WO2017142056A1 - ゼオライト分離膜およびその製造方法 - Google Patents
ゼオライト分離膜およびその製造方法 Download PDFInfo
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- WO2017142056A1 WO2017142056A1 PCT/JP2017/005843 JP2017005843W WO2017142056A1 WO 2017142056 A1 WO2017142056 A1 WO 2017142056A1 JP 2017005843 W JP2017005843 W JP 2017005843W WO 2017142056 A1 WO2017142056 A1 WO 2017142056A1
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- zeolite
- membrane
- silica
- separation membrane
- zeolite separation
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- 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 187
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 175
- 239000010457 zeolite Substances 0.000 title claims abstract description 175
- 239000012528 membrane Substances 0.000 title claims abstract description 171
- 238000000926 separation method Methods 0.000 title claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 138
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 97
- 239000013078 crystal Substances 0.000 claims abstract description 69
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 38
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 25
- 150000002222 fluorine compounds Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 37
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 28
- 239000001569 carbon dioxide Substances 0.000 abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 13
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- -1 fluoride compound Chemical class 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 30
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 28
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 27
- 239000011148 porous material Substances 0.000 description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 20
- 229910004298 SiO 2 Inorganic materials 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 229920006362 Teflon® Polymers 0.000 description 13
- 239000000499 gel Substances 0.000 description 13
- 239000004809 Teflon Substances 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 229960004592 isopropanol Drugs 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000003345 natural gas Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 230000034655 secondary growth Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- 229910018503 SF6 Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
Images
Classifications
-
- 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
- B01D67/0051—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
- 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
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
- B01D2256/245—Methane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Definitions
- the present invention relates to an all-silica zeolite separation membrane and a method for producing an all-silica zeolite separation membrane without using hydrofluoric acid.
- it can be suitably used in zeolite separation membranes having STT type and CHA type zeolite crystal structures.
- Zeolite has many regularly arranged micropores and is generally used in various fields because it has many heat resistant and chemically stable materials.
- zeolite is an aluminosilicate in which a part of Si is substituted with Al (a basic skeleton structure having a three-dimensional network structure in which SiO 4 and AlO 4 are bonded together by sharing oxygen).
- Al a basic skeleton structure having a three-dimensional network structure in which SiO 4 and AlO 4 are bonded together by sharing oxygen.
- liquid separation, vapor separation, gas separation, membrane reactor, solid acid catalyst separation because it has pores of molecular order (about 0.3-1 nm) up to the member ring and has a stereoselective adsorption action.
- adsorbents ion exchangers, etc.
- zeolite is a molecule that passes through the pores in the zeolite membrane due to the hydrophilicity / hydrophobicity of the zeolite membrane, depending on the ratio of the constituent SiO 2 and Al 2 O 3 (silica ratio: SiO 2 / Al 2 O 3 ). It is known that the selectivity and permeation performance of the material changes. It is also known that chemical resistance and the like differ depending on the change in the ratio of SiO 2 and Al 2 O 3 .
- natural gas such as methane mined in a natural gas oil field includes water having a molecular diameter close to that of carbon dioxide. Therefore, when natural gas and carbon dioxide are to be separated, water molecules and the like enter the pores of the zeolite membrane in addition to carbon dioxide.
- an all-silica zeolite membrane is desired.
- STT-type and CHA-type zeolite separation membranes for separating methane, carbon dioxide, and the like have not been industrially realized due to problems with the production method described later.
- the zeolite separation membrane is synthesized from a raw material composition using a method called thermal synthesis.
- This raw material composition includes a silica source such as sodium silicate and colloidal silica, aluminum hydroxide, sodium aluminate and the like.
- a structure-directing agent such as an aluminum source, water, an organic template, and a mineralizer such as an alkali metal hydroxide are included.
- This mineralizer has a function of dissolving the metal component contained in the raw material composition in water.
- NaOH sodium hydroxide
- the zeolite does not crystallize (solid phase) even if hydrothermal synthesis is performed.
- hydrofluoric acid instead of NaOH.
- Patent Documents 1 to 3 show a method for producing pure silica zeolite crystals of particles such as STT type and CHA type (not zeolite membrane) for the purpose of separating carbon dioxide and the like by an adsorption method. Hydrofluoric acid is used as the agent.
- This hydrofluoric acid has a crystallization-promoting effect that promotes dissolution and crystallization of the raw material composition gel, a structure-determining effect in which a compound of a certain structure and composition is synthesized by the coexistence of fluoride ions, and It is said that there is a template effect that is incorporated into the skeleton and stabilizes the structure, similar to the organic template.
- hydrofluoric acid is very toxic and unsuitable for the production of large structures such as zeolite membrane composites, and hydrofluoric acid still adheres to the surface of the zeolite separation membrane after synthesis. There is a problem that it takes a lot of labor to completely wash off, and the manufacturing method becomes very complicated.
- JP 2009-114007 A JP 2009-214101 A Japanese Patent Laying-Open No. 2015-116532
- an object of the present invention is to provide an all-silica zeolite separation membrane that does not cause a decrease in the processing amount due to adsorption of water molecules (separates carbon dioxide and the like).
- Another object of the present invention is to provide a safe method for producing an all-silica zeolite separation membrane that does not use hydrofluoric acid, in view of the above-described problems in the production of the prior art.
- the present invention provides the following zeolite separation membrane, a membrane synthesis raw material composition for producing the zeolite separation membrane, and a method for producing the zeolite separation membrane.
- the zeolitic crystal structure skeleton formed on the porous support is an all-silica zeolite separation membrane, and the zeolite crystal structure formed on the porous support is fluorine-free. Zeolite separation membrane.
- a method for producing a zeolite separation membrane having a zeolite crystal structure on a porous support the step of producing a seed crystal, the step of applying the seed crystal on the porous support, and membrane synthesis
- a method for producing a zeolite separation membrane comprising an organic template and no fluorine compound is
- fluorine-free is synthesized without using a fluorine-containing mineralizer such as hydrofluoric acid in hydrothermal synthesis of a zeolite membrane, so that hydrofluoric acid remains in the zeolite membrane. It means that there is no fluorine in the zeolite membrane structure crystallized by hydrothermal synthesis.
- the fluorine-containing mineralizer used in the step of producing the seed crystal may be contained in the zeolite membrane. However, since the amount is extremely small compared to the entire synthesized zeolite membrane, the zeolite membrane can be said to be substantially free of fluorine.
- water contained in natural gas is separated from natural gas such as methane mined in a natural gas oil field and carbon dioxide.
- natural gas such as methane mined in a natural gas oil field and carbon dioxide.
- Carbon dioxide and the like can be separated without causing a reduction in throughput by adsorption of molecules or the like.
- an all-silica zeolite separation membrane can be produced safely without using a fluorine compound (hydrofluoric acid or the like).
- FIG. 2 is an electron microscopic image of an all-silica STT type zeolite membrane obtained in Example 1.
- FIG. 2 shows an X-ray diffraction pattern of an all-silica STT zeolite separation membrane obtained in Example 1 and an X-ray diffraction pattern of all-silica STT zeolite particles. It is an electron microscope image of the all-silica zeolite membrane surface of Example 2 synthesized by shortening the hydrothermal synthesis time.
- 2 is a correlation diagram between carbon dioxide permeation rate and temperature in the all-silica STT type zeolite separation membrane obtained in Example 1 and a high silica (Si / Al ratio is 25) CHA type zeolite separation membrane.
- FIG. 1 shows an X-ray diffraction pattern of an all-silica STT zeolite separation membrane obtained in Example 1 and an X-ray diffraction pattern of all-silica STT zeolite particles. It is an electron microscope image of the all-sili
- FIG. 2 shows an X-ray diffraction pattern of an all-silica CHA-type zeolite separation membrane obtained in Example 3 and an X-ray diffraction pattern of all-silica CHA-type zeolite particles.
- FIG. 5 shows an X-ray diffraction pattern of an all-silica STT type zeolite separation membrane obtained in Example 4 and an X-ray diffraction pattern of all-silica STT type zeolite particles. It is the microscope picture and elemental analysis result of the cross section of the all-silica STT type zeolite separation membrane obtained in Example 1.
- the all-silica zeolite separation membrane of the present invention has an all-silica zeolite membrane formed on the surface of a porous support.
- the crystal skeleton of the all-silica zeolite membrane of the present invention is substantially free of aluminum and is entirely composed of silica (SiO 2 ).
- Aluminum in general zeolite membrane pores has a strong adsorption action, and when it is desired to perform multi-component separation, it becomes the resistance of the target separation. Also, the collapse of the zeolite membrane due to acidity and high water content occurs in the aluminum portion in the framework of the zeolite crystal structure. Therefore, the all-silica zeolite membrane of the present invention that does not contain aluminum has very high acid resistance and low adsorption performance for water molecules and the like.
- the term “substantially free of aluminum” as used herein is because aluminum contained in the porous support during hydrothermal synthesis may be contained in a very small amount.
- the all-silica zeolite separation membrane of the present invention is separated mainly by the molecular sieve effect.
- the STT type zeolite membrane suitably used in the present invention has two kinds of pores, and each pore is ⁇ 5.3 ⁇ 3.7 mm and ⁇ 2.4 ⁇ 3.5 mm.
- the CHA-type zeolite membrane has ⁇ 3.8 ⁇ 3.8 ⁇ pores.
- STT and CHAIN are codes classified by structure according to the zeolite determined by the International Zeolite Association (IZA).
- the thickness of the zeolite membrane is not particularly limited, but may be as thin as possible, and is preferably about 1.0 ⁇ m to 10.0 ⁇ m.
- the porous support is not particularly limited as long as it can be crystallized as a thin film of zeolite on the support, and examples thereof include porous supports such as alumina, silica, zirconia, titania, and stainless steel.
- the porous support has pores larger than the pores of the zeolite membrane, and molecular sieving is performed by the molecules passing through the zeolite membrane passing through the pores of the porous support.
- the shape of the porous support is not particularly limited, and various shapes such as a tubular shape, a flat plate shape, a honeycomb shape, a hollow fiber shape, and a pellet shape can be used.
- the size of the porous support is not particularly limited, but is practically about 2 to 200 cm in length, 0.5 to 2.0 cm in inner diameter, and about 0.5 to 4.0 mm in thickness. .
- ⁇ Method for producing zeolite separation membrane In the synthesis step of the zeolite membrane, an all-silica zeolite seed crystal is coated on the porous support, and the porous support with the seed crystal is immersed in the membrane synthesis raw material composition (gel) and hydrothermally synthesized. To form an all-silica zeolite membrane.
- the seed crystal organic template and the silica source are preferably the same as those used for the synthesis of the target zeolite crystal.
- the zeolite seed crystal uses hydrofluoric acid (hereinafter also referred to as “HF”), and the hydrothermal synthesis and basic of the zeolite crystal (separation membrane) except that the porous support is not used. In the same manner, a seed crystal is produced.
- the seed synthesis raw material composition (gel) is transferred to a pressure vessel, usually an autoclave, and hydrothermal synthesis is performed. Thereafter, the autoclave is cooled, the gel is washed with ion-exchanged water, filtered, and dried under reduced pressure.
- the size of the seed crystal is preferably 100 nm to 1 ⁇ m, more preferably 100 to 800 nm.
- the particle diameter of the seed crystal can be measured using a particle diameter measuring instrument (trade name, FPAR-1000) manufactured by Otsuka Electronics Co., Ltd.
- seed crystals prepared in advance it is preferable to add seed crystals prepared in advance to a synthesis solution (synthetic gel).
- a synthesis solution synthetic gel
- the crystallization of zeolite can be promoted and the particle size can be controlled.
- Step of applying seed crystal to porous support First, for a porous support, when using a zeolite membrane formed on the support as a molecular sieve or the like, (a) the zeolite membrane can be firmly supported, (b) the pressure loss is as small as possible, And (c) It is preferable to set the average pore diameter and the like of the porous support so as to satisfy the condition that the porous support has sufficient self-supporting property (mechanical strength).
- the surface of the porous support is preferably treated by a method such as washing with water or ultrasonic cleaning.
- the support surface may be cleaned by ultrasonic cleaning with water for 1 to 10 minutes.
- the surface may be polished with a sandpaper or a grinder.
- the particle diameter of the seed crystal is desirably small, and may be used after being pulverized as necessary.
- a dip method in which the seed crystal is dispersed in a solvent such as water and the support is immersed in the dispersion to deposit the seed crystal, or the seed crystal is adhered to water or the like.
- a method of applying a slurry mixed with a solvent onto the surface of the support can be used.
- the amount of seed crystal applied is preferably 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 ⁇ 3 wt% with respect to the weight of the support.
- the support after the seed crystal is applied is preferably baked at 450 ° C. to 700 ° C., for example, in order to improve the adhesion.
- the silica source is not particularly limited, but preferred examples include amorphous silica, colloidal silica, silica gel, sodium silicate, tetraorthosilicate (TEOS), trimethylethoxysilane and the like.
- N, N, N-trialkyl-1-adamantanammonium cation derived from 1-adamantanamine is preferable, and these hydroxides are preferably used.
- N, N, N-trimethyl-adamantanammonium hydroxide (TMAdaOH) is more preferable.
- Other examples include N, N, N-trialkylbenzylammonium hydroxide. It is considered that the hydroxyl group of these organic templates in the gel functions as a mineralizer.
- the hydrothermal synthesis method of the all-silica zeolite separation membrane is a porous support in which an all-silica zeolite seed crystal is applied after aging a membrane synthesis raw material composition (gel) containing a silica source and an organic template and not containing a fluorine compound.
- the body is inserted into the membrane synthesis raw material composition, and hydrothermal synthesis is performed using a sealed container, usually an autoclave.
- the aging temperature and time are preferably 10 to 24 hours at room temperature.
- the organic template and the silica source are mixed, stirred and heated to evaporate and remove the generated water and ethanol, and then ion-exchanged water is added to the remaining solid and stirred while heating.
- coated the seed crystal to the Teflon (trademark) inner cylinder is installed, and it fills with a secondary growth solution.
- This is charged into an autoclave and hydrothermal synthesis is performed.
- the produced zeolite separation membrane is boiled and washed with ion-exchanged water, and after drying under reduced pressure, firing is performed to remove the organic template remaining in the membrane.
- the firing temperature and time are preferably 450 to 700 ° C. and 8 to 24 hours.
- Ethanol is produced by hydrolysis and condensation when TEOS is used as the silica source.
- the hydrothermal synthesis temperature and time for forming the all-silica STT type zeolite membrane and the all-silica CHA type zeolite membrane are preferably 140 to 180 ° C. for 6 to 12 days, and preferably 8 to 12 days. Particularly preferred.
- Example 1 Production of all-silica STT type zeolite separation membrane] (Preparation of seed crystal) TMAdaOH (organic template) and TEOS (silica source) water were mixed in a beaker and stirred for 12 hours to hydrolyze TEOS. Then, it heated at 150 degreeC and the produced
- generated water and ethanol were completely evaporated. Hydrofluoric acid and ion-exchanged water were added to the solid remaining in the beaker and stirred. The molar composition of each substance is SiO 2 : TMAdaOH: HF: H 2 O 1: 0.5: 0.5: 7.5.
- the gel was transferred to a Teflon autoclave and subjected to hydrothermal synthesis at 150 ° C. for 3.5 days.
- the autoclave was cooled, and the gel in the Teflon inner cylinder was washed with ion-exchanged water, filtered, and dried under reduced pressure.
- the prepared all-silica STT-type zeolite seed crystal is 3 ⁇ 10 3 on the surface of a porous alumina support (outer diameter: 3 mm, length: about 25 mm, pore diameter: 1.5 ⁇ m) as a test piece with respect to the weight of the support. -4 wt% was applied by rubbing. Thereafter, it was calcined at 700 ° C. for 12 hours.
- the autoclave was charged and hydrothermal synthesis was performed at 150 ° C. for 8 days.
- the autoclave was cooled, the zeolite separation membrane completed from the Teflon inner cylinder was taken out, boiled and washed with ion-exchanged water, and dried under reduced pressure. Finally, in order to remove TMAdaOH remaining in the film, baking was performed at 500 ° C. for 10 hours in an electric furnace.
- FIG. 1 shows an SEM image of the surface of the synthesized all-silica zeolite separation membrane.
- FIG. 2 shows an X-ray diffraction pattern (XRD) of all-silica STT type zeolite particles and an X-ray diffraction pattern of the zeolite separation membrane prepared by the above production method.
- the lower X-ray diffraction pattern is an X-ray diffraction pattern of all-silica STT type zeolite particles.
- the upper X-ray diffraction pattern is an X-ray diffraction pattern of the all-silica zeolite separation membrane produced by the above production method. From these two X-ray diffraction patterns, the produced zeolite separation membrane was identified as an all-silica STT type zeolite membrane.
- FIG. 3 shows an electron microscope image of the surface of the all-silica zeolite membrane of Example 2 synthesized by shortening the hydrothermal synthesis time.
- a membrane was synthesized using the same membrane synthesis raw material composition (gel) as in Example 1.
- coated the seed crystal to the Teflon inner cylinder was installed, and it filled with the secondary growth solution.
- An autoclave was charged and hydrothermal synthesis was performed at 150 ° C. for 7 days.
- the autoclave was cooled, the zeolite separation membrane completed from the Teflon inner cylinder was taken out, boiled and washed with ion-exchanged water, and dried under reduced pressure. Finally, in order to remove TMAdaOH remaining in the film, baking was performed at 500 ° C. for 10 hours in an electric furnace.
- Example 2 had a very large IPA permeation flow rate. That is, while the pore diameter of the STT type zeolite membrane is 0.37 nm, the molecular diameter of IPA is 0.47 nm, and the IPA molecule cannot theoretically penetrate into the pores of the membrane due to the molecular sieve effect. Therefore, it was considered that IPA molecules from defects such as crystal grain boundaries were permeated, and it was concluded that a dense STT type zeolite membrane could not be obtained after a synthesis time of 7 days. On the other hand, in Example 1, the IPA permeation flow rate was dramatically reduced as compared with Example 2, and a separation factor of 15 or less was obtained, confirming densification of the zeolite membrane. Although Example 2 was not dense, an STT type zeolite membrane was formed.
- Example 2 a change in crystal form was observed depending on the synthesis time.
- the zeolite separation membrane of Example 2 was composed of elliptical particles of about several tens of ⁇ m.
- the surface of the zeolite membrane of Example 1 is covered with very large crystals that are angular, and no defects such as pinholes and cracks are observed, confirming that a dense crystal layer is obtained. did.
- FIG. 4 is a diagram showing the correlation between the carbon dioxide permeation rate and temperature in the all-silica STT zeolite separation membrane obtained in Example 1 and the high silica (Si / Al ratio is 25) CHA-type zeolite separation membrane. .
- a high-silica (Si / Al ratio: 25) CHA-type zeolite separation membrane is synthesized by carrying a CHA-type seed crystal on the outer surface of a porous alumina support and subjecting it to hydrothermal treatment in the membrane synthesis raw material composition. It was.
- the seed crystal was obtained by preparing a gel using FAU-type zeolite powder (manufactured by Tosoh), sodium hydroxide, organic template (TMAdaOH) and ion-exchanged water and subjecting it to hydrothermal treatment at a predetermined temperature and time.
- the porous support carrying the seed crystal by dipping or rubbing and the membrane synthesis raw material composition were charged into an autoclave and hydrothermally treated at a predetermined temperature and time to form a polycrystalline layer. After washing, TMAdaOH was removed by calcination to obtain a high silica CHA type zeolite separation membrane.
- FIG. 4 shows changes in the measurement temperature and CO 2 permeation rate of the high silica CHA type zeolite membrane and the all silica STT type zeolite membrane synthesized in Example 1.
- the measurement was performed at a temperature of 40 to 120 ° C., the flow rate of CO 2 gas permeating the zeolite membrane was measured, and the permeation rate was calculated.
- TMAdaOH organic template
- colloidal silica silicon source
- the prepared all-silica CHA-type zeolite seed crystal is 3 ⁇ 10 3 on the surface of a porous alumina support (outer diameter: 16 mm, length: about 40 mm, pore diameter: 1.0 ⁇ m) as a test piece with respect to the weight of the support. -4 wt% was applied by rubbing. Thereafter, it was calcined at 700 ° C. for 12 hours.
- the autoclave was charged and hydrothermal synthesis was performed at 150 ° C. for 8 days.
- the autoclave was cooled, the zeolite separation membrane completed from the Teflon inner cylinder was taken out, boiled and washed with ion-exchanged water, and dried under reduced pressure. Finally, in order to remove TMAdaOH remaining in the film, baking was performed at 500 ° C. for 10 hours in an electric furnace.
- FIG. 5 shows an X-ray diffraction pattern (XRD) of all-silica CHA-type zeolite particles and an X-ray diffraction pattern of the zeolite separation membrane produced by the above production method.
- the lower X-ray diffraction pattern is an X-ray diffraction pattern of all-silica CHA-type zeolite particles.
- the upper X-ray diffraction pattern is an X-ray diffraction pattern of the zeolite separation membrane prepared by the above production method. From these two X-ray diffraction patterns, the produced zeolite separation membrane was identified as an all-silica CHA type zeolite membrane.
- Example 4 Production of all-silica STT type zeolite separation membrane
- the all-silica STT-type zeolite seed crystal synthesized in Example 1 is 6 ⁇ 10 ⁇ 4 wt on the surface of a porous aluminum support having an outer diameter of 16 mm, a length of 40 mm, and a pore diameter of 1.0 ⁇ m. % was applied by rubbing. Thereafter, it was calcined at 700 ° C. for 12 hours.
- the autoclave was charged and hydrothermal synthesis was performed at 150 ° C. for 8 days.
- the autoclave was cooled, the zeolite separation membrane completed from the Teflon inner cylinder was taken out, boiled and washed with ion-exchanged water, and dried under reduced pressure. Finally, in order to remove TMAdaOH remaining in the film, baking was performed at 500 ° C. for 10 hours in an electric furnace.
- FIG. 6 shows the X-ray diffraction pattern (XRD) of all-silica STT type zeolite particles and the X-ray diffraction pattern of the zeolite separation membrane prepared by the above production method.
- the lower X-ray diffraction pattern is an X-ray diffraction pattern of all-silica STT type zeolite particles.
- the upper X-ray diffraction pattern is an X-ray diffraction pattern of the zeolite separation membrane prepared by the above production method. From these two X-ray diffraction patterns, the produced zeolite separation membrane was identified as an all-silica STT type zeolite membrane.
- FIG. 7 shows an electron micrograph of a cross section of the all-silica STT type zeolite membrane obtained in Example 1.
- Each element in FIG. 7 was subjected to elemental analysis by EDX measurement (manufactured by HORIBA (trade name): EMAXAENERGY EX-350). As a result, no fluorine atom was detected at any site, and it was found that fluorine was not present in the zeolite membrane synthesized by the method of the present invention. The detection limit of this EDX measurement is 0.00 Atom%.
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Abstract
Description
〈ゼオライト分離膜〉
本発明のオールシリカのゼオライト分離膜は、多孔質支持体表面にオールシリカゼオライト膜が形成されている。
ゼオライト膜の合成ステップは、多孔質支持体上にオールシリカゼオライトの種結晶を塗布し、この種結晶付き多孔質支持体を膜合成原料組成物(ゲル)内に浸漬させて水熱合成することでオールシリカゼオライト膜を製膜する。
種結晶の有機テンプレートとシリカ源として好ましくは目的ゼオライト結晶の合成に用いるものと同じものを用いる。ゼオライト種結晶は、フッ化水素酸(以下、「HF」と称することもある。)を用い、多孔質支持体を用いない点を除いて、ゼオライト結晶(分離膜)の水熱合成と基本的に同様の操作で種結晶を製造する。
オールシリカSTT型ゼオライト分離膜の製造のための種結晶は、例えばSiO2: 有機テンプレート:HF:H2O=1:0.2~1.5:0.5~1.5:5.0~15.0の組成で製造することが望ましい。特に、SiO2: 有機テンプレート:HF:H2O=1:0.2~1.0:0.5~1.5:5.0~15.0の組成で製造することが望ましい。
まず、多孔質支持体については、同支持体上にゼオライト膜を形成したものを分子篩等として利用する場合、(a)ゼオライト膜を強固に担持することができ、(b)圧損ができるだけ小さく、かつ(c)多孔質支持体が十分な自己支持性(機械的強度)を有するという条件を満たすように、多孔質支持体の平均細孔径等を設定するのが好ましい。
シリカ源は、特に限定されるものではないが、好ましくは、無定形シリカ、コロイダルシリカ、シリカゲル、ケイ酸ナトリウム、テトラオルトシリケート(TEOS)、トリメチルエトシキシシラン等が挙げられる。
オールシリカゼオライト分離膜の水熱合成方法は、シリカ源および有機テンプレートを含み、フッ素化合物を含まない膜合成原料組成物(ゲル)を熟成させた後、オールシリカゼオライト種結晶を塗布した多孔質支持体を膜合成原料組成物に挿入して、密閉容器、通常はオートクレーブを用いて水熱合成を行う。熟成の温度および時間は、室温で10~24時間であることが好ましい。具体的には、有機テンプレートとシリカ源を混合し、攪拌して加熱し、生成した水とエタノールを蒸発除去させた後、残った固体にイオン交換水を加え加熱しながら攪拌する。その後、テフロン(登録商標)内筒に種結晶を塗布した多孔質支持体を設置し、二次成長溶液で満たす。これをオートクレーブに仕込み、水熱合成を行なう。その後、生成したゼオライト分離膜をイオン交換水で煮沸洗浄し、減圧乾燥後に、膜内に残存している有機テンプレートを除去するため、焼成する。焼成温度および時間は、450℃~700℃で8~24時間であることが好ましい。なお、エタノールは、シリカ源にTEOSを用いた場合に、加水分解・縮合により生成する。
(種結晶の調製)
ビーカーにTMAdaOH(有機テンプレート)とTEOS(シリカ源)水を混合し、12時間攪拌しTEOSを加水分解させた。その後、150℃で熱し、生成した水とエタノールを完全に蒸発させた。ビーカーに残った固体に、フッ化水素酸及びイオン交換水を加え攪拌を行った。各物質のモル組成は、SiO2: TMAdaOH:HF:H2O=1:0.5:0.5:7.5である。攪拌後、ゲルをテフロン製オートクレーブに移し、150℃で3.5日間水熱合成を行った。オートクレーブを冷却し、テフロン内筒内のゲルをイオン交換水で洗浄・ろ過し、減圧乾燥した。
次いで、ゼオライト膜を製膜するための膜合成のための膜合成原料組成物を以下の手順で調製した。まず、ビーカーに有機テンプレートであるTMAdaOHとシリカ源であるTEOSを混合し、12時間攪拌を行った。150℃で加熱し、生成した水とエタノールを完全に蒸発させた。ビーカーに残った固体にイオン交換水を加え、150℃で加熱しながら攪拌を行った。各物質のモル組成は、SiO2: TMAdaOH: H2O=1:0.25:44である。その後、テフロン内筒に種結晶を塗布した多孔質支持体を設置し、二次成長溶液で満たした。オートクレーブに仕込み、150℃で8日間水熱合成を行なった。オートクレーブを冷却し、テフロン内筒から出来上がったゼオライト分離膜を取り出し、イオン交換水で煮沸洗浄し、減圧乾燥した。最後に、膜内に残存しているTMAdaOHを除去するため、電気炉にて500℃で10時間焼成を行った。
図3に、水熱合成時間を短くして合成した実施例2のオールシリカゼオライト膜表面の電子顕微鏡像を示す。
オールシリカSTT型分離膜の緻密性について、IPA(Iso propyl alcohol)水溶液(IPA:90wt%)の浸透気化分離(PV)にて評価実験をした。ゼオライト分離膜を75℃のIPA水溶液に浸漬し、内側を真空ポンプにより減圧した。そして、ゼオライト分離膜により分離された浸透蒸気を液体窒素により捕集し、その重量及び濃度をカールフィッシャ―水分計で測定しゼオライト分離膜の透過流速、分離係数を得た。
図4は、実施例1で得られたオールシリカSTT型ゼオライト分離膜と高シリカ(Si/Al比が25)のCHA型ゼオライト分離膜における二酸化炭素透過速度と温度との相関を示す図である。
(種結晶の調製)
ビーカーにTMAdaOH(有機テンプレート)とコロイダルシリカ(シリカ源)を混合し、フッ化水素酸を加えた。その後、攪拌を行いながら加熱し、水を完全に除去した。固体をメノウ乳鉢で粉砕し、イオン交換水を加えた。各物質のモル組成は、SiO2: TMAdaOH:HF:H2O=1:1.4:1.4:6.0である。ゲルをテフロン製オートクレーブに移し、150℃で24日間水熱合成を行った。オートクレーブを冷却し、テフロン内筒内のゲルをイオン交換水で洗浄・ろ過し、減圧乾燥した。
次いで、ゼオライト膜を製膜するための膜合成のための膜合成原料組成物を以下の手順で調製した。まず、ビーカーに有機テンプレートであるTMAdaOHとシリカ源であるTEOSを混合し、12時間攪拌を行った。150℃で加熱し、生成した水とエタノールを完全に蒸発させた。ビーカーに残った固体にイオン交換水を加え、150℃で加熱しながら攪拌を行った。各物質のモル組成は、SiO2: TMAdaOH: H2O=1:0.5:44である。その後、テフロン内筒に種結晶を塗布した多孔質支持体を設置し、二次成長溶液で満たした。オートクレーブに仕込み、150℃で8日間水熱合成を行なった。オートクレーブを冷却し、テフロン内筒から出来上がったゼオライト分離膜を取り出し、イオン交換水で煮沸洗浄し、減圧乾燥した。最後に、膜内に残存しているTMAdaOHを除去するため、電気炉にて500℃で10時間焼成を行った。
実施例1にて合成したオールシリカSTT型ゼオライト種結晶を外径16mm、長さ40mm、細孔径1.0μmの多孔質アルミア支持体表面上に、重さに対して、6×10-4wt%を擦り込むことで塗布した。その後700℃で12時間焼成した。
Claims (5)
- 多孔質支持体上に形成されたゼオライト結晶構造の骨格がオールシリカのゼオライト分離膜であって、
多孔質支持体上に形成されたゼオライト結晶構造がフッ素フリーであることを特徴とするゼオライト分離膜。 - 請求項1に記載のゼオライト分離膜であって、
上記ゼオライト結晶構造はSTT型またはCHA型であることを特徴とするゼオライト分離膜。 - 請求項1または2に記載に記載のゼオライト分離膜を製造するための原料組成物であって、
上記原料組成物は、シリカ源および有機テンプレートを含み、フッ素化合物を含まないことを特徴とする原料組成物。 - 多孔質支持体上にゼオライト結晶構造を有するゼオライト分離膜の製造方法であって、
種結晶を製造するステップと、
上記種結晶を上記多孔質支持体上に塗布するステップと、
膜合成原料組成物を製造するステップと、
上記種結晶が塗布された上記多孔質支持体を上記膜合成原料組成物に浸漬して水熱合成するステップを含み、
上記膜合成原料組成物は、シリカ源および有機テンプレートを含み、フッ素化合物を含まないことを特徴とするゼオライト分離膜の製造方法。 - 請求項4のゼオライト分離膜の製造方法であって、
水熱合成の温度および時間が、140℃~180℃で8日~12日であることを特徴とするゼオライト分離膜の製造方法。
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JP2019089058A (ja) * | 2017-11-16 | 2019-06-13 | コリア ユニバーシティ リサーチ アンド ビジネス ファウンデーションKorea University Research And Business Foundation | 有機構造規定剤フリーのcha型ゼオライト分離膜の製造方法、およびそれから製造された分離膜 |
JP2019155219A (ja) * | 2018-03-07 | 2019-09-19 | 日立造船株式会社 | Cha型チタノシリケート分離膜およびその製造方法、並びにガス分離方法 |
JP2019181456A (ja) * | 2018-03-30 | 2019-10-24 | 日本碍子株式会社 | ゼオライト膜複合体、ゼオライト膜複合体の製造方法、および、分離方法 |
WO2021186959A1 (ja) * | 2020-03-18 | 2021-09-23 | 日本碍子株式会社 | ガス分離方法およびゼオライト膜 |
JP2021191577A (ja) * | 2018-01-16 | 2021-12-16 | 日本碍子株式会社 | 分離方法 |
JP2023504063A (ja) * | 2019-11-29 | 2023-02-01 | 寧波大学 | 分子ふるい膜の継代合成方法 |
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MY190500A (en) | 2022-04-25 |
CN108697997A (zh) | 2018-10-23 |
JP6999114B2 (ja) | 2022-02-10 |
US11666867B2 (en) | 2023-06-06 |
JPWO2017142056A1 (ja) | 2018-12-13 |
US20190224630A1 (en) | 2019-07-25 |
US20210220779A1 (en) | 2021-07-22 |
EP3417929A1 (en) | 2018-12-26 |
US10994246B2 (en) | 2021-05-04 |
CN108697997B (zh) | 2021-05-14 |
EP3417929A4 (en) | 2019-10-23 |
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