WO2007058388A1 - ゼオライト配向膜配設体 - Google Patents
ゼオライト配向膜配設体 Download PDFInfo
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- WO2007058388A1 WO2007058388A1 PCT/JP2006/323523 JP2006323523W WO2007058388A1 WO 2007058388 A1 WO2007058388 A1 WO 2007058388A1 JP 2006323523 W JP2006323523 W JP 2006323523W WO 2007058388 A1 WO2007058388 A1 WO 2007058388A1
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- WIPO (PCT)
- Prior art keywords
- zeolite
- plane
- film
- peak intensity
- support
- Prior art date
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- 239000010457 zeolite Substances 0.000 title claims abstract description 352
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 351
- 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 350
- 239000013078 crystal Substances 0.000 claims abstract description 194
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 138
- 239000012528 membrane Substances 0.000 claims description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 72
- 238000002441 X-ray diffraction Methods 0.000 claims description 57
- 238000000926 separation method Methods 0.000 claims description 57
- 238000005259 measurement Methods 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000010408 film Substances 0.000 description 184
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 50
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 36
- 238000010899 nucleation Methods 0.000 description 30
- 239000000377 silicon dioxide Substances 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000002245 particle Substances 0.000 description 20
- 229910001220 stainless steel Inorganic materials 0.000 description 20
- 239000010935 stainless steel Substances 0.000 description 20
- 238000001027 hydrothermal synthesis Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 17
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 17
- 239000000126 substance Substances 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- 239000002994 raw material Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 239000012466 permeate Substances 0.000 description 13
- 238000005373 pervaporation Methods 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 241000408939 Atalopedes campestris Species 0.000 description 8
- 230000007547 defect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 8
- 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 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000010981 drying operation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910016523 CuKa Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- FLVKFIUSROZKPN-UHFFFAOYSA-N azane;tetrapropylazanium Chemical compound N.CCC[N+](CCC)(CCC)CCC FLVKFIUSROZKPN-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 235000021438 curry Nutrition 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 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
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
-
- 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
- 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
-
- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
- B01D2325/023—Dense layer within the membrane
-
- 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
Definitions
- the present invention relates to a zeolite alignment film-arranged body, and more specifically, the c-axis of the zeolite crystal is oriented in a direction perpendicular to the support surface, and the thin zeolite alignment film is a surface of the support.
- the present invention relates to a zeolite alignment film provided on a surface.
- Zeolite is a kind of silicate having a network crystal structure in which fine pores having a uniform diameter are formed, and has a general formula: WmZnO n- sH 0 (W: sodium, potassium, Power
- MFI-type zeolite is a zeolite in which pores of about 0.5 nm are formed by a 10-membered oxygen ring in a crystal.
- nitrogen oxide (NO 2) in automobile exhaust gas It is used in applications such as adsorbents for adsorbing harmful substances such as hydrocarbons (HC) or catalysts for decomposing these harmful substances.
- zeolite is in the form of powder or granules, but it has also become possible to use it as a zeolite membrane by forming it into a membrane shape and as a separation membrane.
- a zeolite membrane can be obtained by reacting a zeolite raw material by hydrothermal synthesis in which it is heated in the presence of water vapor and depositing a zeolite crystal in the form of a film on the surface of the support.
- such a zeolite film may have a random crystal axis orientation relative to the surface of the zeolite film, or the b-axis and c-axis may be perpendicular to the zeolite film surface. (For example, see Patent Documents 1 to 4).
- Patent Document 1 Japanese Unexamined Patent Publication No. 2000-26115 Patent Document 2: JP 2004-250290 A
- Patent Document 3 Japanese Patent Publication No. 10-502609
- Patent Document 4 Japanese Patent Publication No. 2000-507909
- Patent Documents 1 and 2 disclose a zeolite film in which the b-axis of the zeolite crystal is oriented in a direction perpendicular to the surface of the support
- Patent Documents 3 and 4 disclose c of the zeolite crystal.
- a zeolite membrane having an axis oriented in a direction perpendicular to the support surface is disclosed.
- These zeolite membranes can be used as separation membranes for separating various substances depending on their structure, but they are a mixed liquid of water and ethanol. The use as a separation membrane (water Z ethanol separation membrane) was not disclosed.
- the present invention has been made in view of the above-mentioned problems, and is suitable as a water-ethanol separation membrane in which the c-axis of the zeolite crystal is oriented in a direction perpendicular to the support surface and the film thickness is thin.
- the present invention provides a zeolite alignment film-arranged body in which a zeolite alignment film that can be used in the above is disposed on the surface of a support.
- the present invention provides the following zeolite alignment film-provided body.
- the c-axis is oriented within a range of 90 ° ⁇ 33.76 ° with respect to the support surface, and the ratio of the zeolite crystals is 90% or more of the entire zeolite crystals, and the zeolite orientation Zeolite alignment film arrangement body having a film thickness of 1 to 30 / im.
- XRD X-ray diffraction
- Peak intensity derived from the 101 plane Is divided by (peak intensity derived from the 501 plane) ((peak intensity derived from the 101 plane) (peak intensity derived from the 501 plane)) is 1 or more, ((peak intensity derived from the 101 plane) // ( Zeolite alignment film arrangement according to [1] or [4], wherein the surface-derived peak intensity)) is 3 or more.
- Zeolite alignment film force The zeolite alignment film assembly according to any one of [1] to [6], which is a separation film that separates ethanol from a mixed solution of water and ethanol.
- the c-axis is oriented within a range of 90 ° ⁇ 33.76 ° with respect to the support surface.
- the ratio of zeolite crystals is 90% or more of the entire zeolite crystals, and the thickness of the zeolite alignment membrane is 1 to 30 / im, so when used as a water Z ethanol separation membrane, in a short time, It becomes possible to separate water and ethanol with high separation efficiency.
- water and eta It is suitable for use as a separation membrane when separating nor from the perparation method.
- FIG. 1 is a cross-sectional view schematically showing a state in which a support and silica zone are placed in a pressure resistant container in Example 1.
- FIG. 2 is an SEM photograph showing a state where zeolite seed crystals are precipitated on the support in Example 1.
- FIG. 3 is a cross-sectional SEM photograph showing a state in which a zeolite alignment film is formed on a support in Example 1.
- FIG. 4 is a cross-sectional SEM photograph showing a state where a zeolite film is formed on a support in Comparative Example 1.
- FIG. 5 is a graph showing X-ray diffraction measurement results of the zeolite oriented membrane of Example 1 and the zeolite membrane of Comparative Example 1.
- FIG. 6 is a schematic diagram showing an entire test apparatus for performing a pervaporation test.
- FIG. 7 is a perspective view schematically showing an MFI-type zeolite crystal.
- FIG. 8 is a schematic diagram showing a state in which MFI-type zeolite crystals are oriented in a specific direction with respect to the support surface.
- FIG. 9 shows an embodiment (monolith shape) of a support used in the method for producing a zeolite membrane of the present invention
- FIG. 9 (a) is a perspective view
- FIG. 9 (b) is a plan view. is there.
- FIG. 10 is a cross-sectional view showing a state in which a support is fixed to a pressure-resistant container and seeding or film forming zones are inserted in Examples or Comparative Examples.
- FIG. 11 is an SEM photograph showing the surface of the Zeoli alignment film formed on the surface of the support in Example 2.
- FIG. 11 (a) is an SEM photograph magnified 1500 times
- FIG. b) is a SEM photograph magnified 150 times.
- FIG. 12 is a cross-sectional SEM photograph showing a state in which a zeolite alignment film is formed on the surface of a support in Example 2.
- FIG. 13 is an SEM photograph showing the surface of the zeolite alignment film formed on the surface of the support in Example 3, and FIG. I 3 (a) is an SEM photograph magnified 1500 times, and FIG. b) 15 It is a SEM photograph magnified 0 times.
- FIG. 14 is a cross-sectional SEM photograph showing a state where a zeolite alignment film is formed on the surface of a support in Example 3.
- FIG. 15 is a SEM photograph showing the surface of the zeolite membrane formed on the surface of the support in Comparative Example 2.
- FIG. 16 is a cross-sectional SEM photograph showing a state where a zeolite alignment film is formed on the surface of a support in Comparative Example 2.
- FIG. 17 is a graph showing the results of X-ray diffraction measurement of a zeolite (orientation) film
- FIG. 17 (a) is a graph for the zeolite orientation film of Example 2
- FIG. Fig. 17 (c) is a graph for the zeolite oriented film of Example 3
- Fig. 17 (c) is a graph for the zeolite film of Comparative Example 2.
- 61 pressure vessel
- 62 inner cylinder
- 63 stainless steel vessel
- 64 fixing jig
- 65 porous alumina support
- 66 sol for seeding
- 66 ' sol for film formation
- 71 zeolitic orientation Membrane
- 72 Zeolite membrane.
- the zeolite orientation film provided body of the present invention includes a support and a film provided on the surface of the support.
- the ratio force of the zeolite crystals oriented in the range is 90% or more of the entire zeolite crystals, and the thickness of the zeolite alignment film is 1 to 30 m.
- the zeolite alignment film constituting the zeolite alignment film-provided body of the present invention has a film-like MFI-type zeolite crystal.
- the zeolite alignment film constituting the zeolite alignment film-provided body of the present invention is preferably composed of 100% by mass of a film-like MFI-type zeolite crystal, but may inevitably contain impurities.
- the zeolite oriented film constituting the zeolite oriented film-arranged body of the present invention is an MFI-type zeolite crystal (hereinafter sometimes simply referred to as “zeolite crystal”), and its c-axis is relative to the support surface. 90% ⁇ 33.
- the degree of MFI-type zeolite crystals is 90% or more of the whole MFI-type zeolite crystals, and the thickness of the zeolite-oriented film is 1 to 30 / im. is there.
- the zeolite oriented membrane constituting the zeolite oriented membrane-provided body of the present invention is constituted in this way, when used as a water Z ethanol separation membrane, water and ethanol can be separated with high efficiency in a short time. Can be separated. In particular, it can be suitably used as a separation membrane when water and ethanol are separated by a perparation method. .
- the zeolite oriented membrane constituting the zeolite oriented membrane-provided body of the present invention has a c-axis of 90 ° ⁇ 33.76 ° with respect to the surface of the support in the MFI type zeolite crystal.
- the ratio of the material (zeolite crystal) that is oriented within the range (c-axis orientation) is 90% or more of the entire MFI-type zeolite crystal, and is preferably closer to 100%.
- the angle between the c-axis and the surface of the support means an acute angle or a right angle formed by the c-axis and the surface of the support.
- c-axis oriented zeolite crystal force must be 75% or more of the entire zeolite crystal 90% or more is particularly preferable. By setting it as such a range, when it uses as a water ethanol separation membrane, it becomes possible to permeate
- the c-axis orientation ratio is calculated from the results of observation with a scanning electron microscope (SEM) on the film surface.
- each crystal axis (a-axis, b-axis and c-axis) of the zeolite orientation film can be obtained by X-ray diffraction (XRD) measurement. Specifically, it can be obtained by comparing the peak intensity derived from the crystal plane or crystal axis oriented in the direction perpendicular to the surface of the support and the peak intensity derived from other directions.
- the X-ray diffraction measurement device uses Rigaku Co., Ltd.'s MiniFl ex (first X-ray diffractometer).
- X-ray source CuKa
- tube current 30 kV
- tube voltage 15 mA
- filter Ni
- scan speed 4 ° Zmin.
- the zeolite orientation film constituting the zeolite orientation film-provided body of the present invention is a force in which the crystal axis of the zeolite crystal has the above orientation. Furthermore, the specific crystal plane has the following orientation. Is preferred.
- the zeolite alignment film constituting the zeolite alignment film arrangement of the present invention has a peak intensity derived from each crystal plane obtained by X-ray diffraction (XRD) measurement using the first X-ray diffraction apparatus.
- the value obtained by dividing (peak intensity derived from the 002 plane) by (peak intensity derived from the 020 plane) ((peak intensity derived from the 002 plane) / (peak intensity derived from the 020 plane)) is preferably 2 or more. More preferably, it is 3 to 10 5 .
- (peak intensity derived from 002 plane) / (peak intensity derived from 101 plane) is preferably 0.5 to: I.5.
- the peak intensity derived from the 101 plane / preferably (peak click intensity from 501 surface) is 1.5 or more, and more preferably 2 to 10 5 les. Further, it is more preferable that the (peak intensity derived from the 303 plane) Z (peak intensity derived from the 501 plane) is 2 or more, preferably 3 to 10 5 . Due to the above-mentioned specific crystal planes having such a relationship, when the zeolite alignment film constituting the present invention is used as a water-Z ethanol separation film, it is possible to efficiently transmit ethanol. .
- the zeolite orientation film constituting the present invention has such crystal plane orientation characteristics, it suppresses water permeation and allows ethanol to permeate efficiently, resulting in a film having high water and ethanol separation performance. . In particular, it exhibits high performance as a separation membrane when ethanol is separated from a mixture of water and ethanol by the pervaporation method.
- the first X-ray diffraction apparatus is Rigaku MiniFlex, and the X-ray diffraction (XRD) measurement conditions are preferably the same as the conditions for measuring the orientation of the crystal axes.
- the zeolite oriented film constituting the present invention contains a lot of c-axis oriented crystals as described above.
- the zeolite alignment film constituting the zeolite alignment film provided body of the present invention is the above first Among the peak intensities derived from each crystal plane obtained by X-ray diffraction (XRD) measurement using the X-ray diffractometer, 001, 002, 004, 101, 102, 103, 104, 105 Peak strength derived from surface, 202, 303 and 404 surfaces Peaks derived from 010, 020, 040, 060, 100, 200, 400, 600, and 501 surfaces It is preferred to be at least twice the total strength, and even more preferred to be at least 3.
- XRD X-ray diffraction
- XRD peak strength force derived from a specific crystal plane With this relationship, water permeation can be suppressed and ethanol can be permeated efficiently, resulting in a membrane with high water and ethanol separation performance. In particular, it exhibits high performance as a separation membrane when ethanol is separated from a mixture of water and ethanol by the pervaporation method.
- Total force of peak bow intensity derived from 001, 002, 004, 101, 102, 103, 104, 105, 202, 303, and 404 Ethanol separation performance may be reduced.
- the crystal plane of the zeolite alignment film (MFI type zeolite crystal) constituting the zeolite alignment film of the present invention using the second X-ray diffraction apparatus shown below, It is preferable that the crystal plane of have the following orientation.
- the peak intensities derived from each crystal plane obtained by X-ray diffraction (XRD) measurement using the second X-ray diffractometer the 001 plane, 002 plane, 004 plane, 101 plane, 10
- the total peak intensity derived from 2, 103, 104, 105, 202, and 303 surfaces is 010, 020, 040, 051, 100, 200, 400, 301, and It is more than twice the total peak intensity derived from the 501 plane, but more preferably more than 4 times. Due to this relationship, the peak intensity of XRD derived from a specific crystal plane This prevents the permeation of water and allows ethanol to permeate efficiently, resulting in a membrane with high water and ethanol separation performance.
- the second X-ray diffractometer is RINT-TTR III manufactured by Rigaku Corporation. Measurement conditions are X-ray source: CuK ⁇ , tube current: 50kV, tube voltage: 300mA, scan axis: 20/0, scan mode: continuous, sampling width: 0.02 °, scan speed: 1 ° Zmin Divergence slit: 1. Omm, divergence longitudinal slit: 10 mm, scattering slit: open, light receiving slit: open, long solar slit opening angle: 0.114 ° is preferable.
- the zeolite alignment film (MFI type zeolite crystal) constituting the zeolite alignment film provided body of the present invention is obtained by X-ray diffraction (XRD) measurement using the second X-ray diffractometer.
- XRD X-ray diffraction
- peak intensity derived from crystal plane (peak intensity derived from 101 plane) divided by (peak intensity derived from 501 plane) ((peak intensity derived from 101 plane) / (peak derived from 501 plane) Strength)) force; preferably 1 or more, more preferably 4 or more.
- ((peak intensity derived from the 101 plane) / (peak intensity derived from the 020 plane)) is preferably 3 or more, more preferably 8 or more. Since the specific crystal plane has such a relationship, when the zeolite oriented membrane constituting the present invention is used as a water / ethanol separation membrane, ethanol can be efficiently permeated.
- Peak intensity derived from the 101 plane No (peak intensity derived from the 501 plane) is in the range of 1 or more, which means that the crystal is oriented so that the 101 plane is parallel to the surface of the support. This ratio is larger than the ratio of zeolite crystals in which the a-axis is oriented almost perpendicularly to the surface of the support (inclined by the angle of the 501 plane). When the ratio of the peak intensity derived from the 101 plane is smaller than the above range, the ethanol separation performance may be lowered.
- peak intensity derived from the 101 plane (peak intensity derived from the 020 plane) is in the range of 3 or more, which means that the proportion of zeolite crystals with the b-axis oriented perpendicular to the surface of the support is small. It shows that there are many crystals oriented so that the 101 plane is parallel to the surface of the support. If the ratio of the peak strength derived from the 101 surface is smaller than the above range, the ethanol separation performance will decrease. Power.
- the zeolite oriented membrane constituting the present invention has such characteristics in the orientation of crystal planes, it suppresses the permeation of water and efficiently permeates ethanol, and a membrane having a high separation performance of water and ethanol. Become. In particular, it shows high performance as a separation membrane when ethanol is separated from a mixture of water and ethanol by the pervaporation method.
- X-ray diffraction (XRD) measurement using the second X-ray diffractometer is as follows: X-ray source used: CuK ⁇ , tube current: 50 kV, tube voltage: 300 mA, scan axis: 20 Z 0, scan mode: Continuous, Sampling width: 0.02 °, Scanning speed: ⁇ / min, Divergence slit: 1. Omm, Divergence longitudinal slit: 10mm, Scattering slit: Open, Receiving slit: Open, Long-sole slit opening angle: 0 It is preferably 114 °.
- the zeolite alignment film constituting the zeolite alignment film-arranged body of the present invention has a thickness of 1 to 30 ⁇ m. ⁇ 20 / m is preferred! Particularly preferred is ⁇ 15 ⁇ m.
- the thickness of the zeolite alignment film is a value obtained by observing the section of the zeolite alignment film with a scanning electron microscope (SEM).
- SEM scanning electron microscope
- the zeolite alignment film constituting the zeolite alignment film-provided body of the present invention preferably has a uniform film thickness. Since the film thickness is uniform, even when the zeolite alignment film is formed thin, no portion that is too thin is formed, and when ethanol or the like permeates, the entire zeolite alignment film can be transmitted uniformly. . In addition, defects or the like hardly occur in the zeolite alignment film.
- the degree of uniformity of the zeolite alignment film is determined by the SEM image of the fracture surface of the zeolite alignment film, and expressed as ((maximum film thickness – minimum film thickness) / maximum film thickness) X 100 (%). It can be shown by the sex formula.
- the zeolite alignment film constituting the zeolite alignment film-provided body of the present invention is preferably dense. By being dense, when used as a separation membrane, it is possible to efficiently separate the mixed solution over the entire surface of the membrane where the mixed solution does not escape from the gaps between the zeolite crystals.
- the term “dense” refers to a state in which the surface of the support is not exposed when observed with a scanning electron microscope (SEM).
- the zeolite alignment film-provided body of the present invention has a zeolite alignment film disposed on the surface of the support, but the zeolite alignment film is disposed on the surface of the support so that the zeolite alignment film is thinned. However, it is supported by the support and can maintain its shape and prevent damage and the like.
- the support is not particularly limited as long as it can form a zeolite seed crystal on the surface and form a zeolite alignment film.
- the material, shape and size of the support can be appropriately determined according to the application. Examples of the material constituting the support include alumina ( ⁇ -alumina, ⁇ -alumina, anodized alumina, etc.), ceramics such as zirconia, and metals such as stainless steel.
- alumina is preferable.
- Alumina is preferably formed and sintered using an anolemina particle having an average particle diameter of 0.001 to 30 / m as a raw material.
- the support is preferably a porous body.
- the shape of the support may be any of a plate shape, a cylindrical shape, a tubular shape with a polygonal cross section, a monolith shape, a spiral shape, etc., but a monolith shape is preferred.
- the monolith shape refers to a columnar shape in which a plurality of flow passages (channels) 52 are formed in parallel in the axial direction 53 like the support 51 shown in FIGS. 9 (a) and 9 (b). Say things.
- FIG. 9 (a) and 9 (b) see things.
- FIG. 9 shows one embodiment (monolith shape) of a support used in the method for producing a zeolite membrane of the present invention
- FIG. 9 (a) is a perspective view
- FIG. 9 (b) is a plan view.
- the support 51 is particularly preferably a monolithic porous body 54.
- Such a support made of a monolithic porous body can be formed by a known manufacturing method, and can be formed by, for example, extrusion molding.
- the zeolite alignment membrane constituting the zeolite alignment membrane assembly of the present invention is preferably used as a separation membrane for separating ethanol from a mixed solution of ethanol and water.
- Power S can be.
- it has an excellent function as a separation membrane when ethanol is separated by a pervaporation method.
- an ethanol Z water mixed solution having an ethanol concentration of 3 to 20% by volume can be made into a solution having an ethanol concentration of 50 to 95% by volume after passing through the separation membrane.
- the permeation flux:! ⁇ 8kgZm 2 it is possible to time
- the separation factor may be a 15 to 80.
- the permeation flux is the mass of all substances permeated through the separation membrane per unit time (hour) and unit area (m 2 ).
- the separation factor is the ethanol concentration (volume%) and water concentration (volume) in the permeate with respect to the ratio of ethanol concentration (volume%) and water concentration (volume%) in the feed liquid as shown by the following formula. %) And the ratio value.
- the method for producing a zeolite orientation film-provided body of the present invention comprises a pressure-resistant container such that a seeding zone containing silica, water and a structure-directing agent and a support are immersed in the seedling zone.
- the heating temperature of the pressure vessel is 90 to 130 °. It is preferable to be C.
- the c-axis is oriented within the range of 90 ° ⁇ 33.76 ° with respect to the support surface in the zeolite crystals constituting the zeolite aligned membrane.
- the ratio force of the zeolite crystals is 90% or more of the entire zeolite crystals and the film thickness power of the zeolite alignment film is 20 ⁇ .
- the seeding sol used in the method for producing an oriented zeolite membrane of the present invention is a sol in which silica fine particles are dispersed in water and contains at least a structure-directing agent therein.
- This seeding sol can be obtained by mixing a predetermined amount of silica sol having a predetermined concentration, water for adjusting the concentration, and a structure directing agent aqueous solution having a predetermined concentration.
- This seeding sol is crystallized into zeolite by hydrothermal treatment, which will be described later, to form a structure in which silica atoms derived from the silica sol are surrounded around the molecules of the structure directing agent.
- the structure-directing agent is removed from the structure by heat treatment described later, and a zeolite crystal having a pore shape specific to the structure-directing agent can be formed.
- silica sol a commercially available silica sol (for example, trade name: Snowtex S, manufactured by Nissan Chemical Industries, Ltd., solid content concentration: 30 mass / 0 ) can be suitably used.
- the solid content means silica.
- one prepared by dissolving silica fine powder in water or one prepared by hydrolyzing alkoxysilane may be used.
- the zeolite seed crystals can be made into fine particles and adhered to the support surface.
- the hydrosilica molar ratio is less than 10
- the zeolite seed crystals may be deposited heterogeneously and excessively on the support surface, and when it is more than 50, the zeolite seed crystals may not precipitate on the support surface.
- the state where the zeolite seed crystals are attached to the surface of the support is, for example, quantitatively expressed as a ratio (area ratio on the photograph) of the surface covered with the surface of the support electron microscope (SEM). 5 to 100% is preferable.
- tetrapropyl ammonium hydroxide (TPAOH) or tetrapropyl ammonium bromide (TP ABr) capable of generating tetrapropyl ammonium ion (TPA) is used. Therefore, an aqueous solution containing TPA 0H and / or TP ABr can be suitably used as the structure directing agent aqueous solution.
- TP AOH used as a structure-directing agent for MFI-type zeolite is a relatively expensive reagent.
- a TPA source and an alkali source can be obtained from ABr and a hydroxide such as an alkali metal. That is, in this method, the amount of expensive TPAOH used can be reduced, so that raw material costs can be reduced and zeolite can be produced at low cost.
- the two should be mixed so that the mole ratio of TPA to silica (TPA / silica ratio) is within the range of 0.05-0.5. Is more preferable, and it is more preferable to set it within the range of 0.1 to 0.3. If the TPA / silica ratio is less than 0.05, seed crystals may not be precipitated, and if it exceeds 0.5, it may be excessively deposited on the support surface.
- the water added at the time of preparing the seeding sol preferably does not contain impurity ions, and specifically, is preferably distilled water or ion-exchanged water.
- the support is preferably the same as the support used for supporting the zeolite alignment film provided body of the present invention. That is, the material, shape, and size are not particularly limited as long as a zeolite seed crystal can be formed on the surface and a zeolite oriented film can be formed, and the material, shape, and size can be appropriately determined according to the application.
- the material constituting the support include alumina (c-alumina, ananoremina, anodized alumina, etc.), ceramics such as zirconia, and metals such as stainless steel. From the standpoint of easy preparation and availability of the support. Alumina is preferred. Alumina is preferably molded and sintered using alumina particles having an average particle size of 0.001-3 Ozm as a raw material.
- the shape of the support may be any shape such as a plate shape, a cylindrical shape, a tubular shape having a polygonal cross section, a monolith shape, and a spiral shape.
- the support and the seeding sol are placed in a pressure resistant container. At this time, it arrange
- the pressure vessel is not particularly limited, but a stainless steel pressure vessel with a fluororesin inner cylinder, a nickel metal pressure vessel, or the like can be used.
- Sol for seeding support In the case of dipping in the seeding sol, it is preferable to submerge at least a portion where the zeolite seed crystal is precipitated in the seeding sol, and the entire support may be submerged in the seeding sol.
- the temperature is 90 to L30 ° C, more preferably 100 to 120 ° C. If the temperature is lower than 90 ° C, hydrothermal synthesis is difficult to proceed. If the temperature is higher than 130 ° C, the resulting zeolite crystal cannot be atomized.
- the temperature of the hydrothermal synthesis is set in the above range (90 to 130 ° C), so that each of the alumina particles positioned on the support surface can be obtained.
- the surface can be covered with zeolite seed crystals.
- the synthesis time of hydrothermal synthesis is preferably 3 to 18 hours, more preferably 6 to 12 hours. If it is shorter than 3 hours, hydrothermal synthesis may not proceed sufficiently, and if it is longer than 18 hours, the zeolite seed crystal may become too large. In this way, if the zeolite seed crystals are deposited directly on the surface of the support by hydrothermal synthesis, the zeolite seed crystals are difficult to peel off from the support. It is possible to prevent problems such as non-uniformity.
- examples of the heating method include a method in which a pressure vessel is put in a hot air dryer and heated, or a heater is directly attached to the pressure vessel and heated.
- the particle size of the obtained zeolite seed crystal is preferably as small as possible.
- the particle diameter is preferably 1 / m or less, more preferably 0.5 or less, and particularly preferably 0.01 to 0.5 ⁇ m.
- V is greater than 1 m, a dense zeolite alignment film with few defects and a uniform film thickness may not be formed during the film formation process.
- the particle size of the zeolite seed crystal is a value obtained by observation with a scanning electron microscope (SEM). When the particle size is 1 ⁇ m or less, the maximum particle size is 1 ⁇ m or less. .
- the zeolite seed crystals are precipitated on the surface of the support, it is preferable to boil and wash the support using water. Thereby, generation
- the washing time is not particularly limited as long as the seedling is washed away, but it is preferable to repeat the washing for 0.5 to 3 hours:! To 5 times. After washing, drying at 60 to 120 ° C for 4 to 48 hours is preferable.
- the film-forming sol uses the same silica sol, structure directing agent, and water contained in the seeding sol as described above, and uses more water than the seeding sol. It is preferable to use one having a concentration lower than that of the sol.
- water / silica molar ratio is 100 to 700, it is possible to form a dense zeolite alignment film with uniform thickness and few defects, and the thickness of the zeolite alignment film can be controlled to a desired thickness. If the water / silica molar specific force is smaller, the silica concentration becomes higher, so that zeolite crystals are deposited in the film-forming sol and deposited on the surface of the zeolite alignment film, so that cracks are likely to occur during activation treatment such as firing. May be.
- the water-silica molar ratio is greater than 700, and the zeolite alignment film is difficult to become dense.
- the film-forming sol when mixing the silica sol and the structure directing agent aqueous solution, both are adjusted so that the molar ratio of TPA to silica (TPAZ silica ratio) is within the range of 0.01-0.5. Mixing is preferred. More preferably, it is within the range of 02-0.3. If the TPA / silica ratio is less than 0.01, the membrane is difficult to become dense. If it exceeds 0.5, zeolite crystals may be deposited on the membrane surface.
- Zeolite seed crystals deposited on the surface of the support are grown by hydrothermal synthesis to form a zeolite alignment film made of zeolite crystals grown in a film form on the surface of the support.
- the support on which the zeolite seed crystal was precipitated and the film-forming sol were placed in a pressure-resistant container. Put in. At this time, the support is disposed so as to be immersed in the film-forming sol. Thereafter, the inside of the pressure vessel is heated and a zeolite alignment film is formed on the support surface by hydrothermal synthesis.
- the zeolite alignment film obtained by hydrothermal synthesis contains tetrapropyl ammonium, it is preferable to perform heat treatment after that in order to finally obtain the zeolite alignment film.
- the pressure vessel it is preferable to use the pressure vessel used for producing the zeolite seed crystal.
- a support in a sol for film formation at least a zeolite orientation film It is preferable to submerge the entire support in the seeding sol, in which it is preferable to submerge the site for forming the seed in the seeding sol.
- the temperature for hydrothermal synthesis is preferably 100 to 200 ° C. force S, more preferably 120 to 180 ° C. By setting the temperature within such a range, it is possible to obtain a fine zeolite alignment film having a uniform thickness and few defects.
- a high quality film can be produced with good reproducibility, and the production efficiency is high.
- the temperature is lower than 100 ° C, hydrothermal synthesis may be difficult to proceed, and if the temperature is higher than 200 ° C, the resulting zeolite alignment film may be difficult to be made dense with few defects of uniform thickness. is there.
- the synthesis time of hydrothermal synthesis is preferably 3 to 120 hours, more preferably 6 to 90 hours, and even more preferably 10 to 72 hours. If it is shorter than 3 hours, hydrothermal synthesis may not proceed sufficiently, and if it is longer than 120 hours, it may become too thick with a non-uniform thickness.
- the zeolite alignment film when the zeolite alignment film is dense, it means that the surface of the support is not exposed when observed with a scanning electron microscope (SEM). Further, the defects of the zeolite alignment film can be observed visually by rinsing with water quickly after applying a colorant such as rhodamine B solution to the support surface, and there are few defects. If this is the case, check that the color remains almost unchanged.
- SEM scanning electron microscope
- the thickness of the obtained zeolite alignment film is preferably 30 / im or less, more preferably 1 to 30 ⁇ : particularly preferably! To 20 ⁇ .
- the power to be between 1 and 15 ⁇ . Most preferred. If it is thicker than 30 ⁇ , the separation efficiency may decrease when used as a separation membrane.
- the thickness of the zeolite orientation film is a value obtained by observation with a scanning electron microscope (SEM). Since a thin film can be formed in this way, it is possible to obtain a separation film with high separation performance in combination with the above-described characteristics when the film thickness is uniform and dense with few defects.
- the obtained zeolite orientation film is one in which the c-axis of the zeolite crystal is oriented in a direction perpendicular to the support surface (c-axis orientation), and in the zeolite crystal, the c-axis is Proportion of zeolite crystals oriented in the range of 90 ° ⁇ 33.76 ° with respect to the support surface More than 90% of the entire zeolite crystals. That is, the zeolite alignment film obtained by the above method is a zeolite alignment film constituting the zeolite alignment film arrangement of the present invention described above, The properties of the zeolite orientation film constituting the present invention are satisfied.
- the zeolite membrane obtained by the production method of the present invention can be used for separation of a mixture of other low molecular weight substances that is not only a mixed solution of water and ethanol.
- the zeolite alignment film is formed on the surface of the support by hydrothermal synthesis, it is preferable to boil and wash the support using water. As a result, it is possible to prevent excessive zeolite crystals from being deposited on the zeolite alignment film.
- the washing time is not particularly limited, it is preferable to repeat the washing for 0.5 to 3 hours 1 to 5 times. After washing, it is preferably dried at 60 to 120 ° C. for 4 to 48 hours.
- the zeolite oriented film formed on the surface of the support obtained by the above method is subjected to a calothermal treatment (activation treatment) to remove tetrapropyl ammonium, and finally the zeolite.
- An alignment film is formed.
- the heating temperature is preferably 400 to 600 ° C.
- the heating time is preferably 1 to 60 hours.
- An example of equipment used for heating is an electric furnace.
- the obtained seeding sol 3 is placed in a stainless steel 300 ml pressure vessel 1 in which a fluororesin inner cylinder 4 is disposed, and has a diameter of 12 mm and a thickness of 2 to 2 mm. Then, a cylindrical porous alumina support 2 having a length of 16 Omm was immersed and reacted in a hot air dryer at 110 ° C. for 10 hours.
- Alumina support 2 is made of pressure-resistant container 1 by fixing jigs 5 and 6 made of fluororesin. Fixed inside. The support after the reaction was dried at 80 ° C. for 16 hours after washing with boiling five times. The surface of the support after the reaction was observed with a scanning electron microscope (SEM).
- the obtained film-forming sol 3 ′ is made of a stainless steel 300 ml pressure-resistant container having a fluororesin inner cylinder 4 disposed therein as shown in FIG.
- the porous alumina support 2 on which the zeolite seed crystals were deposited was immersed in 1 and reacted in a hot air drier at 180 ° C. for 60 hours. After the reaction, the support was dried at 80 ° C. for 16 hours after being boiled and washed 5 times.
- SEM scanning electron microscope
- a dense layer (zeolite alignment film) 12 having a thickness of about 13 ⁇ was formed.
- the dense layer was analyzed by X-ray diffraction under the following conditions, it was confirmed to be an MFI-type zeolite crystal.
- Figure 5 shows the X-ray diffraction measurement results.
- This sol is placed in a stainless steel 300 ml pressure vessel with a fluororesin inner cylinder, immersed in a porous alumina support with a diameter of 12 mm ⁇ , a thickness of 1 to 2 mm, and a length of 160 mm, and is heated in a 160 ° C hot air dryer. The reaction was allowed for 30 hours. The support after the reaction was washed with hot water 5 times and then dried at 80 ° C. for 16 hours. The film thickness was 26 m.
- ethanol was separated from a mixture of water and ethanol by pervaporation according to the following method ( Transmission). In the mixture of water and ethanol, the ethanol content was 10% by volume.
- X-ray diffraction (XRD) pattern uses Min iFlex made by Rigaku Co., Ltd., the first X-ray diffractometer. Used X-ray source: CuKa, tube current: 30kV, tube voltage: 15mA, filter: Obtained as Ni, scan speed: 4 ° no min. In FIG. 4, the vertical axis represents intensity (a.u.), and the horizontal axis represents 20 (°).
- FIG. 6 is a schematic diagram showing an entire test apparatus for performing a pervaporation test.
- an aqueous solution containing 10% by volume of ethanol placed in the raw material tank 21 is heated to about 70 ° C.
- SUS stainless steel
- the permeated vapor that passes through the zeolite alignment film 28 and is discharged from the permeated vapor recovery port 30 is recovered by the liquid N trap 31.
- the pressure on the permeate space 27 is a pressure controller.
- the stainless steel 25 is divided into a raw material side space 26 and a permeate side space 27 by a zeolite orientation film 28, and the supply liquid inlet port 23 and the supply liquid discharge port 24 are connected to the raw material side space 26.
- a permeated vapor recovery port 30 for discharging the permeated vapor to the outside is formed at the upper end of the permeate side space 27.
- the SUS module 25 is mounted with a cylindrical zeolitic alignment film disposed on the outer surface of a cylindrical support (not shown) in a cylindrical outer container made of SUS. It is a structured. The mass of the obtained liquid was weighed with an electronic balance, and the composition of the liquid was analyzed by gas chromatography.
- Table 1 shows the separation factor and permeation flux (kg m 2 / hour) obtained as a result of the above pareparation test.
- Tables 2 and 3 show the relationship of specific peak intensities obtained from the X-ray diffraction pattern.
- “c-axis” is derived from 001, 002, 004, 101, 102, 103, 104, 105, 202, 303, and 404, respectively. Indicates the sum of peak intensities.
- “A-axis b-axis” refers to the sum of the peak intensities derived from the 100, 200, 400, 600, and 501 planes (total a) and the 010, 020, 040, and 060 planes.
- FIG. 7 and 8 are explanatory diagrams of MFI-type zeolite crystals and c-axis orientation.
- FIG. 7 is a perspective view schematically showing crystal planes in the abc crystal axis system 42 of the crystal 41 of the MFI type zeolite.
- FIG. 8 is a schematic diagram showing a state in which MFI-type zeolite crystals are oriented in a specific direction with respect to the support surface 43.
- the angle formed by its c-axis 44a and the support surface 43 is 90 degrees + 33.76 degrees
- the 101 crystal plane of the zeolite crystal is parallel to the support surface 43. It is in a state of being arranged.
- the MFI-type zeolite crystal 41b has an angle formed by its c-axis 44b and the support surface 43 of 90 degrees, and the 001 crystal plane of the zeolite crystal is arranged parallel to the support surface 43. It is the state that was done.
- the reference examples in Tables 2 and 3 show X-ray diffraction of single crystal powder MFI-type zeolite with a particle size of 230 X 200 X 150 m (c-axis length X a-axis length X b-axis length). The relationship between the peak intensities obtained by measurement is shown.
- the reference MFI-type zeolite powder was obtained by hydrothermal synthesis.
- Comparative Example 1 0.4 0.6 0.6 0.3
- the zeolite orientation film obtained in Example 1 shows that the c-axis is in the range of 90 ° ⁇ 33.76 ° with respect to the support surface from the peak data derived from each crystal plane. It can be seen that the proportion of oriented zeolite crystals is large.
- Example 1 The zeolite alignment film obtained in Example 1 and the zeolite film obtained in Comparative Example 1 were subjected to the "X-ray diffraction 2" conditions using the second X-ray diffraction apparatus shown below. X-ray diffraction (XRD) measurement was performed.
- XRD X-ray diffraction
- Tables 4 and 5 show the relationship between specific peak intensities obtained from the X-ray diffraction pattern in the above measurement.
- X-ray diffraction measurement results first XRD apparatus
- X-ray diffraction 1 X-ray diffraction 1
- X-ray diffraction 2 Tables 6 and 7 compare the measurement results (second XRD device).
- “c-axis” refers to the sum of peak intensities derived from the 001, 002, 004, 101, 102, 103, 104, 105, 202, and 303 surfaces. Indicates.
- A-axis b-axis refers to the total peak intensity derived from the 100, 200, 400, 301, and 501 planes (total a) and the 010, 020, 040, and 051 planes. The sum of the peak intensities derived from each of these (total b) is the total value (total a and total b).
- the “c-axis / a-axis b-axis” indicates a value obtained by dividing the “c-axis” by the “a-axis b-axis”.
- ⁇ “101/020” means a value obtained by dividing the peak intensity derived from the 101 crystal plane by the peak intensity derived from the 020 crystal plane in the measured zeolite orientation film.
- the reference examples in Table 4 and Table 8 are X-rays of single crystal powder MFI-type zeolite with a particle size of 230 X 200 X 150 im (c-axis direction length X a-axis direction length X b-axis direction length). The relationship between the peak intensities obtained by diffraction measurement is shown.
- the reference MFI-type zeolite powder was obtained by hydrothermal synthesis.
- the zeolite orientation film force obtained in Example 1 indicates that the c-axis is oriented within the range of 90 ° ⁇ 33, 76 ° with respect to the support surface from the peak data derived from each crystal plane. Thus, it can be seen that the ratio of ruzelite crystals is large.
- Example 1 From Tables 6 and 7, even if the zeolite alignment film obtained in Example 1 was measured with the first X-ray diffractometer MiniFlex manufactured by Rigaku Corporation, it was the second X-ray diffractometer. , Even when measured with RINT-TTR III manufactured by Rigaku Corporation, the c-axis is oriented within the range of 90 ° ⁇ 33.76 ° with respect to the support surface from the peak data derived from each crystal plane. It can be seen that there is a large proportion of zeolite crystals.
- the obtained seeding sol 66 is placed in a stainless steel 300 ml pressure vessel 61 formed by placing a fluororesin inner cylinder 62 inside a stainless steel vessel 63, and the outer periphery is previously fluorinated.
- a monolithic porous alumina support 65 (see Fig. 9) with a diameter of 30 mm, a cell (channel) inner diameter of 3 mm, a cell (channel) number of 37, and a length of 180 mm covered with a resin temap is immersed in hot air at 110 ° C. The reaction was allowed to proceed for 10 hours in the dryer.
- Example 10 is a cross-sectional view showing a state in which the support is fixed to the pressure vessel and the seeding sol 66 or the film forming sol 6 6 ′ is put in Example 2.
- the alumina support 65 was fixed in the pressure vessel 61 by a fixing tool 64 made of fluororesin.
- the support after the reaction was dried at 80 ° C. for 16 hours after boiling and washing 5 times.
- SEM scanning electron microscope
- the entire surface of the porous alumina support was covered with approximately 0.5 m of zeolite crystal particles (zeolite seed crystal 21) without any gaps. .
- X-ray diffraction measurement of the crystal particles confirmed that it was MFI type zeolite.
- the obtained film-forming sol 66 ′ was used in the same manner as in the above-mentioned “generation of zeolite seed crystals”, as shown in FIG.
- the porous alumina support on which the zeolite seed crystals were deposited was immersed and reacted in a hot air dryer at 180 ° C. for 60 hours (reaction operation).
- the support after the reaction is boiled 5 times After boiling washing (washing operation), drying was performed at 80 ° C. for 16 hours (drying operation).
- the series of operations including the above reaction operation, washing operation and drying operation was repeated twice in total.
- SEM scanning electron microscope
- FIG. 11 is a SEM photograph showing the surface of the zeolite alignment film formed on the surface of the support.
- Fig. 11 (a) is a 1500 times SEM photograph
- Fig. 11 (b) is a 150 times SEM photograph. Is true.
- FIG. 12 is a cross-sectional SEM photograph showing a state in which a zeolite film is formed on the support.
- the obtained MFI type zeolite membrane formed on the surface of the porous alumina support was heated to 500 ° C. in an electric furnace and held for 4 hours to remove tetrapropyl ammonium, and a zeolite oriented membrane was formed.
- a zeolite alignment film-arranged body disposed on the support was obtained. .
- the obtained seeding sol 66 is placed in a stainless steel 300 ml pressure vessel 61 formed by placing a fluororesin inner cylinder 62 inside a stainless steel vessel 63.
- a monolithic porous alumina support 65 (see Fig. 9) with a diameter of 30 mm, a cell (channel) inner diameter of 3 mm, a cell (channel) number of 37, and a length of 180 mm is coated.
- the reaction was carried out in a hot air dryer at 110 ° C for 10 hours.
- the alumina support 65 was fixed in the pressure vessel 61 with a fixing jig 64 made of fluororesin.
- the support after the reaction was dried at 80 ° C. for 16 hours after boiling and washing 5 times.
- the obtained film-forming sol was placed in a stainless steel 300 ml pressure vessel having a fluororesin inner cylinder as shown in FIG.
- the porous alumina support on which the zeolite seed crystals were deposited was immersed and reacted in a hot air drier at 180 ° C. for 60 hours (reaction operation).
- the support after the reaction was dried (drying operation) for 16 hours at 80 ° C. after 5 boiling washings (washing operation).
- a series of operations including the above reaction operation, washing operation and drying operation was repeated twice in total.
- SEM scanning electron microscope
- FIG. 13 is an SEM photograph showing the surface of the zeolite membrane formed on the support surface.
- Fig. 13 (a) is a 1500 times SEM photograph, and Fig. 13 (b) is a 150 times SEM photograph.
- FIG. 14 is a cross-sectional SEM photograph showing a state where a zeolite film is formed on a support.
- a film-forming sol was prepared by adding 70 g of 30 wt% silica sol (Snowtex S, manufactured by Nissan Chemical Co., Ltd.) and stirring with a magnetic stirrer at room temperature for 30 minutes. As shown in FIG.
- this lens is placed in a stainless steel 300 ml pressure vessel formed by placing a fluororesin inner cylinder 62 inside a stainless steel container 63, and the outer periphery is preliminarily placed on a fluororesin tape.
- a monolithic porous alumina support 65 (see Fig. 9) with a diameter of 30 mm, a cell (channel) inner diameter of 3 mm, a number of cells (channels) of 37, and a length of 180 mm is immersed in hot water at 120 ° C. The reaction was allowed to proceed for 48 hours in the dryer. The support after the reaction was dried at 80 ° C. for 16 hours after washing with hot water 5 times. The film thickness was 10 ⁇ m.
- Measurement conditions are: X-ray source: CuKa, tube current: 50kV, tube voltage: 300mA, scan axis: 20/0, scan mode: continuous, sampling width: 0.02 °, scan speed: ⁇ Zmin, divergence Slit: 1. Omm, divergence longitudinal slit: 10 mm, scattering slit: open, receiving slit: open, long solar slit opening angle: 0 ⁇ 114 °.
- Table 8 shows the separation factor and permeation flux (kg / m 2 ⁇ hour) obtained as a result of the above parsing test.
- Tables 9 and 10 show the relationship between specific peak intensities obtained from the X-ray diffraction pattern.
- “c-axis” refers to peak intensities derived from the 001, 002, 004, 101, 102, 103, 104, 105, 202, and 303 surfaces, respectively. Indicates the total.
- A-axis b-axis refers to the total of the peak strength derived from 100, 200, 400, 301 and 501 (total a), 010, 020, 040 and 051
- the sum of the peak intensities derived from each of these (total b) is the total value (total value of total a and total b).
- the “c-axis Za-axis b-axis” indicates a value obtained by dividing the “c-axis” by the “a-axis b-axis”.
- “101 no 020” means a value obtained by dividing the peak intensity derived from the 101 crystal plane by the peak intensity derived from the 020 crystal plane of the measured zeolite orientation film.
- the reference examples in Table 9 and Table 10 are based on a single crystal powder MFI-type zeolite with a particle size of 2.30 X 200 XI 50 ⁇ m (c-axis length X a-axis length X b-axis length) X The relationship between the peak intensities obtained by line diffraction measurement is shown.
- the reference MFI-type zeolite powder was obtained by hydrothermal synthesis.
- the zeolite oriented film of Example 2 has a higher c-axis orientation rate than the zeolite oriented film of Example 3. From Table 8, it can be seen that the separation factor and the permeation flow force S of the zeolite oriented membrane of Example 2 having a high c-axis orientation rate are excellent. Since the zeolite membrane of Comparative Example 2 is not c-axis oriented from Tables 9 and 10, the separation factor and the permeation flow rate of the zeolite oriented membranes of Example 2 and Example 3 are different from those of the zeolite membrane of Comparative Example 2. It was superior.
- the present invention relates to a separation membrane capable of separating a specific substance from a mixture of low molecular weight substances.
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- Organic Chemistry (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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JP2007545350A JPWO2007058388A1 (ja) | 2005-11-17 | 2006-11-17 | ゼオライト配向膜配設体 |
BRPI0618690-4A BRPI0618690A2 (pt) | 2005-11-17 | 2006-11-17 | estrutura provida com pelìcula de zeólito orientada |
CA002629756A CA2629756A1 (en) | 2005-11-17 | 2006-11-17 | Oriented zeolite film-provided structure |
US12/118,929 US20080217240A1 (en) | 2005-11-17 | 2008-05-12 | Oriented zeolite film-provided structure |
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JP2005-332535 | 2005-11-17 | ||
JP2005332535 | 2005-11-17 |
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US12/118,929 Continuation US20080217240A1 (en) | 2005-11-17 | 2008-05-12 | Oriented zeolite film-provided structure |
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WO2007058388A1 true WO2007058388A1 (ja) | 2007-05-24 |
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PCT/JP2006/323523 WO2007058388A1 (ja) | 2005-11-17 | 2006-11-17 | ゼオライト配向膜配設体 |
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US (1) | US20080217240A1 (ja) |
JP (1) | JPWO2007058388A1 (ja) |
BR (1) | BRPI0618690A2 (ja) |
CA (1) | CA2629756A1 (ja) |
WO (1) | WO2007058388A1 (ja) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2010106881A1 (ja) | 2009-03-16 | 2010-09-23 | 日本碍子株式会社 | ゼオライト分離膜配設体、その製造方法、混合流体の分離方法、及び混合流体分離装置 |
JP2015160186A (ja) * | 2014-02-28 | 2015-09-07 | 日本ゼオン株式会社 | 膜分離方法 |
JP2016034917A (ja) * | 2014-08-01 | 2016-03-17 | Jx日鉱日石エネルギー株式会社 | ノルマルパラフィンまたはパラキシレンの分離方法およびゼオライト膜複合体 |
JP2016073956A (ja) * | 2014-10-08 | 2016-05-12 | 学校法人早稲田大学 | ノルマルパラフィンの分離方法 |
WO2016121377A1 (ja) * | 2015-01-27 | 2016-08-04 | 日本ゼオン株式会社 | 分離膜およびその製造方法 |
CN106957062A (zh) * | 2017-05-05 | 2017-07-18 | 南京工业大学 | 一种取向sapo‑34分子筛膜的制备方法 |
JP2017140568A (ja) * | 2016-02-09 | 2017-08-17 | 日本特殊陶業株式会社 | ゼオライト分離膜及びそれを用いた分離膜構造体 |
WO2018131707A1 (ja) * | 2017-01-16 | 2018-07-19 | 住友電気工業株式会社 | 分離膜の製造方法 |
CN110446543A (zh) * | 2017-03-31 | 2019-11-12 | 日本碍子株式会社 | Afx结构的沸石膜、膜结构体以及膜结构体的制造方法 |
Families Citing this family (5)
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KR101695496B1 (ko) * | 2010-09-08 | 2017-01-11 | 서강대학교산학협력단 | 기재상에 3개의 결정축 배향이 모두 정렬된 종자 결정들을 2차 성장시켜 형성된 막 |
JP6167484B2 (ja) * | 2012-08-21 | 2017-07-26 | 三菱ケミカル株式会社 | 多孔質支持体−ゼオライト膜複合体 |
US9186622B1 (en) * | 2014-06-11 | 2015-11-17 | Hamilton Sundstrand Corporation | Device for separation of oxygen and nitrogen |
TWI552879B (zh) * | 2015-02-13 | 2016-10-11 | 國立高雄大學 | 高方向性抗腐蝕沸石膜之製備方法 |
CN107427783A (zh) | 2015-03-31 | 2017-12-01 | 日本碍子株式会社 | 沸石膜结构体 |
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US5824617A (en) * | 1994-07-08 | 1998-10-20 | Exxon Research & Engineering Company | Low alkaline inverted in-situ crystallized zeolite membrane |
US5871650A (en) * | 1994-07-08 | 1999-02-16 | Exxon Research And Engineering Company | Supported zeolite membranes with controlled crystal width and preferred orientation grown on a growth enhancing layer |
SE9600970D0 (sv) * | 1996-03-14 | 1996-03-14 | Johan Sterte | Förfarande för framställning av mycket tunna filmer av molekylsiktar |
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2006
- 2006-11-17 CA CA002629756A patent/CA2629756A1/en not_active Abandoned
- 2006-11-17 JP JP2007545350A patent/JPWO2007058388A1/ja active Pending
- 2006-11-17 BR BRPI0618690-4A patent/BRPI0618690A2/pt not_active IP Right Cessation
- 2006-11-17 WO PCT/JP2006/323523 patent/WO2007058388A1/ja active Application Filing
-
2008
- 2008-05-12 US US12/118,929 patent/US20080217240A1/en not_active Abandoned
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JPH10506363A (ja) * | 1994-07-08 | 1998-06-23 | エクソン リサーチ アンド エンジニアリング カンパニー | 本来の場所で結晶化されたゼオライト含有組成物(lai−isc) |
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WO2010106881A1 (ja) | 2009-03-16 | 2010-09-23 | 日本碍子株式会社 | ゼオライト分離膜配設体、その製造方法、混合流体の分離方法、及び混合流体分離装置 |
CN102348494A (zh) * | 2009-03-16 | 2012-02-08 | 日本碍子株式会社 | 沸石分离膜构件、其制造方法、混合流体的分离方法以及混合流体分离装置 |
JPWO2010106881A1 (ja) * | 2009-03-16 | 2012-09-20 | 日本碍子株式会社 | ゼオライト分離膜配設体、その製造方法、混合流体の分離方法、及び混合流体分離装置 |
US8361197B2 (en) | 2009-03-16 | 2013-01-29 | Ngk Insulators, Ltd. | Structure provided with zeolite separation membrane, method for producing same, method for separating mixed fluids and device for separating mixed fluids |
JP2015160186A (ja) * | 2014-02-28 | 2015-09-07 | 日本ゼオン株式会社 | 膜分離方法 |
JP2016034917A (ja) * | 2014-08-01 | 2016-03-17 | Jx日鉱日石エネルギー株式会社 | ノルマルパラフィンまたはパラキシレンの分離方法およびゼオライト膜複合体 |
JP2016073956A (ja) * | 2014-10-08 | 2016-05-12 | 学校法人早稲田大学 | ノルマルパラフィンの分離方法 |
WO2016121377A1 (ja) * | 2015-01-27 | 2016-08-04 | 日本ゼオン株式会社 | 分離膜およびその製造方法 |
JPWO2016121377A1 (ja) * | 2015-01-27 | 2017-11-02 | 日本ゼオン株式会社 | 分離膜およびその製造方法 |
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WO2018131707A1 (ja) * | 2017-01-16 | 2018-07-19 | 住友電気工業株式会社 | 分離膜の製造方法 |
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CN106957062A (zh) * | 2017-05-05 | 2017-07-18 | 南京工业大学 | 一种取向sapo‑34分子筛膜的制备方法 |
Also Published As
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JPWO2007058388A1 (ja) | 2009-05-07 |
BRPI0618690A2 (pt) | 2011-09-06 |
US20080217240A1 (en) | 2008-09-11 |
CA2629756A1 (en) | 2007-05-24 |
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