WO2016084846A1 - ゼオライト膜構造体の製造方法 - Google Patents
ゼオライト膜構造体の製造方法 Download PDFInfo
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- WO2016084846A1 WO2016084846A1 PCT/JP2015/083070 JP2015083070W WO2016084846A1 WO 2016084846 A1 WO2016084846 A1 WO 2016084846A1 JP 2015083070 W JP2015083070 W JP 2015083070W WO 2016084846 A1 WO2016084846 A1 WO 2016084846A1
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- Prior art keywords
- zeolite membrane
- zeolite
- membrane
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- forming
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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 456
- 239000010457 zeolite Substances 0.000 title claims abstract description 454
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 453
- 239000012528 membrane Substances 0.000 title claims abstract description 418
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims description 27
- 230000007547 defect Effects 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 116
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 71
- 239000000377 silicon dioxide Substances 0.000 description 58
- 239000010408 film Substances 0.000 description 34
- 150000001768 cations Chemical class 0.000 description 21
- 239000011148 porous material Substances 0.000 description 21
- 238000005342 ion exchange Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 230000026683 transduction Effects 0.000 description 11
- 238000010361 transduction Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 9
- 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 8
- 230000008569 process Effects 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000010899 nucleation Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000009423 ventilation Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 241000408939 Atalopedes campestris Species 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 3
- HXQQNYSFSLBXQJ-UHFFFAOYSA-N COC1=C(NC(CO)C(O)=O)CC(O)(CO)CC1=NCC(O)=O Chemical compound COC1=C(NC(CO)C(O)=O)CC(O)(CO)CC1=NCC(O)=O HXQQNYSFSLBXQJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 230000004913 activation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical group [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920006268 silicone film Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
-
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1214—Chemically bonded layers, e.g. cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
- B01D71/022—Metals
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
-
- 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
- C01B39/023—Preparation of physical mixtures or intergrowth products of zeolites chosen from group C01B39/04 or two or more of groups C01B39/14 - C01B39/48
-
- 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
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/205—Faujasite type, e.g. type X or Y using at least one organic template directing agent; Hexagonal faujasite; Intergrowth products of cubic and hexagonal faujasite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
Definitions
- the present invention relates to a method for producing a zeolite membrane structure including laminated zeolite membranes.
- a zeolite membrane structure in which a FAU zeolite membrane and a hydrophobic zeolite membrane are sequentially laminated on a porous support is known (see Patent Document 1).
- the hydrophobic zeolite membrane a silicalite membrane or a DDR type zeolite membrane is used.
- the hydrophobic zeolite membrane is formed by crystal growth of a seed crystal deposited on the FAU zeolite membrane by a hydrothermal synthesis method.
- the present invention has been made in view of the above situation, and an object thereof is to provide a method for producing a zeolite membrane structure capable of suppressing membrane defects.
- the first zeolite membrane is formed on the porous support by hydrothermal synthesis while the porous support is immersed in the first zeolite membrane-forming solution.
- the first zeolite membrane and the second zeolite membrane share at least one composite building unit constituting the skeleton structure.
- a method for producing a zeolite membrane structure capable of suppressing membrane defects can be provided.
- the zeolite membrane structure 10 includes a porous support 20, a first zeolite membrane 30, and a second zeolite membrane 40.
- the porous support 20 supports the first zeolite membrane 30 and the second zeolite membrane 40.
- the porous support 20 has chemical stability such that the first zeolite membrane 30 and the second zeolite membrane 40 can be formed (crystallized or precipitated) on the surface 20S.
- a material constituting the porous support 20 for example, a ceramic sintered body, a metal, an organic polymer, glass, carbon, and the like can be used.
- the ceramic sintered body include alumina, silica, mullite, zirconia, titania, yttria, silicon nitride, and silicon carbide.
- the metal include aluminum, iron, bronze, and stainless steel.
- the organic polymer include polyethylene, polypropylene, polytetrafluoroethylene, polysulfone, and polyimide.
- the porous support 20 may have any shape that can supply the liquid mixture or gas mixture to be separated to the first zeolite membrane 30 and the second zeolite membrane 40.
- Examples of the shape of the porous support 20 include, but are not limited to, a honeycomb shape, a monolith shape, a flat plate shape, a tubular shape, a cylindrical shape, a columnar shape, and a prismatic shape.
- the porous support 20 has pores.
- the average pore diameter of the porous support 20 should just be a magnitude
- the average pore diameter of the porous support 20 is increased, the permeation amount of the permeation component tends to increase.
- the average pore diameter of the porous support 20 is reduced, the strength of the porous support itself can be increased, and the surface becomes flat, so that the dense first zeolite membrane 30 can be easily formed.
- the porous support 20 may have a single layer structure having a uniform average pore diameter or a multilayer structure having different average pore diameters.
- each layer may be made of a different material among the above materials, or may be made of the same material.
- the first zeolite membrane 30 is formed on the surface 20S of the porous support 20.
- the porous support 20 is formed in a honeycomb shape or a monolith shape, the first zeolite membrane 30 is formed inside each of the plurality of through holes of the porous support 20.
- the framework structure (type) of the zeolite mainly composed of the first zeolite membrane 30 is not particularly limited.
- the composition X “contains the substance Y as a main component” means that the substance Y preferably accounts for 60% by weight or more, more preferably 70% by weight or more in the entire composition X. Means more preferably 90% by weight or more.
- the Si / Al atomic ratio in the first zeolite membrane 30 is not particularly limited, but may be, for example, 1.5 or more, and preferably 200 or more.
- a high silica zeolite having an Si / Al atomic ratio of 200 or more contains substantially no or no aluminum.
- the Si / Al atomic ratio in the first zeolite membrane 30 can be adjusted by controlling the composition of the raw material solution and the reaction conditions during hydrothermal synthesis, as will be described later.
- the Si / Al atomic ratio in the first zeolite film 30 can be measured by SEM-EDX (scanning electron microscope-energy dispersive X-ray spectroscopy).
- the first zeolite membrane 30 may contain an inorganic binder (such as silica or alumina), an organic binder (such as a polymer), or a silylating agent.
- an inorganic binder such as silica or alumina
- an organic binder such as a polymer
- the first zeolite membrane 30 is formed in a film shape.
- the thickness of the first zeolite membrane 30 is not particularly limited, but may be, for example, 0.1 ⁇ m to 10 ⁇ m.
- the thickness of the first zeolite membrane 30 can be adjusted by controlling the hydrothermal synthesis time and the synthesis temperature.
- the first zeolite membrane 30 has pores.
- the average pore diameter of the first zeolite membrane 30 is not particularly limited and can be adjusted according to the separation target.
- the average pore diameter of the first zeolite membrane 30 is a value derived from the framework structure and composition.
- the average pore diameter of the first zeolite membrane 30 is the arithmetic average of the major axis and the minor axis of the largest pore among the pore structures having an oxygen 8-membered ring or more existing in the skeleton structure.
- the average pore diameter of the first zeolite membrane 30 can be set to 0.2 nm to 2.0 nm, for example.
- the second zeolite membrane 40 is formed on the surface 30S of the first zeolite membrane 30.
- the framework structure of the zeolite contained in the second zeolite membrane 40 as a main component is not particularly limited, and the same structure as the first zeolite membrane 30 described above can be used.
- MFI, DDR, MEL, BEA, CHA, MOR, FAU, LTA, FER, and SOD are preferred because the zeolite is easily crystallized.
- a zeolite composite building unit is a single unit structure constituting the framework structure of zeolite.
- IZA International Zeolite Association
- the adhesion between the first zeolite membrane 30 and the second zeolite membrane 40, the film formation property of the second zeolite membrane 40, and the first zeolite membrane 30 and the second zeolite membrane 4 Separation performance can be improved.
- the framework structures of the first zeolite membrane 30 and the second zeolite membrane 40 are the same, it is more preferable because all the composite building units are common.
- the Si / Al atomic ratio in the second zeolite membrane 40 is not particularly limited, but can be, for example, less than 200, and is preferably 60 or less.
- Low silica zeolite having a Si / Al atomic ratio of 60 or less has a characteristic that more cations can be introduced.
- the second zeolite membrane 40 can have various functions. Therefore, by forming the second zeolite membrane 40 on the first zeolite membrane 30, the second zeolite membrane 40, which is a functional layer, can be densified in a thin film state.
- the Si / Al atomic ratio in the second zeolite membrane 40 may be different from the Si / Al atomic ratio in the first zeolite membrane 30.
- the Si / Al atomic ratio in the second zeolite membrane 40 and the Si / Al atomic ratio in the first zeolite membrane 30 are different. It is preferable because a structure in which zeolites having different functions are laminated can be obtained.
- the Si / Al atomic ratio in the second zeolite membrane 40 can be adjusted by controlling the composition of the raw material solution and the reaction conditions during hydrothermal synthesis, as will be described later.
- the Si / Al atomic ratio in the second zeolite membrane 40 can be measured by SEM-EDX.
- the second zeolite membrane 40 may contain an inorganic binder, an organic binder, a silylating agent, or the like.
- the second zeolite membrane 40 is formed in a film shape.
- the separation performance of the zeolite membrane structure 10 can be further improved as compared with the case where zeolite particles are fixed on the surface 30S of the first zeolite membrane 30. .
- the second zeolite membrane 40 is in the form of a film that covers 80% or more of the surface 30S of the first zeolite membrane 30 when the surface of the second zeolite membrane is observed by SEM. Means that.
- the second zeolite membrane 40 particularly preferably covers 90% or more of the surface 30S of the first zeolite membrane 30.
- the separation performance of the zeolite membrane structure 10 can be further improved.
- the second zeolite membrane 40 can be easily formed into a membrane shape even if the second zeolite membrane 40 is distributed in a band shape along the surface direction. I can confirm that there is.
- the thickness of the second zeolite membrane 40 is not particularly limited, but can be, for example, 0.1 ⁇ m to 3.0 ⁇ m.
- the second zeolite membrane 40 is thinned, the amount of permeation tends to increase, and when the second zeolite membrane 40 is thickened, the selectivity and membrane strength tend to be improved.
- the thickness of the second zeolite membrane 40 is less than 0.1 ⁇ m, the selectivity may be reduced, and when it is 3.0 ⁇ m or more, cracks may be generated in the second separation membrane and the selectivity may be reduced.
- the thickness of the second zeolite membrane 40 can be adjusted by controlling the hydrothermal synthesis time and synthesis temperature.
- the second zeolite membrane 40 has pores.
- the average pore diameter of the second zeolite membrane 40 is not particularly limited and can be adjusted according to the separation target.
- the average pore diameter of the second zeolite membrane 40 is the arithmetic average of the major and minor diameters of the largest pore among the pore structures having an oxygen 8-membered ring or more present in the skeleton structure.
- the average pore diameter of the second zeolite membrane 40 can be set to 0.2 nm to 2.0 nm, for example.
- the raw material of the porous support 20 is formed into a desired shape using an extrusion molding method, a press molding method, a cast molding method, or the like.
- the molded body of the porous support 20 is fired (for example, 900 ° C. to 1450 ° C.), and both ends are sealed with glass to form the porous support 20.
- the first zeolite membrane 30 is formed on the surface 20S of the porous support 20.
- a method for forming the first zeolite membrane 30 a well-known method such as a hydrothermal synthesis method can be used according to the framework structure of the zeolite membrane.
- a zeolite seed crystal may be used or may not be used.
- a seed crystal for forming a first zeolite membrane is prepared using a conventional method.
- a CHA type zeolite membrane is formed as the first zeolite membrane 30
- M.I. Itakura et al. Chemistry Letters vol. 37, no. 9 (2008) 908
- the FAU-type zeolite structure conversion method can be used.
- the method described in JP-A-2004-83375 can be used.
- a seeding slurry liquid in which the first zeolite film-forming seed crystals are dispersed is applied to the surface of the porous support 20, and then the seeding slurry liquid is air-dried.
- a first zeolite membrane forming solution is prepared using a conventional method.
- a CHA-type zeolite membrane is formed as the first zeolite membrane 30
- the technique described in JP2011-16123A can be used.
- the method described in JP-A-2004-83375 can be used.
- the Si / Al atomic ratio in the first zeolite membrane 30 is adjusted by adjusting the compounding ratio between the Si source (such as silica sol) and the Al source (such as sodium aluminate) in the first zeolite membrane forming solution. be able to.
- the first zeolite membrane 30 is formed on the porous support 20 by hydrothermal synthesis while the porous support 20 is immersed in the first zeolite membrane forming solution.
- hydrothermal synthesis conditions conventionally known conditions (see JP 2011-16123 A and JP 2004-83375 A) can be used.
- the thickness of the first zeolite membrane 30 can be adjusted by controlling the hydrothermal synthesis time and the synthesis temperature.
- the organic template may be burned and removed after the first zeolite membrane 30 is formed, or may be burned and removed after the second zeolite membrane 40 is formed. Even if a defect occurs in the removal of the organic template of the first zeolite membrane 30, it can be covered with the second zeolite membrane 40. Therefore, it is more preferable that the organic template is removed by combustion after the formation of the first zeolite membrane 30.
- a second zeolite film forming solution is prepared.
- a preparation method of the second zeolite membrane forming solution a conventional method according to the framework structure of the second zeolite membrane 40 can be used.
- the amount of template (1-adamantanamine, etc.), alkali compound, etc. is adjusted so that the pH of the second zeolite film forming solution is 10 or more.
- the pH is more preferably 10.5 or more, and particularly preferably 11 or more. By setting the pH to 10 or more, the surface activation action described later can be made obvious.
- the upper limit of the pH is not particularly limited, but is preferably 14 or less from the viewpoint of suppressing excessive erosion of the first zeolite membrane 30.
- the Si / Al atomic ratio in the second zeolite membrane 40 can be adjusted by adjusting the blending ratio of the Si source and the Al source in the second zeolite membrane forming solution.
- the second zeolite membrane forming solution is set to 10 ° C. or higher and 70 ° C. or lower, and the porous support 20 on which the first zeolite membrane 30 is formed is immersed for 5 minutes or longer.
- the foreign matter adhering to the surface of the first zeolite membrane 30 is removed and the skeleton structure is exposed on the entire surface, so that the surface is activated.
- the adhesion between the first zeolite membrane 30 and the second zeolite membrane 40 is improved, film defects of the second zeolite membrane 40 can be suppressed.
- the upper limit of the time for immersing the porous support 20 having the first zeolite membrane 30 in the second zeolite membrane forming solution is not particularly limited, but is 100 hours or less from the viewpoint of productivity. It is preferable that it is 50 hours or less.
- the second zeolite membrane 40 is formed on the first zeolite membrane 30 by hydrothermal synthesis of the porous support 20 on which the first zeolite membrane 30 has been formed immersed in the second zeolite membrane forming solution.
- hydrothermal synthesis conditions conventionally known conditions can be used.
- the nitrogen gas permeation rate of the second zeolite membrane 40 before combustion removal of the organic template is 0.75 nmol / (m 2 ⁇ s ⁇ Pa) or less. Preferably there is. Further, when an organic template is not used for forming the second zeolite membrane 40 (when the organic template is not included in the second zeolite membrane 40), the second zeolite membrane 40 is sufficiently exposed to saturated water vapor. 2
- the nitrogen gas permeation rate of the zeolite membrane 40 is preferably 0.75 nmol / (m 2 ⁇ s ⁇ Pa) or less.
- the nitrogen gas permeation rate being 0.75 nmol / (m 2 ⁇ s ⁇ Pa) or less means that the second zeolite membrane 40 is formed in a film shape.
- the zeolite membrane structure 10 preferably contains at least one cation selected from alkali metal, alkaline earth metal, Au, Ag, Cu, Ni, Co, Pd, and Pt.
- the second zeolite membrane 40 is formed without using the second zeolite membrane forming seed crystal, but the second zeolite membrane forming seed crystal is used in the same manner as the first zeolite membrane 30.
- the second zeolite membrane 40 may be formed.
- a method that does not use the second zeolite membrane forming seed crystal is preferable in that the adhesion of the second zeolite membrane 40 can be improved.
- “not using a seed crystal” includes not only the case where no seed crystal is used, but also the case where the seed crystal is present to the extent that the adhesion of the second zeolite membrane 40 is not affected. It is a concept. Specifically, the content of the second zeolite membrane forming seed crystal in the second zeolite membrane forming solution is 0.1 wt% or less, or the second zeolite membrane attached to the surface of the first zeolite membrane 30. When the mass per unit area of the forming seed crystal is 0.01 g / cm 2 or less, it can be said that substantially no seed crystal is used.
- the zeolite membrane structure 10 is provided with the first zeolite membrane 30 and the second zeolite membrane 40 laminated on the porous support 20.
- the zeolite membrane structure 10 is laminated on the second zeolite membrane 40.
- a functional film or a protective film may be provided.
- Such a functional film or a protective film is not limited to a zeolite film, but may be an inorganic film such as a carbon film or a silica film, or an organic film such as a polyimide film or a silicone film.
- a monolith-type alumina base compact was formed by extruding the prepared porous material. Subsequently, the alumina substrate molded body was fired (1250 ° C., 1 hour) to form an alumina substrate. Next, PVA (organic binder) was added to alumina to prepare a slurry, and a surface layer formed body was formed on the inner surface of the cell of the alumina base material by a filtration method using the slurry. Subsequently, the compact of the surface layer was fired (1250 ° C., 1 hour), and then both ends of the alumina base material were sealed with glass to produce a monolith type alumina support.
- PVA organic binder
- a high silica MFI type zeolite membrane having a Si / Al atomic ratio of 200 or more was formed as a first zeolite membrane on the cell inner surface of the alumina support.
- a seeding slurry liquid prepared by diluting MFI-type zeolite seed crystals (Si / Al atomic ratio ⁇ 200) with ethanol to a concentration of 0.1% by mass is contained in the cell of the alumina support. Poured into.
- the inside of the cell was dried by ventilation under predetermined conditions (room temperature, wind speed 5 m / s, 10 minutes).
- the obtained film-forming sol was placed in a fluororesin inner cylinder (with an internal volume of 300 ml) of a stainless pressure vessel, and then the alumina support to which the MFI type zeolite seed crystal was attached was immersed and dried with hot air at 160 ° C.
- a high silica MFI type zeolite membrane was formed by reacting in the machine for 20 hours.
- the alumina support was washed and dried at 80 ° C. for 12 hours or more.
- the alumina support was heated to 500 ° C. in an electric furnace and held for 4 hours to remove tetrapropylammonium from the high silica MFI type zeolite membrane.
- a low silica MFI type zeolite membrane having an Si / Al atomic ratio of 20 was formed as a second zeolite membrane on the surface of the high silica MFI type zeolite membrane.
- a low silica MFI type zeolite membrane having an Si / Al atomic ratio of 20 was formed as a second zeolite membrane on the surface of the high silica MFI type zeolite membrane.
- SACHEM 40% by mass tetrapropylammonium hydroxide solution
- 4.97 g of tetrapropylammonium bromide manufactured by Wako Pure Chemical Industries
- 26.3 g of sodium hydroxide manufactured by Sigma-Aldrich
- 0.54 g of aluminum sulfate manufactured by Wako Pure Chemical Industries, Ltd.
- 147.1 g of distilled water and 14.8 g of about 30% by mass silica sol (trade name: Snowtex S, manufactured by Nissan Chemical Co., Ltd.) are added to the magnetic stirrer.
- the film forming sol was prepared by stirring at room temperature (room temperature, 30 minutes).
- the obtained sol for film formation was placed in a fluororesin inner cylinder (internal volume 300 ml) of a stainless pressure-resistant container while maintaining the temperature at 10 ° C. to 20 ° C., and an alumina support having a high silica MFI type zeolite membrane 5
- a low silica MFI type zeolite membrane was formed by reacting in a hot air dryer at 160 ° C. for 10 hours.
- the alumina support was washed and dried at 80 ° C. for 12 hours or more.
- the alumina support was heated to 500 ° C. in an electric furnace and held for 4 hours to remove tetrapropylammonium from the low silica MFI type zeolite membrane.
- the silver ion exchange solution prepared by adding silver nitrate (manufactured by Kanto Chemical) to water to be 0.1 mol / L is kept in contact with the second zeolite membrane for 24 hours. 2 Ag was introduced as a cation into the zeolite membrane. Thereafter, the second zeolite membrane was rinsed with water and dried (70 ° C., 12 hours).
- sample no. 2 The same alumina support as 1 was prepared.
- sample No. 1 was formed as the first zeolite membrane on the cell inner surface of the alumina support.
- the same high silica MFI type zeolite membrane as 1 was formed.
- a low silica MFI type zeolite membrane was formed as a second zeolite membrane on the surface of the first zeolite membrane.
- the film-forming sol was put in a fluororesin inner cylinder of a stainless pressure-resistant container while maintaining the temperature at 65 to 70 ° C., and the alumina support on which the high silica MFI zeolite film was formed was immersed for 10 hours.
- a second zeolite membrane was formed by the same process as in 1.
- transduction operation by ion exchange was not performed to the 2nd zeolite membrane.
- sample no. The same alumina support as 1 was prepared.
- sample No. 1 was formed as the first zeolite membrane on the cell inner surface of the alumina support.
- the same high silica MFI type zeolite membrane as 1 was formed.
- a low silica MFI type zeolite membrane was formed as a second zeolite membrane on the surface of the first zeolite membrane. Specifically, except that the film forming sol was placed in a fluororesin inner cylinder of a stainless pressure-resistant container while maintaining the temperature at 0 ° C., and the alumina support on which the high silica MFI type zeolite film was formed was immersed for 10 hours. No. A second zeolite membrane was formed by the same process as in 1. In addition, the cation introduction
- sample no. 4 The same alumina support as 1 was prepared.
- sample No. 1 was formed as the first zeolite membrane on the cell inner surface of the alumina support.
- the same high silica MFI type zeolite membrane as 1 was formed.
- a low silica MFI type zeolite membrane was formed as a second zeolite membrane on the surface of the first zeolite membrane.
- the film forming sol was placed in a fluororesin inner cylinder of a stainless steel pressure-resistant container while maintaining the temperature at 90 to 95 ° C., and the alumina support on which the high silica MFI zeolite film was formed was immersed for 5 minutes.
- a second zeolite membrane was formed by the same process as in 1.
- transduction operation by ion exchange was not performed to the 2nd zeolite membrane.
- sample No. 5 First, sample no. The same alumina support as 1 was prepared.
- sample No. 1 was formed as the first zeolite membrane on the cell inner surface of the alumina support.
- the same high silica MFI type zeolite membrane as 1 was formed.
- a low silica MFI type zeolite membrane was formed as a second zeolite membrane on the surface of the first zeolite membrane. Specifically, No. 1 except that sulfuric acid was further dropped into the film-forming sol to adjust the pH to 9.5. A second zeolite membrane was formed by the same process as in 1. In addition, the cation introduction
- sample no. The same alumina support as 1 was prepared.
- sample No. 1 was formed as the first zeolite membrane on the cell inner surface of the alumina support.
- the same high silica MFI type zeolite membrane as 1 was formed.
- a low silica MFI type zeolite membrane was formed as a second zeolite membrane on the surface of the first zeolite membrane.
- SACHEM 40% by mass tetrapropylammonium hydroxide solution
- SACHEM 40% by mass tetrapropylammonium hydroxide solution
- a second zeolite membrane was formed by the same process as in 1. Thereafter, sample No. In the same manner as in Example 1, Ag was introduced as a cation into the second zeolite membrane.
- sample no. The same alumina support as 1 was prepared.
- sample No. 1 was formed as the first zeolite membrane on the cell inner surface of the alumina support.
- the same high silica MFI type zeolite membrane as 1 was formed.
- the inside of the cell was dried by ventilation under predetermined conditions (room temperature, wind speed 5 m / s, 10 minutes).
- a low silica MFI type zeolite membrane was formed as a second zeolite membrane on the surface of the first zeolite membrane. Specifically, sample no. A second zeolite membrane was formed by the same process as in 1.
- transduction operation by ion exchange was not performed to the 2nd zeolite membrane.
- sample no. The same alumina support as 1 was prepared.
- a high silica DDR type zeolite membrane having an Si / Al atomic ratio of 200 or more was formed as a first zeolite membrane on the inner surface of the alumina support cell.
- a seeding slurry prepared by diluting a DDR type zeolite seed crystal (Si / Al atomic ratio ⁇ 200) with ethanol to a concentration of 0.1% by mass is contained in a cell of an alumina support. Poured into.
- the inside of the cell was dried by ventilation under predetermined conditions (room temperature, wind speed 5 m / s, 10 minutes).
- the obtained film-forming sol was placed in a fluororesin inner cylinder (internal volume 300 ml) of a stainless pressure vessel, and then the alumina support to which the DDR type zeolite seed crystal was attached was immersed in hot air drying at 130 ° C.
- a high silica DDR type zeolite membrane was formed by reacting in the machine for 10 hours.
- the alumina support was washed and dried at 80 ° C. for 12 hours or more.
- the alumina support was heated to 450 ° C. in an electric furnace and held for 50 hours to burn and remove 1-adamantanamine of the high silica DDR type zeolite membrane.
- a low silica DDR type zeolite membrane having a Si / Al atomic ratio of 40 was formed as a second zeolite membrane on the surface of the high silica DDR type zeolite membrane.
- 152.4 g of distilled water was put into a fluoric resin wide-mouth bottle (internal volume 500 ml), and then 1.32 g of 1-adamantanamine (Aldrich) and sodium hydroxide (Sigma Aldrich) 0 .35 g and 30 wt% silica sol (trade name: Snowtex S, manufactured by Nissan Chemical Co., Ltd.) 52.6 g and sodium aluminate (manufactured by Wako Pure Chemical Industries) 0.36 g were added and stirred to prepare a film-forming sol.
- the obtained film-forming sol was placed in a fluororesin inner cylinder (internal volume 300 ml) of a stainless steel pressure-resistant container while maintaining the temperature at 20 ° C. to 30 ° C., and an alumina support having a high silica DDR type zeolite membrane 5 After soaking for a minute, a low silica DDR type zeolite membrane was formed by reacting in a hot air dryer at 160 ° C. for 12 hours. Next, after the alumina support was washed, it was dried at 80 ° C. for 12 hours or more. Next, the alumina support was heated to 450 ° C.
- sample no. The same alumina support as 1 was prepared.
- sample No. 1 was formed as the first zeolite membrane on the cell inner surface of the alumina support.
- the same high silica DDR type zeolite membrane as 8 was formed.
- sample No. On the surface of the high silica DDR type zeolite membrane, sample No. The same DDR type zeolite membrane as 8 was formed.
- sample no. The same alumina support as 1 was prepared.
- sample No. 1 was formed as the first zeolite membrane on the cell inner surface of the alumina support.
- the same high silica MFI type zeolite membrane as 1 was formed.
- a high silica BEA type zeolite membrane having a Si / Al atomic ratio of 200 or more was formed as a second zeolite membrane on the surface of the high silica MFI type zeolite membrane.
- a high silica BEA type zeolite membrane having a Si / Al atomic ratio of 200 or more was formed as a second zeolite membrane on the surface of the high silica MFI type zeolite membrane.
- 87.7 g of 35 mass% tetraethylammonium hydroxide manufactured by Sigma Aldrich
- 34.9 g of distilled water 34.9 g
- silica sol trade name: Snowtex S, manufactured by Nissan Chemical Co., Ltd. 83.5 g was added and stirred with a magnetic stirrer (room temperature, 90 minutes) to prepare a sol for film formation.
- the obtained film-forming sol was placed in a fluororesin inner cylinder (internal volume 300 ml) of a stainless pressure-resistant container while maintaining the temperature at 20 ° C. to 30 ° C., and an alumina support 1 on which a high silica MFI type zeolite membrane was formed was 1 After soaking for a period of time, a high silica BEA type zeolite membrane was formed by reacting in a hot air dryer at 140 ° C. for 20 hours. Next, the alumina support was washed and dried at 80 ° C. for 12 hours or more.
- the tetraethylammonium was removed from the high silica BEA type zeolite membrane by raising the alumina support to 500 ° C. in an electric furnace and holding it for 4 hours.
- transduction operation by ion exchange was not performed to the 2nd zeolite membrane.
- sample no. The same alumina support as 1 was prepared.
- the obtained film-forming sol was placed in a fluororesin inner cylinder (internal volume 300 ml) of a stainless pressure vessel, immersed in an alumina support to which a FAU-type zeolite seed crystal was adhered, and then in a hot air dryer at 160 ° C. Were reacted for 24 hours to form a FAU-type zeolite membrane. Next, the alumina support was washed and dried at 80 ° C. for 12 hours or more.
- an LTA type zeolite membrane having an Si / Al atomic ratio of 1 was formed as a second zeolite membrane on the surface of the FAU type zeolite membrane.
- a second zeolite membrane was formed as a second zeolite membrane on the surface of the FAU type zeolite membrane.
- 67.4 g of 25% by mass tetramethylammonium hydroxide manufactured by Sigma Aldrich
- 14.1 g of aluminum sulfate manufactured by Wako Pure Chemical Industries
- 0.47 g of sodium hydroxide manufactured by Sigma Aldrich
- distillation After mixing 107.4 g of water, 35.6 g of about 30% by mass silica sol (trade name: Snowtex S, manufactured by Nissan Chemical Co., Ltd.) is added and stirred with a magnetic stirrer (room temperature, 30 minutes) to form a sol for film formation Was prepared.
- the obtained film-forming sol was placed in a fluororesin inner tube (internal volume 300 ml) of a stainless steel pressure-resistant container while maintaining the temperature at 10 ° C. to 20 ° C., and the alumina support on which the FAU-type zeolite membrane was formed was treated for 15 minutes.
- an LTA type zeolite membrane was formed by reacting in a hot air dryer at 115 ° C. for 10 hours.
- the alumina support was washed and dried at 80 ° C. for 12 hours or more.
- tetramethylammonium was removed from the LTA-type zeolite membrane by raising the alumina support to 450 ° C. in an electric furnace and holding it for 4 hours.
- transduction operation by ion exchange was not performed to the 2nd zeolite membrane.
- sample no. The same alumina support as 1 was prepared.
- sample No. 1 was formed as the first zeolite membrane on the cell inner surface of the alumina support.
- the same high silica MFI type zeolite membrane as 1 was formed.
- a high silica DDR type zeolite membrane having an Si / Al atomic ratio of 200 or more was formed as a second zeolite membrane on the surface of the high silica MFI type zeolite membrane.
- ethylenediamine manufactured by Wako Pure Chemical Industries, Ltd.
- 1-adamantanamine manufactured by Aldrich
- the alumina support was washed and dried at 80 ° C. for 12 hours or more.
- the alumina support was heated to 450 ° C. in an electric furnace and held for 50 hours to burn and remove 1-adamantanamine of the high silica DDR type zeolite membrane.
- transduction operation by ion exchange was not performed to the 2nd zeolite membrane.
- sample no. 13 The same alumina support as 1 was prepared.
- sample No. 1 was formed as the first zeolite membrane on the cell inner surface of the alumina support.
- the same high silica MFI type zeolite membrane as 1 was formed.
- DDR type zeolite seed crystals (Si / Al atomic ratio ⁇ 200) were diluted with ethanol, and a seeding slurry prepared to a concentration of 0.1% by mass was poured into the cell of the alumina support.
- the inside of the cell was dried by ventilation under predetermined conditions (room temperature, wind speed 5 m / s, 10 minutes).
- a high silica DDR type zeolite membrane was formed as a second zeolite membrane on the surface of the first zeolite membrane. Specifically, sample no. A second zeolite membrane was formed in the same process as in No. 12.
- transduction operation by ion exchange was not performed to the 2nd zeolite membrane.
- sample no. The same alumina support as 1 was prepared.
- sample No. 1 was formed as the first zeolite membrane on the cell inner surface of the alumina support.
- the same high silica DDR type zeolite membrane as 8 was formed.
- sample No. 11 On the surface of the high silica DDR type zeolite membrane, sample No. The same LTA type zeolite membrane as No. 11 was formed. In addition, the cation introduction
- sample no. The same alumina support as 1 was prepared.
- sample No. 1 was formed as the first zeolite membrane on the cell inner surface of the alumina support.
- the same high silica DDR type zeolite membrane as 8 was formed.
- the denseness of the second zeolite membrane is evaluated by randomly checking the surface of each sample with 20 SEM (magnification 1000 times) and calculating the surface coverage of the second zeolite membrane over the entire 20 locations. did.
- Table 1 shows that the surface coverage of the first zeolite membrane by the second zeolite membrane is 90% or more, and the surface coverage of the first zeolite membrane by the second zeolite membrane is 80% or more and less than 90% , B, and C, where the surface coverage of the first zeolite membrane by the second zeolite membrane is less than 80%.
- the cross section of each sample was randomly checked with SEM (magnification 2000 times) at 20 locations, and the first zeolite membrane and the second zeolite membrane over the entire 20 locations. It evaluated by calculating the ratio of the clearance gap which occupies for the interface.
- A is a sample with no gap
- B is a sample with a gap of less than 5%
- C is a sample with a gap of 5% or more but less than 10%
- the composite building unit of the first zeolite membrane and the second zeolite membrane is common, and the porous support on which the first zeolite membrane is formed has a first temperature of 10 ° C. or higher and 70 ° C. or lower and a pH of 10 or higher.
- Sample No. 2 immersed in a zeolite membrane forming solution for 5 minutes or more. For 1, 2, 6 to 11, it was found that both the denseness and adhesion of the first zeolite membrane and the second zeolite membrane were good.
- sample No. 1 in which the framework structure of the first zeolite membrane and the second zeolite membrane was the same. For 1, 2, 8, and 9, it was found that the adhesion was particularly good.
- FIG. 2 shows a HAADF (high angle scattering annular dark field) image when sample No. 1 is observed with a STEM.
- CO 2 carbon dioxide
- CH 4 methane
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Abstract
Description
ゼオライト膜構造体10は、多孔質支持体20と、第1ゼオライト膜30と、第2ゼオライト膜40とを備える。
ゼオライト膜構造体10の製造方法について説明する。
以上、本発明の一実施形態について説明したが、本発明は上記実施形態に限定されるものではなく、発明の要旨を逸脱しない範囲で種々の変更が可能である。
以下のようにして、サンプルNo.1に係るゼオライト膜構造体を作製した。
まず、サンプルNo.1と同じアルミナ支持体を作製した。
まず、サンプルNo.1と同じアルミナ支持体を作製した。
まず、サンプルNo.1と同じアルミナ支持体を作製した。
まず、サンプルNo.1と同じアルミナ支持体を作製した。
まず、サンプルNo.1と同じアルミナ支持体を作製した。
まず、サンプルNo.1と同じアルミナ支持体を作製した。
まず、サンプルNo.1と同じアルミナ支持体を作製した。
まず、サンプルNo.1と同じアルミナ支持体を作製した。
まず、サンプルNo.1と同じアルミナ支持体を作製した。
まず、サンプルNo.1と同じアルミナ支持体を作製した。
まず、サンプルNo.1と同じアルミナ支持体を作製した。
まず、サンプルNo.1と同じアルミナ支持体を作製した。
まず、サンプルNo.1と同じアルミナ支持体を作製した。
まず、サンプルNo.1と同じアルミナ支持体を作製した。
サンプルNo.1~15について、調製した第2ゼオライト膜形成用ゾルのpHを測定したところ、サンプルNo.5以外は、pHが10以上であることを確認した。
サンプルNo.1~15について、以下の手法によって第2ゼオライト膜の緻密性と第1ゼオライト膜と第2ゼオライト膜の密着性を定量的に測定した。
サンプルNo.1~15について、以下の手法によって第2ゼオライト膜の主析出部を確認した。第2ゼオライト膜の成膜前後の重量差を「第2ゼオライト膜の重量」とした。また、第2ゼオライト膜合成によって溶液中に析出した粉末を遠心分離によって回収した後、洗浄して80℃で12時間以上乾燥させて得られた粉末の重量を「第2ゼオライト膜形成用溶液中に析出した第2ゼオライトの合計重量」とした。「第2ゼオライト膜の重量」>「第2ゼオライト膜形成用溶液中に析出した第2ゼオライトの合計重量」の場合に第2ゼオライト膜の主析出部を「膜」、そうでない場合に第2ゼオライト膜の主析出部を「溶液」とした。
Agを導入したサンプルNo.1,6,8について、エチレン/エタンの分離性能を評価した。エチレン(C2H4)とエタン(C2H6)の25℃の混合ガス(各ガスの体積比=50:50)を0.4MPaでセル内に導入し、第1ゼオライト膜と第2ゼオライト膜を透過したガスを、ガスクロマトグラフを用いて成分分析した。その結果、Agを導入したサンプルNo.1,6,8は、いずれもエチレンが選択透過することが分かった。
20 多孔質支持体
30 第1ゼオライト膜
40 第2ゼオライト膜
Claims (7)
- 多孔質支持体を第1ゼオライト膜形成用溶液に浸漬した状態で水熱合成することによって、前記多孔質支持体上に第1ゼオライト膜を形成する工程と、
前記第1ゼオライト膜が形成された前記多孔質支持体を10℃以上70℃以下かつpH10以上の第2ゼオライト膜形成用溶液に5分以上浸漬する工程と、
前記第1ゼオライト膜が形成された前記多孔質支持体を前記第2ゼオライト膜形成用溶液に浸漬した状態で水熱合成することによって、前記第1ゼオライト膜上に第2ゼオライト膜を形成する工程と、
を備え、
前記第1ゼオライト膜と前記第2ゼオライト膜は、骨格構造を構成する少なくとも1種のコンポジットビルディングユニットを共有している、
ゼオライト膜構造体の製造方法。 - 前記第2ゼオライト膜形成用溶液における第2ゼオライト膜形成用種結晶の含有量は0.1wt%以下である、
請求項1に記載のゼオライト膜構造体の製造方法。 - 前記第1ゼオライト膜の表面に付着された第2ゼオライト膜形成用種結晶の単位面積当たりの質量は0.01g/cm2以下である、
請求項1に記載のゼオライト膜構造体の製造方法。 - 前記第2ゼオライト膜の形成後において、前記第2ゼオライト膜の重量は、前記第2ゼオライト膜形成用溶液中に析出した第2ゼオライトの合計重量よりも大きい、
請求項1乃至3のいずれかに記載のゼオライト膜構造体の製造方法。 - 前記第1ゼオライト膜の骨格構造は、前記第2ゼオライト膜の骨格構造と同じである、
請求項1乃至4のいずれかに記載のゼオライト膜構造体の製造方法。 - 前記第1ゼオライトにおけるSi/Al原子比は、前記第2ゼオライトにおけるSi/Al原子比と異なる、
請求項5に記載のゼオライト膜構造体の製造方法。 - 前記第1ゼオライト膜及び前記第2ゼオライト膜の少なくとも一方の骨格構造は、MFI、DDR、MEL、BEA、CHA、MOR、FAU、LTA、FER、SODのいずれかである、
請求項1乃至6のいずれかに記載のゼオライト膜構造体の製造方法。
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JP2019042710A (ja) * | 2017-09-06 | 2019-03-22 | 国立大学法人 名古屋工業大学 | 分離膜 |
WO2023162854A1 (ja) * | 2022-02-28 | 2023-08-31 | 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 |
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KR102115301B1 (ko) * | 2019-03-18 | 2020-05-26 | 고려대학교 산학협력단 | 이종 제올라이트 분리막의 제조방법 |
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