifications
-
- 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
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
- B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
- B01D46/2418—Honeycomb filters
- B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
- B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
- B01D46/2418—Honeycomb filters
- B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
- B01D46/2429—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material of the honeycomb walls or cells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
- B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
- B01D46/2418—Honeycomb filters
- B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
- B01D46/2476—Monolithic structures
-
- 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
- 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
- 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
- B01D69/1214—Chemically bonded layers, e.g. cross-linking
-
- 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
- B01D71/021—Carbon
-
- 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
- B01D71/024—Oxides
- B01D71/025—Aluminium oxide
-
- 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
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
-
- 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
- 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
- B01D2325/06—Surface irregularities
-
- 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
- B01D71/024—Oxides
Definitions
- the present invention relates to a monolithic separation membrane structure and a method for producing the monolithic separation membrane structure.
- a monolithic separation membrane structure including a monolithic base material including a plurality of through holes and a separation membrane formed on the inner surface of the through holes is known (see Patent Document 1).
- the separation membrane can be composed of an inorganic material such as zeolite, carbon and silica, or a metal material such as palladium.
- the present invention has been made in view of the above-described circumstances, and an object thereof is to provide a monolithic separation membrane structure capable of suppressing cracks in the separation membrane and a method for manufacturing the monolithic separation membrane structure.
- the monolith type separation membrane structure according to the present invention includes a porous monolith type base material and a separation membrane.
- the monolithic base material has a first end surface, a second end surface, and a plurality of through holes penetrating from the first end surface to the second end surface.
- the separation membrane is formed on the inner surface of each of the plurality of through holes.
- the surface roughness Ra of the separation membrane is 1 ⁇ m or less.
- the thickness of the separation membrane is 5 ⁇ m or less.
- the present invention it is possible to provide a monolithic separation membrane structure capable of suppressing cracks in the separation membrane and a method for producing the monolithic separation membrane structure.
- “monolith” means a shape having a plurality of through holes formed in the longitudinal direction, and is a concept including a honeycomb shape.
- FIG. 1 is a perspective view of a monolith type separation membrane structure 10.
- FIG. 2 is a cross-sectional view of the monolith type separation membrane structure 100.
- the monolith type separation membrane structure 100 includes a monolith type substrate 200 and a separation membrane 300.
- the monolith type substrate 200 has a substrate body 210, a first seal portion 220, and a second seal portion 230.
- the base body 210 is a porous body.
- the base body 210 is formed in a cylindrical shape.
- the length of the base body 210 in the longitudinal direction can be 150 to 2000 mm, and the diameter of the base body 210 in the short direction can be 30 to 220 mm, but is not limited thereto.
- the base body 210 has a first end surface 210a, a second end surface 210b, a side surface 210c, and a plurality of through holes 210d.
- the first end surface 210a is provided opposite to the second end surface 210b.
- the side surface 210c is continuous with the first end surface 210a and the second end surface 210b.
- the through hole 210d penetrates the base body 210 from the first end surface 210a to the second end surface 210b.
- the cross-sectional shape of the through hole 210d is circular.
- the inner diameter of the through hole 210d can be 1 to 5 mm, but is not limited thereto.
- the first seal portion 220 covers the entire first end surface 210a and a part of the side surface 210c.
- sticker part 220 suppresses that the mixed fluid which is the filtration object which flows into the cell C mentioned later enters into the base-material main body 210 directly from the 1st end surface 210a.
- the first seal part 220 is formed so as not to block the inlet of the cell C. Glass, metal, or the like can be used as the material constituting the first seal portion 220, but glass is suitable in consideration of consistency with the thermal expansion coefficient of the base body 210.
- the second seal portion 230 covers the entire surface of the second end surface 210b and a part of the side surface 210c.
- the second seal portion 230 suppresses the fluid flowing out from the cell C from entering the base body 210 from the second end surface 210b.
- the second seal portion 230 is formed so as not to block the outlet of the cell C.
- the second seal part 230 can be made of the same material as the first seal part 220.
- the separation membrane 300 is formed on the inner surfaces of the plurality of through holes 210d.
- the separation membrane 300 is formed in a cylindrical shape.
- a cell C through which the mixed fluid passes is formed inside the separation membrane 300.
- the separation membrane 300 is used as, for example, a gas separation membrane, a PV (Pervaporation) membrane, and a VP (Vapor Permeation) membrane.
- FIG. 3 is a partially enlarged view of FIG.
- the base body 210 includes an extruded base layer 211 and a support layer 212.
- the extruded base material layer 211 has a monolith structure.
- the extruded base material layer 211 is made of a porous material.
- the porous material of the extruded base material layer 211 ceramics, metal, resin, or the like can be used, and a porous ceramic material is particularly preferable.
- aggregate particles of the porous ceramic material alumina (Al 2 O 3 ), titania (TiO 2 ), mullite (Al 2 O 3 .SiO 2 ), cerven and cordierite (Mg 2 Al 4 Si 5 O 18 ) In view of easy availability, stability of clay, and corrosion resistance, alumina is particularly preferable.
- the extruded base material layer 211 may contain an inorganic binder in addition to the porous material.
- 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 porosity of the extruded base material layer 211 can be 25% to 50%.
- the average pore diameter of the extruded base material layer 211 can be 5 ⁇ m to 25 ⁇ m.
- the average particle diameter of the porous material constituting the extruded base material layer 211 can be 10 ⁇ m to 100 ⁇ m.
- the “average particle diameter” is an arithmetic average value of the maximum diameters of 30 measurement target particles measured by cross-sectional microstructure observation using an SEM (Scanning Electron Microscope).
- the support layer 212 is disposed between the extruded base material layer 211 and the separation membrane 300.
- the support layer 212 supports the separation membrane 300.
- the support layer 212 includes a first intermediate layer 212a, a second intermediate layer 212b, and a surface layer 212c.
- the first intermediate layer 212a, the second intermediate layer 212b, and the surface layer 212c are sequentially stacked on the extruded base material layer 211 in a direction perpendicular to the central axis of the cell C (hereinafter referred to as a radial direction).
- the first intermediate layer 212a is formed on the inner surface of the extruded base material layer 211.
- the first intermediate layer 212a is made of a porous material.
- a porous material used in the extruded base material layer 211 can be used.
- the porous material of the first intermediate layer 212a may be the same as or different from the porous material of the extruded base material layer 211.
- the first intermediate layer 212a may include an inorganic binder used in the extruded base material layer 211.
- the inorganic binder of the first intermediate layer 212a may be the same as or different from the inorganic binder of the extruded base material layer 211.
- the first intermediate layer 212a is produced by a filtration method using a slurry containing an organic binder (solvent).
- the porosity of the first intermediate layer 212a can be 15% to 70%.
- the average pore diameter of the first intermediate layer 212a may be smaller than the average pore diameter of the extruded base material layer 211.
- the average pore diameter of the first intermediate layer 212a can be 0.005 ⁇ m to 2 ⁇ m.
- the average particle diameter of the porous material constituting the first intermediate layer 212a may be smaller than the average particle diameter of the porous material constituting the extruded base material layer 211.
- the average particle diameter of the porous material constituting the first intermediate layer 212a can be 0.1 ⁇ m to 5 ⁇ m.
- the thickness of the first intermediate layer 212a in the radial direction can be 50 ⁇ m to 300 ⁇ m.
- the second intermediate layer 212b is formed on the inner surface of the first intermediate layer 212a.
- the second intermediate layer 212b is made of a porous material.
- the porous material of the second intermediate layer 212b the porous material used in the extruded base material layer 211 can be used, but it is preferable to contain alumina as aggregate particles.
- the second intermediate layer 212b may include an inorganic binder used in the extruded base material layer 211. As will be described later, the second intermediate layer 212b is produced by a filtration method using a slurry containing an organic binder.
- the porosity of the second intermediate layer 212b can be 15% to 70%.
- the average pore diameter of the second intermediate layer 212b may be smaller than the average pore diameter of the first intermediate layer 212a.
- the average pore diameter of the second intermediate layer 212b can be 0.001 ⁇ m to 0.5 ⁇ m.
- the average particle diameter of the porous material constituting the second intermediate layer 212b may be smaller than the average particle diameter of the porous material constituting the first intermediate layer 212a.
- the average particle diameter of the porous material constituting the second intermediate layer 212b can be 0.05 ⁇ m to 1.0 ⁇ m.
- the average particle diameter of alumina is preferably 0.4 ⁇ m to 3 ⁇ m, and more preferably 1 ⁇ m or less.
- the thickness of the second intermediate layer 212b in the radial direction can be 2 ⁇ m to 80 ⁇ m.
- the thickness of the second intermediate layer 212b is preferably 5 ⁇ m to 80 ⁇ m, and more preferably 10 ⁇ m to 40 ⁇ m.
- the surface layer 212c is formed on the inner surface of the second intermediate layer 212b.
- the surface layer 212 c is the innermost layer for forming the separation membrane 300 in the support layer 212.
- the surface layer 212c is made of a porous material.
- the porous material of the surface layer 212c the porous material used in the extruded base material layer 211 can be used, but it is preferable that the aggregate particles contain at least one of alumina and titania.
- the surface layer 212c may include an inorganic binder used in the extruded base material layer 211. It is preferable to unravel the slurry used for the surface layer 212c by a ball mill, a bead mill or the like.
- the constituent material of the surface layer 212c may be the same as or different from the constituent material of the second intermediate layer 212b. If the constituent material of the surface layer 212c is the same as the constituent material of the second intermediate layer 212b, the surface layer 212c and the second intermediate layer 212b are integrated and no interface is formed between them. As will be described later, the surface layer 212c is produced by a flow-down method using a slurry containing no organic binder.
- the porosity of the surface layer 212c can be 15% to 70%.
- the average pore diameter of the surface layer 212c may be equal to or smaller than the average pore diameter of the second intermediate layer 212b.
- the average pore diameter of the surface layer 212c can be 0.001 ⁇ m to 0.5 ⁇ m.
- the average particle diameter of the porous material constituting the surface layer 212c can be 0.01 ⁇ m to 0.5 ⁇ m.
- the average particle size of alumina is preferably 0.03 ⁇ m to 1 ⁇ m, and more preferably 0.5 ⁇ m or less.
- the thickness of the surface layer 212c in the radial direction can be 1 ⁇ m to 10 ⁇ m.
- the surface layer 212c has an inner surface 212S in contact with the separation membrane 300.
- the inner surface 212S is the innermost surface of the support layer 212.
- the surface roughness Ra of the inner surface 212S is preferably 1.0 ⁇ m or less, and more preferably 0.7 ⁇ m or less.
- the surface roughness Ra of the inner surface 212S can be measured from a surface curve in the 25 ⁇ m range obtained using an SEM.
- the separation membrane 300 is formed on the inner surface 212S of the surface layer 212c.
- the separation membrane 300 is preferably made of an inorganic material, metal, or the like.
- the inorganic material for the separation membrane 300 include zeolite, carbon, and silica.
- the metal material of the separation membrane 300 include palladium.
- a zeolite membrane a zeolite having a crystal structure such as LTA, MFI, MOR, FER, FAU, DDR, CHA, or BEA can be used.
- the separation membrane 300 is a DDR type zeolite membrane, it can be suitably used as a gas separation membrane for selectively separating carbon dioxide.
- the thickness of the separation membrane 300 in the radial direction is preferably 5 ⁇ m or less, and more preferably 1.1 ⁇ m or less.
- the thickness of the separation membrane 300 may be a measured value obtained by observing a cross section at one place under a microscope, or an arithmetic average value of measured values obtained by observing a cross section at a plurality of places under a microscope.
- the separation membrane 300 has a surface 300S.
- the surface roughness Ra of the surface 300S is preferably 1.0 ⁇ m or less, and more preferably 0.61 ⁇ m or less.
- the surface roughness Ra of the surface 300S can be measured by a contact-type measuring device in accordance with the arithmetic average roughness Ra measurement method defined in JIS standard B0601.
- a molded body of the extruded base material layer 211 having a plurality of through holes is formed using clay containing a porous material.
- a press molding method or a casting method can be used in addition to the extrusion molding method using a vacuum extrusion molding machine.
- the extruded base material layer 211 is formed by firing (for example, 1000 ° C. to 1550 ° C., 1 hour to 100 hours).
- an organic binder, a sintering aid, a pH adjuster, a surfactant, and the like are added to the porous material of the first intermediate layer 212a to prepare a first intermediate layer slurry.
- a molded body of the first intermediate layer 212a is formed by a filtration method using the first intermediate layer slurry. Specifically, the first intermediate layer slurry is sucked by a pump from the outer peripheral surface of the extruded base material layer 211 while being supplied to the through holes of the extruded base material layer 211, so that the first intermediate layer slurry is formed on the inner surface of the extruded base material layer 211. A formed body of the first intermediate layer 212a is formed.
- the first intermediate layer 212a is formed by firing the molded body of the first intermediate layer 212a (eg, 900 ° C. to 1450 ° C., 1 hour to 100 hours).
- an organic binder, a sintering aid, a pH adjuster, a surfactant, and the like are added to the porous material of the second intermediate layer 212b to prepare a second intermediate layer slurry.
- a molded body of the second intermediate layer 212b is formed by a filtration method using the second intermediate layer slurry. Specifically, the second intermediate layer slurry is sucked by a pump from the outer peripheral surface of the extruded base material layer 211 while being supplied into the first intermediate layer 212a, so that the first intermediate layer 212a has a first slurry on the inner surface. A formed body of the two intermediate layers 212b is formed.
- the second intermediate layer 212b is formed by firing the molded body of the second intermediate layer 212b (for example, 900 ° C. to 1450 ° C., 1 hour to 72 hours).
- a slurry for surface layer not containing an organic binder is prepared by adding a sintering aid, a pH adjuster, a surfactant, and the like to the porous material of the surface layer 212c and unraveling with a ball mill.
- “not including an organic binder” is a concept including not only the case where no organic binder is included, but also the case where an organic binder is not substantially included.
- the content of the organic binder contained in the surface layer slurry is preferably 1 wt% or less, and more preferably 0.5 wt% or less.
- a formed body of the surface layer 212c is formed by a flow-down method using the surface layer slurry. Specifically, the molded body of the surface layer 212c is formed on the inner surface of the second intermediate layer 212b by allowing the surface layer slurry to flow down into the second intermediate layer 212b by its own weight. The surface of the molded body of the surface layer 212c formed by the flow-down method is formed more smoothly than when the filtration method is used.
- the surface layer 212c is formed by firing the molded body of the surface layer 212c (for example, 600 ° C. to 1450 ° C., 1 hour to 72 hours).
- the surface roughness Ra of the surface layer 212c is preferably 1.0 ⁇ m or less, and more preferably 0.7 ⁇ m or less.
- the surface roughness Ra of the surface layer 212c can be adjusted by changing the conditions of the flow-down method in the previous step. For example, the surface roughness can be changed by changing the time for unraveling the surface layer slurry by a ball mill, a bead mill or the like.
- the surface roughness Ra of the surface layer 212c can be measured from a surface curve in the 25 ⁇ m range obtained using an SEM.
- a separation membrane 300 having a thickness of 5.0 ⁇ m or less is formed on the inner surface 212S of the surface layer 212c.
- an appropriate method according to the type of the separation membrane 300 may be used.
- the surface roughness Ra of the separation membrane 300 can be easily set to 1.0 ⁇ m or less.
- the surface roughness Ra of the separation membrane 300 can be confirmed by a contact-type measuring device in accordance with the arithmetic average roughness Ra measurement method defined in JIS standard B0601.
- the process of forming the separation membrane 300 includes a heating process.
- the formation process of the DDR type zeolite membrane includes a seeding process by a flow-down method, a hydrothermal synthesis process of a sol, and a heating process for removing a structure-directing agent (400 ° C. to 800 ° C., 1 hour to 200 hours) It is included.
- the film thickness of the DDR type zeolite membrane can be adjusted by changing the synthesis time in the hydrothermal synthesis process of the sol.
- the silica film forming process includes a silica sol solution attaching process and a firing process (350 ° C. to 600 ° C., 1 hour to 100 hours).
- the film thickness of the silica film can be adjusted by changing the number of times these steps are repeated or the method of attaching the silica sol solution (for example, the flow-down method, the dip method, the spin coating method, etc.).
- the carbon film forming process includes a precursor solution coating process, a heat treatment process (150 ° C. to 250 ° C., 1 hour to 50 hours), and a carbonization process in a non-oxidizing atmosphere (500 ° C. to 600 ° C., 1 Hours to 50 hours).
- the film thickness of the carbon film can be adjusted by changing the number of times the precursor solution coating step is repeated and the deposition method (for example, the flow-down method, the dipping method, the spin coating method, etc.).
- the monolithic separation membrane structure 100 includes a monolithic base material 200 and a separation membrane 300.
- the surface roughness Ra of the separation membrane 300 is 1.0 ⁇ m or less. Therefore, since the thickness of the separation membrane 300 can be made substantially uniform, it is possible to suppress the concentration of thermal stress on a part of the separation membrane 300 in the heating process.
- the thickness of the separation membrane 300 is 5.0 ⁇ m or less. Therefore, it can suppress that a thermal stress arises because the separation membrane 300 is too thick. By the above, it can suppress that a crack and peeling generate
- the manufacturing method of the monolith type separation membrane structure 100 includes a step of forming the first and second intermediate layers 212a and 212b by a filtration method using a slurry containing an organic binder, and a slurry that does not contain an organic binder.
- the surface layer 212c is formed by the flow-down method using the slurry containing no organic binder, the surface roughness Ra of the surface layer 212c can be suppressed to 1.0 ⁇ m or less.
- the film formability of the separation membrane 300 is improved, and the surface roughness Ra of the separation membrane 300 can be suppressed to 1.0 ⁇ m or less while the thickness of the separation membrane 300 is 5.0 ⁇ m or less.
- the support layer 212 includes the first intermediate layer 212a, the second intermediate layer 212b, and the surface layer 212c, but one of the first intermediate layer 212a and the second intermediate layer 212b. May be included.
- the base body 210 is formed in a cylindrical shape, but may be formed in a polygonal column shape or an elliptical column shape.
- the cross-sectional shapes of the through-hole 210d and the cell C are circular, but may be polygonal or elliptical.
- each of the first seal portion 220 and the second seal portion 230 covers a part of the side surface 210c, it does not need to cover the side surface 210c.
- a support layer constituted by the first intermediate layer, the second intermediate layer, and the surface layer was formed.
- a first intermediate layer slurry is prepared by adding PVA (organic binder) to alumina and titania, and a first intermediate layer molded body is formed on the inner surface of the through hole by a filtration method using the first intermediate layer slurry. Formed. Subsequently, the molded product of the first intermediate layer was fired (1250 ° C., 2 hours) to form the first intermediate layer.
- PVA organic binder
- alumina alumina
- the second intermediate layer is formed on the inner surface of the first intermediate layer by a filtration method using the second intermediate layer slurry. Formed body.
- the molded body of the second intermediate layer was fired (1250 ° C., 1 hour) to form a second intermediate layer.
- a surface layer slurry was prepared without adding an organic binder to the materials shown in Table 1 (alumina in sample Nos. 1 to 9, 11, and 12 and titania in sample No. 10), and the surface layer slurry was used.
- a surface layer molded body was formed on the inner surface of the second intermediate layer by the flow-down method.
- the average particle size was adjusted by changing the time for unraveling the surface layer slurry by a ball mill for each sample.
- the surface layer compact was fired (1250 ° C. for 1 hour for sample Nos. 1 to 9, 11, 12 and 1 hour at 950 ° C. for sample No. 10) to form a surface layer.
- Sample No. In 1 to 12 the surface layer of the support layer is the innermost layer for forming the separation membrane.
- the cross-sectional SEM image of the surface layer was observed, and the arithmetic average value of the maximum diameter of each of the 30 particles was calculated as the average particle size.
- the average particle diameter of the surface layer (the innermost layer of the support layer) is summarized in Table 1.
- a separation membrane was formed on the inner surface of the surface layer.
- Sample No. In 1 to 10 a DDR type zeolite membrane was formed as a separation membrane.
- Sample No. In Nos. 1 to 10 the thickness of the DDR type zeolite was varied from sample to sample as shown in Table 1 by changing the hydrothermal synthesis time of the sol.
- Sample No. In No. 11 a carbon membrane was formed as a separation membrane as follows.
- a precursor solution was obtained by mixing and dissolving phenolic resin in an organic solvent.
- the precursor solution was formed on the inner surface of the surface layer by dip coating.
- a polyimide resin as a precursor was disposed on the surface of the formed precursor solution by heat treatment (300 ° C., 1 hour).
- the carbon film was formed by heat-processing a polyimide resin (non-oxidizing atmosphere, 600 degreeC, 5 hours).
- Sample No. In No. 12 a silica membrane was formed as a separation membrane.
- a precursor solution (silica sol solution) obtained by diluting a tetrasoloxysilane hydrolyzed in the presence of nitric acid with ethanol was poured into a cell and dried at 80 ° C.
- a silica film was formed by repeating such pouring, drying, heating, and cooling operations 3 to 5 times.
- sample No. 13 to 20 Sample No. mentioned above. Samples No. 1 to 12 were processed through the same steps. 13 to 20 were produced. However, sample no. In Nos. 13 to 20, the surface layer of the support layer was not formed. Therefore, sample no. In Nos. 13 to 20, the second intermediate layer of the support layer is the innermost layer for forming the separation membrane. Table 1 summarizes the average particle size and material of the second intermediate layer (the innermost layer of the support layer), the membrane type of the separation membrane, and the average film thickness.
- a gas having a molecular diameter equal to or larger than the pore diameter of the separation membrane was introduced into the cell, and defects in the separation membrane were examined from the gas permeation amount. Specifically, sample no.
- the tetrafluoromethane in the DDR type zeolite membrane is supplied to the cells 1 to 10 and 13 to 18 at a pressure of 0.1 MPa and 0.5 cc of tetrafluoromethane leaks from the cell. The amount of permeation was calculated.
- the surface roughness Ra of the separation membrane in order to set the surface roughness Ra of the separation membrane to 1.0 ⁇ m or less, it is preferable that the surface roughness Ra of the outermost layer in the support layer is 1.0 ⁇ m or less, and It turned out that it is preferable to form the outermost layer among the support layers by the flow-down method.
- monolith type separation membrane structure 200 monolith type substrate 210 substrate body 210a first end surface 210b second end surface 210c side surface 210d through hole 211 extruded substrate layer 212 support layer 212a first intermediate layer 212b second intermediate layer 212c surface layer 212S Inner surface 220 First seal part 230 Second seal part 300 Separation membrane 300S Surface C cell
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Geometry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
Abstract
Description
図1は、モノリス型分離膜構造体10の斜視図である。図2は、モノリス型分離膜構造体100の断面図である。
まず、多孔質材料を含む坏土を用いて、複数の貫通孔を有する押出基材層211の成形体を形成する。押出基材層211の成形体を形成する方法としては、真空押出成形機を用いた押出成形法のほかプレス成型法や鋳込み成型法を用いることができる。
モノリス型分離膜構造体100は、モノリス型基材200と分離膜300とを備える。分離膜300の表面粗さRaは、1.0μm以下である。従って、分離膜300の厚みを略均一化できるため、加熱工程において分離膜300の一部に熱応力が集中することを抑制できる。また、分離膜300の厚みは、5.0μm以下である。従って、分離膜300が厚すぎることによって熱応力が生じることを抑制できる。以上によって、分離膜300にクラックや剥がれが発生することを抑制することができる。
以上、本発明の一実施形態について説明したが、本発明は上記実施形態に限定されるものではなく、発明の要旨を逸脱しない範囲で種々の変更が可能である。
以下のようにして、サンプルNo.1~12を作製した。
上述したサンプルNo.1~12と同様の工程を経てサンプルNo.13~20を作製した。ただし、サンプルNo.13~20では、支持層のうち表層を形成しなかった。従って、サンプルNo.13~20では、支持層のうち第2中間層が分離膜を形成するための最内層となっている。第2中間層(支持層の最内層)の平均粒径及び材質と分離膜の膜種及び平均膜厚を表1にまとめて示す。
サンプルNo.1~No.20について、支持層のうち最内層の断面をSEMで観察することによって、分離膜と接触する内表面の表面粗さRaを25μm範囲で測定した。測定結果を表1に示す。
サンプルNo.1~No.20の分離膜について、JIS規格B0601に従い、接触式測定機によって表面粗さRaを測定した。測定結果を表1に示す。
サンプルNo.1~10,13~18に係るDDR型ゼオライト膜の分離係数を求めた。具体的には、二酸化炭素(CO2)とメタン(CH4)の混合ガス(各ガスの体積比を50:50とし、各ガスの分圧を0.2MPaとした。)をセル内に導入し、DDR型ゼオライト膜を透過したガスを回収した。そして、ガスクロマトグラフを用いて、回収したガスの成分分析を行い、「分離係数α=(透過CO2濃度/透過CH4濃度)/(供給CO2濃度/供給CH4濃度)」の式により分離係数を算出した。
分離膜の細孔径以上の分子径を有するガスをセル内に導入し、ガス透過量から分離膜の欠陥を調べた。具体的には、サンプルNo.1~10,13~18のセル内に四フッ化メタンを0.1MPaで供給し、セルから四フッ化メタンが0.5cc漏れるまでの時間に基づいて、DDR型ゼオライト膜における四フッ化メタンの透過量を算出した。
サンプルNo.1~20について、ローダミンB0.1%をエタノールに溶かした溶液をセル内に導入して1~30秒程度浸漬し、水で洗い流した。その後、乾燥させた分離膜におけるクラックの発生状況を目視にて確認した。確認結果を表1に示す。
200 モノリス型基材
210 基材本体
210a 第1端面
210b 第2端面
210c 側面
210d 貫通孔
211 押出基材層
212 支持層
212a 第1中間層
212b 第2中間層
212c 表層
212S 内表面
220 第1シール部
230 第2シール部
300 分離膜
300S 表面
C セル
Claims (6)
- 第1端面と、第2端面と、前記第1端面から前記第2端面までそれぞれ貫通する複数の貫通孔とを有する多孔質のモノリス型基材と、
前記複数の貫通孔それぞれの内表面に形成された分離膜と、
を備え、
前記分離膜の表面粗さRaは、1.0μm以下であり、
前記分離膜の厚みは、5.0μm以下である、
モノリス型分離膜構造体。 - 前記モノリス型基材は、押出基材層と、前記押出基材層と前記分離膜の間に配置される支持層とを有し、
前記支持層を構成する多孔質材料の平均粒径は、前記押出基材層を構成する多孔質材料の平均粒径よりも小さい、
請求項1に記載のモノリス型分離膜構造体。 - 前記支持層の表面粗さRaは、1.0μm以下である、
請求項1又は2に記載のモノリス型分離膜構造体。 - 前記分離膜の表面粗さRaは、0.61μm以下であり、
前記分離膜の厚みは、1.1μm以下である、
請求項1乃至3のいずれかに記載のモノリス型分離膜構造体。 - 多孔質材料を含む坏土を用いて、複数の貫通孔を有する押出基材層を形成する工程と、
多孔質材料と有機バインダを含むスラリーを用いた濾過法によって、前記複数の貫通孔の内表面に中間層を形成する工程と、
多孔質材料を含み、かつ、有機バインダを含まないスラリーを用いた流下法によって、前記中間層の内表面に表層を形成する工程と、
前記表層の内表面に5.0μm以下の厚みを有する分離膜を形成する工程と、
を備えるモノリス型分離膜構造体の製造方法。 - 前記表層を流下法で形成する工程では、前記表層の表面粗さRaを1.0μm以下とし、
前記分離膜を形成する工程では、前記分離膜の表面粗さRaを1.0μm以下とする、
請求項5に記載のモノリス型分離膜構造体の製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201580012179.5A CN106102879B (zh) | 2014-03-28 | 2015-02-13 | 整体型分离膜结构体及整体型分离膜结构体的制造方法 |
JP2016510114A JP6436974B2 (ja) | 2014-03-28 | 2015-02-13 | モノリス型分離膜構造体及びモノリス型分離膜構造体の製造方法 |
EP15769832.5A EP3124104B1 (en) | 2014-03-28 | 2015-02-13 | Monolithic separation membrane structure, and method for producing monolithic separation membrane structure |
MYPI2016703404A MY183887A (en) | 2014-03-28 | 2015-02-13 | Monolithic separation membrane structure, and method for producing monolithic separation membrane structure |
US15/260,703 US10391454B2 (en) | 2014-03-28 | 2016-09-09 | Monolithic separation membrane structure and method for producing monolithic separation membrane structure |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-069301 | 2014-03-28 | ||
JP2014069301 | 2014-03-28 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/260,703 Continuation US10391454B2 (en) | 2014-03-28 | 2016-09-09 | Monolithic separation membrane structure and method for producing monolithic separation membrane structure |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015146354A1 true WO2015146354A1 (ja) | 2015-10-01 |
Family
ID=54194892
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/054012 WO2015146354A1 (ja) | 2014-03-28 | 2015-02-13 | モノリス型分離膜構造体及びモノリス型分離膜構造体の製造方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US10391454B2 (ja) |
EP (1) | EP3124104B1 (ja) |
JP (1) | JP6436974B2 (ja) |
CN (1) | CN106102879B (ja) |
MY (1) | MY183887A (ja) |
WO (1) | WO2015146354A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017169591A1 (ja) * | 2016-03-31 | 2017-10-05 | 日本碍子株式会社 | 多孔質支持体、多孔質支持体の製造方法、分離膜構造体及び分離膜構造体の製造方法 |
WO2017169865A1 (ja) * | 2016-03-30 | 2017-10-05 | 日本碍子株式会社 | セラミック膜フィルタ及びその製造方法 |
JP2018122282A (ja) * | 2017-01-30 | 2018-08-09 | イーセップ株式会社 | 水素分離膜 |
JP2019098211A (ja) * | 2017-11-29 | 2019-06-24 | 京セラ株式会社 | 炭素膜付き多孔質体 |
JP2019209275A (ja) * | 2018-06-06 | 2019-12-12 | 東芝ライフスタイル株式会社 | 酸素富化膜、及びその製造方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03284328A (ja) * | 1990-03-30 | 1991-12-16 | Ngk Insulators Ltd | セラミック膜フイルタおよびその製造方法 |
JP2007254222A (ja) * | 2006-03-24 | 2007-10-04 | Ngk Insulators Ltd | セラミックス多孔質膜、セラミックスフィルターとその製造方法 |
JP2007284303A (ja) * | 2006-04-18 | 2007-11-01 | Japan Science & Technology Agency | 3次元構造メソポーラスシリカとその薄膜の製造方法 |
WO2011040205A1 (ja) * | 2009-09-29 | 2011-04-07 | 日本碍子株式会社 | ゼオライト膜の製造方法、およびその製造方法により得られたゼオライト膜 |
JP2012066241A (ja) * | 2010-08-26 | 2012-04-05 | Mitsubishi Chemicals Corp | 多孔質支持体―ゼオライト膜複合体およびそれを用いる分離方法 |
JP2013529132A (ja) * | 2010-05-25 | 2013-07-18 | コーニング インコーポレイテッド | コージエライトモノリスにおけるコージエライト膜 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1723999A (en) * | 1927-06-23 | 1929-08-13 | James L Bernard | Facing machine |
WO1993011087A1 (en) * | 1991-12-05 | 1993-06-10 | The Dow Chemical Company | Structure for a filter or a heat exchanger and a method for making the structure |
US7179325B2 (en) * | 2004-02-10 | 2007-02-20 | Virginia Tech Intellectual Properties, Inc. | Hydrogen-selective silica-based membrane |
ZA200607636B (en) * | 2004-03-12 | 2008-02-27 | Ngk Insulators Ltd | Carbon film laminate and method for production thereof, and VOC removing device |
BRPI0508654A (pt) * | 2004-03-12 | 2007-08-14 | Ngk Insulators Ltd | laminado de pelìcula de carbono e método para produção do mesmo e dispositivo de remoção de voc |
US20080093291A1 (en) * | 2006-10-18 | 2008-04-24 | Ngk Insulators, Ltd. | Ceramic porous membrane and ceramic filter |
JP4883364B2 (ja) * | 2007-03-23 | 2012-02-22 | 株式会社豊田中央研究所 | 多孔質支持体/水素選択透過膜基板及び多孔体支持型燃料電池 |
US8959773B2 (en) | 2009-09-28 | 2015-02-24 | Corning Incorporated | Method of making membrane filter |
MY166035A (en) * | 2011-04-25 | 2018-05-21 | Ngk Insulators Ltd | Method for cleaning ceramic filter |
WO2013054794A1 (ja) | 2011-10-11 | 2013-04-18 | 日本碍子株式会社 | セラミックフィルタ |
US9126830B2 (en) * | 2013-08-06 | 2015-09-08 | Bettergy Corp. | Metal doped zeolite membrane for gas separation |
-
2015
- 2015-02-13 EP EP15769832.5A patent/EP3124104B1/en active Active
- 2015-02-13 CN CN201580012179.5A patent/CN106102879B/zh active Active
- 2015-02-13 MY MYPI2016703404A patent/MY183887A/en unknown
- 2015-02-13 WO PCT/JP2015/054012 patent/WO2015146354A1/ja active Application Filing
- 2015-02-13 JP JP2016510114A patent/JP6436974B2/ja active Active
-
2016
- 2016-09-09 US US15/260,703 patent/US10391454B2/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03284328A (ja) * | 1990-03-30 | 1991-12-16 | Ngk Insulators Ltd | セラミック膜フイルタおよびその製造方法 |
JP2007254222A (ja) * | 2006-03-24 | 2007-10-04 | Ngk Insulators Ltd | セラミックス多孔質膜、セラミックスフィルターとその製造方法 |
JP2007284303A (ja) * | 2006-04-18 | 2007-11-01 | Japan Science & Technology Agency | 3次元構造メソポーラスシリカとその薄膜の製造方法 |
WO2011040205A1 (ja) * | 2009-09-29 | 2011-04-07 | 日本碍子株式会社 | ゼオライト膜の製造方法、およびその製造方法により得られたゼオライト膜 |
JP2013529132A (ja) * | 2010-05-25 | 2013-07-18 | コーニング インコーポレイテッド | コージエライトモノリスにおけるコージエライト膜 |
JP2012066241A (ja) * | 2010-08-26 | 2012-04-05 | Mitsubishi Chemicals Corp | 多孔質支持体―ゼオライト膜複合体およびそれを用いる分離方法 |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021120157A (ja) * | 2016-03-30 | 2021-08-19 | 日本碍子株式会社 | セラミック膜フィルタの製造方法 |
CN109070017B (zh) * | 2016-03-30 | 2021-08-24 | 日本碍子株式会社 | 陶瓷膜过滤器及其制造方法 |
JP7198082B2 (ja) | 2016-03-30 | 2022-12-28 | 日本碍子株式会社 | セラミック膜フィルタ |
US10974203B2 (en) | 2016-03-30 | 2021-04-13 | Ngk Insulators, Ltd. | Ceramic membrane filter and method for producing the same |
CN109070017A (zh) * | 2016-03-30 | 2018-12-21 | 日本碍子株式会社 | 陶瓷膜过滤器及其制造方法 |
WO2017169865A1 (ja) * | 2016-03-30 | 2017-10-05 | 日本碍子株式会社 | セラミック膜フィルタ及びその製造方法 |
JP7169401B2 (ja) | 2016-03-30 | 2022-11-10 | 日本碍子株式会社 | セラミック膜フィルタの製造方法 |
JPWO2017169865A1 (ja) * | 2016-03-30 | 2019-02-14 | 日本碍子株式会社 | セラミック膜フィルタ及びその製造方法 |
JP2023011761A (ja) * | 2016-03-30 | 2023-01-24 | 日本碍子株式会社 | セラミック膜フィルタ |
US20190001278A1 (en) * | 2016-03-31 | 2019-01-03 | Ngk Insulators, Ltd. | Porous support, method for manufacturing porous support, separation membrane structure, and method for manufacturing separation membrane structure |
CN108883377A (zh) * | 2016-03-31 | 2018-11-23 | 日本碍子株式会社 | 多孔质支撑体、多孔质支撑体的制造方法、分离膜结构体以及分离膜结构体的制造方法 |
CN108883377B (zh) * | 2016-03-31 | 2021-05-07 | 日本碍子株式会社 | 多孔质支撑体、多孔质支撑体的制造方法、分离膜结构体以及分离膜结构体的制造方法 |
WO2017169591A1 (ja) * | 2016-03-31 | 2017-10-05 | 日本碍子株式会社 | 多孔質支持体、多孔質支持体の製造方法、分離膜構造体及び分離膜構造体の製造方法 |
US11135553B2 (en) | 2016-03-31 | 2021-10-05 | Ngk Insulators, Ltd. | Porous support, method for manufacturing porous support, separation membrane structure, and method for manufacturing separation membrane structure |
JPWO2017169591A1 (ja) * | 2016-03-31 | 2019-01-17 | 日本碍子株式会社 | 多孔質支持体、多孔質支持体の製造方法、分離膜構造体及び分離膜構造体の製造方法 |
JP2018122282A (ja) * | 2017-01-30 | 2018-08-09 | イーセップ株式会社 | 水素分離膜 |
JP2019098211A (ja) * | 2017-11-29 | 2019-06-24 | 京セラ株式会社 | 炭素膜付き多孔質体 |
JP2019209275A (ja) * | 2018-06-06 | 2019-12-12 | 東芝ライフスタイル株式会社 | 酸素富化膜、及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN106102879A (zh) | 2016-11-09 |
JP6436974B2 (ja) | 2018-12-12 |
CN106102879B (zh) | 2019-12-13 |
EP3124104A1 (en) | 2017-02-01 |
MY183887A (en) | 2021-03-17 |
JPWO2015146354A1 (ja) | 2017-04-13 |
US20160375405A1 (en) | 2016-12-29 |
US10391454B2 (en) | 2019-08-27 |
EP3124104A4 (en) | 2017-11-22 |
EP3124104B1 (en) | 2024-02-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6436974B2 (ja) | モノリス型分離膜構造体及びモノリス型分離膜構造体の製造方法 | |
US9149771B2 (en) | Ceramic porous membrane and ceramic filter | |
US7717272B2 (en) | Ceramic porous membrane and ceramic filter | |
EP2083942A1 (en) | Method of manufacturing ceramic porous membrane and method of manufacturing ceramic filter | |
JP2010506700A (ja) | セラミックフィルタの製造方法 | |
WO2016158582A1 (ja) | ゼオライト膜構造体 | |
JP6667614B2 (ja) | 多孔質支持体、多孔質支持体の製造方法、分離膜構造体及び分離膜構造体の製造方法 | |
JP6490665B2 (ja) | モノリス型分離膜構造体、モノリス型分離膜構造体の製造方法及び脱水方法 | |
WO2012111792A1 (ja) | 炭素膜付き複合体およびその製造方法 | |
JP6767876B2 (ja) | 分離膜構造体及びその製造方法 | |
WO2016104048A1 (ja) | ガス分離方法 | |
WO2015151699A1 (ja) | モノリス型分離膜構造体 | |
JP6559146B2 (ja) | 分離膜構造体の製造方法 | |
WO2016104049A1 (ja) | ガス分離方法 | |
JP6541644B2 (ja) | モノリス型基材、モノリス型分離膜構造体及びモノリス型基材の製造方法 | |
JP6417355B2 (ja) | モノリス型分離膜構造体 | |
JP6636932B2 (ja) | 膜構造体及びその製造方法 | |
JP2013027823A (ja) | 炭素膜付き多孔質体およびその製造方法 | |
WO2015146571A1 (ja) | モノリス型分離膜構造体及びその製造方法 | |
JP2015188840A (ja) | モノリス型分離膜構造体 | |
JP2017177078A (ja) | モノリス型分離膜構造体 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15769832 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016510114 Country of ref document: JP Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2015769832 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2015769832 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |