JP3840506B2 - Method for producing mixture separation membrane - Google Patents
Method for producing mixture separation membrane Download PDFInfo
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- JP3840506B2 JP3840506B2 JP2004077302A JP2004077302A JP3840506B2 JP 3840506 B2 JP3840506 B2 JP 3840506B2 JP 2004077302 A JP2004077302 A JP 2004077302A JP 2004077302 A JP2004077302 A JP 2004077302A JP 3840506 B2 JP3840506 B2 JP 3840506B2
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- 239000012528 membrane Substances 0.000 title claims description 96
- 238000000926 separation method Methods 0.000 title claims description 90
- 239000000203 mixture Substances 0.000 title claims description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 239000002994 raw material Substances 0.000 claims description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 23
- 239000010936 titanium Substances 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 59
- 229910021536 Zeolite Inorganic materials 0.000 description 57
- 239000010457 zeolite Substances 0.000 description 57
- 239000000126 substance Substances 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 37
- 239000013078 crystal Substances 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- 229910004298 SiO 2 Inorganic materials 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 23
- 239000011148 porous material Substances 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 22
- 239000000499 gel Substances 0.000 description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 19
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 19
- 239000007788 liquid Substances 0.000 description 19
- 229910010413 TiO 2 Inorganic materials 0.000 description 18
- 229910001220 stainless steel Inorganic materials 0.000 description 18
- 239000010935 stainless steel Substances 0.000 description 18
- 239000007858 starting material Substances 0.000 description 18
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 18
- 239000004809 Teflon Substances 0.000 description 17
- 229920006362 Teflon® Polymers 0.000 description 17
- 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 17
- 229910052863 mullite Inorganic materials 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 239000007789 gas Substances 0.000 description 12
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 238000005373 pervaporation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910003849 O-Si Inorganic materials 0.000 description 2
- 229910003872 O—Si Inorganic materials 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910000971 Silver steel Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 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
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-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
- CQSSPYWOLMVVPR-UHFFFAOYSA-N tetraheptyl silicate Chemical compound CCCCCCCO[Si](OCCCCCCC)(OCCCCCCC)OCCCCCCC CQSSPYWOLMVVPR-UHFFFAOYSA-N 0.000 description 1
- HZYAPKYFYYWOKA-UHFFFAOYSA-N tetrahexyl silicate Chemical compound CCCCCCO[Si](OCCCCCC)(OCCCCCC)OCCCCCC HZYAPKYFYYWOKA-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- OZLXDDRBXFHZNO-UHFFFAOYSA-N tetraoctyl silicate Chemical compound CCCCCCCCO[Si](OCCCCCCCC)(OCCCCCCCC)OCCCCCCCC OZLXDDRBXFHZNO-UHFFFAOYSA-N 0.000 description 1
- KCTGOQZIKPDZNK-UHFFFAOYSA-N tetrapentyl silicate Chemical compound CCCCCO[Si](OCCCCC)(OCCCCC)OCCCCC KCTGOQZIKPDZNK-UHFFFAOYSA-N 0.000 description 1
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
本発明は、気体あるいは液体から成る混合物を分離する混合物分離膜に係り、特には多孔質支持体上にチタノシリケート型ゼオライト結晶層を析出させた混合物分離膜に関する。 The present invention relates to a mixture separation membrane for separating a mixture of gas or liquid, and more particularly to a mixture separation membrane in which a titanosilicate zeolite crystal layer is deposited on a porous support.
従来、気体や液体の混合物の分離には、蒸留法、吸着法、膜分離法等が知られている。しかし、このうち蒸留法は熱を加えるため多くのエネルギーを必要とし、耐熱性の低いものや沸点の近いものや水とエタノールなど共沸混合物では分離が困難である。また、吸着法では、吸着剤の再生のための装置が大型であり、また多くのエネルギーを必要とするという課題がある。 Conventionally, a distillation method, an adsorption method, a membrane separation method, and the like are known for separation of a gas or liquid mixture. However, among them, the distillation method requires a lot of energy to apply heat, and separation is difficult with an azeotropic mixture such as one having low heat resistance, one having a near boiling point, or water and ethanol. Further, the adsorption method has a problem that the apparatus for regenerating the adsorbent is large and requires a lot of energy.
これらの蒸留法や吸着法における課題を解決すべく膜分離法が期待されるが、膜分離法の膜には酢酸セルロース、シリコンゴム、ポリスチレン、ポリアミド、ポリイミドなどの種々の高分子を素材としたものが使用されており、高分子膜の膜性能に限界があり分離性が低いこと、さらに耐熱性や耐薬品性に難点があるため適用範囲が限定されるという課題がある。 Membrane separation methods are expected to solve the problems in these distillation methods and adsorption methods, but membranes of membrane separation methods are made of various polymers such as cellulose acetate, silicon rubber, polystyrene, polyamide, and polyimide. However, there is a limit to the membrane performance of the polymer membrane, the separability is low, and there is a problem in that the application range is limited due to the difficulty in heat resistance and chemical resistance.
そこで、このような高分子材料による課題を解決するため、近年では、無機質材料であるゼオライトを用いた分離膜が注目されている。しかし、ゼオライト結晶単独で形成された膜は、ゼオライト結晶間のつながりが弱く機械的強度が弱いことから、分離膜として利用することは困難である。
このため従来からゼオライトを多孔質の支持体に担持させた形態での使用が検討されてきた。
これまでに開発されたゼオライト膜には、例えば、特許文献１には、「ゼオライト膜及びその製造方法」として、シリカ源およびアルカリ金属源を含む水性混合物を多孔質支持体上で水熱合成して得られるシリカライト型ゼオライト膜が開示されている。この特許文献１に開示された発明によれば、化学的・熱的に安定で機械的強度の高く、分離係数が飛躍的に高いアルコール選択性分離膜が得られる。
また、特許文献２には「液体混合物分離膜」として、多孔質支持体上に析出させたＡ型ゼオライト膜よりなる液体混合物分離膜が開示されている。本特許文献２に開示された発明においても、特許文献１に開示された発明と同様に、ゼオライトの分子ふるい能によって、著しく高い水選択透過性を有している。また、パーベーパレーション法による液体混合率の分離において、分離効率が高く、透過安定性にも優れ、しかも化学的安定性、取扱い性も良好で実用的な液体混合物分離膜を提供することができる。
Therefore, in order to solve the problems caused by such a polymer material, in recent years, a separation membrane using zeolite, which is an inorganic material, has attracted attention. However, a membrane formed of zeolite crystals alone is difficult to use as a separation membrane because the connection between the zeolite crystals is weak and the mechanical strength is weak.
For this reason, the use in the form of zeolite supported on a porous support has been studied.
As for the zeolite membrane developed so far, for example, in Patent Document 1, as a “zeolite membrane and its production method”, an aqueous mixture containing a silica source and an alkali metal source is hydrothermally synthesized on a porous support. A silicalite-type zeolite membrane obtained in this manner is disclosed. According to the invention disclosed in Patent Document 1, an alcohol-selective separation membrane that is chemically and thermally stable, has high mechanical strength, and has a remarkably high separation factor can be obtained.
Patent Document 2 discloses a liquid mixture separation membrane comprising an A-type zeolite membrane deposited on a porous support as a “liquid mixture separation membrane”. The invention disclosed in Patent Document 2 also has a remarkably high water permeability due to the molecular sieving ability of zeolite, as in the invention disclosed in Patent Document 1. Moreover, in the separation of the liquid mixing ratio by the pervaporation method, a practical liquid mixture separation membrane having high separation efficiency, excellent permeation stability, chemical stability, and good handling properties can be provided. .
一方、ゼオライト中にチタンを含める技術についても既に開発されており、例えばシリカ源とチタン源から成るチタノシリケート型ゼオライトの合成例としては、特許文献３に「改良されたチタノシリケート触媒、その製造方法及びこれを触媒として使用する過酸化水素を利用した有機合成反応」として、チタノシリケートの一次粒子同士の結晶質による結合体であって、５０〜３００オングストロームの細孔を有し、粒度分布メジアンが１μｍ以上であるチタノシリケート触媒に関する開示がある。
この特許文献３に開示されたチタノシリケート触媒は、ハンドリング特性及び機械的強度に優れ活性の高いチタノシリケート粒子を提供するものである。
On the other hand, a technique for including titanium in zeolite has already been developed. For example, as a synthesis example of a titanosilicate type zeolite composed of a silica source and a titanium source, Patent Document 3 discloses "improved titanosilicate catalyst, Production method and organic synthesis reaction using hydrogen peroxide as a catalyst ”, a crystalline conjugate of titanosilicate primary particles having pores of 50 to 300 angstroms, There is a disclosure relating to a titanosilicate catalyst having a distribution median of 1 μm or more.
The titanosilicate catalyst disclosed in Patent Document 3 provides titanosilicate particles having excellent handling characteristics and mechanical strength and high activity.
しかしながら、特許文献１及び特許文献２に開示されたゼオライト膜は、いずれも製膜後の乾燥時に、ゼオライトの結晶粒界または支持体と結晶との界面でのクラックの発生、膜の剥離による膜欠陥等が生じ膜として緻密な物が得られず、結果的に分離性能が低いという課題があった。 However, the zeolite membranes disclosed in Patent Literature 1 and Patent Literature 2 are both membranes due to the generation of cracks at the crystal grain boundaries of zeolite or the interface between the support and the crystal during the drying after the membrane formation, and the peeling of the membrane. There was a problem that defects or the like occurred and a dense product could not be obtained, resulting in poor separation performance.
また、特許文献３に開示されたチタノシリケート触媒は、開示された方法で調製されるチタノシリケート型ゼオライトは、そもそも触媒として開発されたため、いずれも粒子ないし粒子の凝集体であり、そのままでは分離膜としては使用できないか膜状に得られた場合でも分離性能が低いという課題があった。 In addition, since the titanosilicate type zeolite prepared by the disclosed method is originally developed as a catalyst, the titanosilicate catalyst disclosed in Patent Document 3 is a particle or an aggregate of particles. There was a problem that the separation performance was low even when it could not be used as a separation membrane or was obtained as a membrane.
本発明は、上記従来技術の課題を解決すべくなされたものであり、チタノシリケート型ゼオライトを用いた高い分離性能を有する混合物分離膜とその製造方法を提供することを目的とする。 The present invention has been made to solve the above-mentioned problems of the prior art, and an object thereof is to provide a mixture separation membrane having a high separation performance using a titanosilicate type zeolite and a method for producing the same.
本発明者らは、多孔質支持体上にチタノシリケート型ゼオライトを膜状に結晶化させた膜が、欠陥が発生し難く、高性能の分離機能を有する優れた分離膜として有用なことを見出して本発明を完成させた。
本発明の混合物分離膜においては、上述の課題を解決すべく、多孔質支持体上に析出させたチタノシリケート型ゼオライト結晶層を有するようにしたものである。
このような混合物分離膜においては、チタノシリケート型ゼオライト結晶層が多孔質支持体を覆うように作用する。支持体の形状を利用しながら、欠陥が少なく分離性能に優れる分離膜を生成する作用を有する。
The present inventors have found that a membrane obtained by crystallizing titanosilicate type zeolite into a membrane on a porous support is less likely to cause defects and is useful as an excellent separation membrane having a high-performance separation function. As a result, the present invention was completed.
In order to solve the above-mentioned problems, the mixture separation membrane of the present invention has a titanosilicate type zeolite crystal layer deposited on a porous support.
In such a mixture separation membrane, the titanosilicate type zeolite crystal layer acts so as to cover the porous support. While using the shape of the support, it has the effect of producing a separation membrane with few defects and excellent separation performance.
また、本発明の請求項１に記載された混合分離膜製造方法においては、構造規定剤として水酸化テトラアルキルアンモニウムと、ケイ素源としてケイ素酸化物と、チタン源としてチタン酸化物と、水と、過酸化水素水とを混合させる工程と、混合後に撹拌してゲル化した原料を調製する工程と、ゲル化した原料に多孔質支持体を浸漬する工程と、浸漬された多孔質支持体を１００℃〜２２０℃で１０時間〜１５０時間水熱合成する工程と、その後焼成する工程とを有するものである。
上記構成に係る混合分離膜製造方法は、ゲル化した原料に多孔質支持体を浸漬し、その状態で水熱合成することで、欠陥のない均質な混合物分離膜を生成するという作用を有する。焼成工程は、不要となった構造規定剤を飛ばす作用を有する。
In the been mixed separation membrane production method according to claim 1 of the present invention, the tetraalkyl ammonium hydroxide as the structure directing agent, and silicon oxide as the silicon source, the titanium oxide as a titanium source, and water, A step of mixing hydrogen peroxide water, a step of preparing a gelled raw material by stirring after mixing, a step of immersing the porous support in the gelled raw material, and a 100% of the immersed porous support It has a step of hydrothermal synthesis at 10 to 150 ° C. for 10 hours to 150 hours and a subsequent firing step.
The method for producing a mixed separation membrane according to the above configuration has an effect that a porous mixed support is immersed in a gelled raw material and hydrothermal synthesis is performed in that state, thereby producing a homogeneous mixed membrane having no defects. The firing step has the effect of skipping unnecessary structure directing agents.
請求項２に記載された混合分離膜製造方法においては、請求項１に記載された発明において、チタン酸化物に対するケイ素酸化物の組成比（以下、組成比はモル比で表す。）は５〜５００であり、ケイ素酸化物に対する水の組成比は１０〜３００であり、ケイ素酸化物に対する水酸化テトラアルキルアンモニウムの組成比は０．０５〜１．０である。
このような混合分離膜製造方法においては、請求項２に記載された発明と同様の作用を有する。
In the mixed separation membrane manufacturing method described in claim 2 , in the invention described in claim 1 , the composition ratio of silicon oxide to titanium oxide (hereinafter, the composition ratio is expressed in molar ratio) is 5 to 5. 500, the composition ratio of water to silicon oxide is 10 to 300, and the composition ratio of tetraalkylammonium hydroxide to silicon oxide is 0.05 to 1.0.
Such a mixed separation membrane manufacturing method has the same operation as that of the invention described in claim 2.
本発明の多孔質支持体上に析出させたチタノシリケート型ゼオライト結晶層を有する混合物分離膜は、製膜性に優れており、その分離性能は著しく改善されている。しかもチタンを含むことから、その疎水性を利用して例えばアルコール／水混合物からアルコールを選択的に分離することができ、また、チタノシリケート型ゼオライト構造が有する細孔径による分子ふるい効果により多種多様の混合物の分離が可能となる。さらに、チタンの触媒作用とこの混合物分離膜の作用の両方を利用して、触媒反応前の反応物から触媒反応後の生成物を分離することが可能となる。 The mixture separation membrane having the titanosilicate type zeolite crystal layer deposited on the porous support of the present invention is excellent in film-forming properties, and its separation performance is remarkably improved. Moreover, because it contains titanium, it can be used to selectively separate alcohol from, for example, an alcohol / water mixture by utilizing its hydrophobicity, and it can be varied due to the molecular sieving effect due to the pore size of the titanosilicate zeolite structure. Separation of the mixture becomes possible. Furthermore, the product after the catalytic reaction can be separated from the reaction product before the catalytic reaction by utilizing both the catalytic action of titanium and the action of the mixture separation membrane.
また、請求項１，２に記載された混合分離膜製造方法においては、段落００１３に記載される混合物分離膜を容易に製造することができる。 Moreover, in the mixed separation membrane manufacturing method described in claims 1 and 2 , the mixture separation membrane described in paragraph 0013 can be easily manufactured.
以下、本発明に係る混合物分離膜の製造方法を実施するための最良の形態について説明する。
本実施の形態における多孔質支持体としては、チタノシリケート型ゼオライトを膜状に結晶化出来るような化学的安定性があり多孔質であれば特に制限されるものではなく、例えばアルミナ、シリカ、ジルコニア、チッ化ケイ素、炭化ケイ素等のセラミックス、アルミニウム、銀、ステンレス等の金属、ポリエチレン、ポリプロピレン、ポリテトラフルオロエチレン、ポリスルホン、ポリイミド等の有機高分子からなる多孔質材料を用いることができる。
The following describes the best mode for carrying out the method for producing a mixture separation membrane according to the present invention.
The porous support in the present embodiment is not particularly limited as long as it is chemically stable and porous so that the titanosilicate zeolite can be crystallized into a film. For example, alumina, silica, Porous materials made of ceramics such as zirconia, silicon nitride, and silicon carbide, metals such as aluminum, silver, and stainless steel, and organic polymers such as polyethylene, polypropylene, polytetrafluoroethylene, polysulfone, and polyimide can be used.
多孔質支持体の平均気孔径は０．０５〜１０μｍ、気孔率が１０〜６０％程度のものが好適である。これらの内、特に平均気孔径０．１〜２μｍ、気孔率３０〜５０％が好ましい。またこれらの多孔質支持体の形状は平板状、管状、円筒状や角柱状の孔が多数存在するハニカム状などいずれの形状のものでもよい。 The porous support preferably has an average pore size of 0.05 to 10 μm and a porosity of about 10 to 60%. Among these, an average pore diameter of 0.1 to 2 μm and a porosity of 30 to 50% are particularly preferable. Further, the shape of these porous supports may be any shape such as a flat plate shape, a tubular shape, a cylindrical shape, or a honeycomb shape having a large number of prismatic holes.
チタノシリケート型ゼオライトとは、ゼオライト構造をもつ結晶性のＳｉＯ２（シリカライト）の結晶格子を形成するＳｉの一部をＴｉで置換することにより得られる化合物で、過酸化水素を酸化剤とした種々の有機化合物の酸化触媒として知られている。結晶格子内にＴｉ原子が導入されると、赤外吸収スペクトルにおいて９６０ｃｍ−１付近にＴｉ−Ｏ−Ｓｉ結合に起因する吸収ピークが観測され、紫外・可視吸収スペクトルでは２１０ｎｍ付近に４配位Ｔｉに基づく吸収が観測される。これらの測定によりＴｉ原子の置換が確認できる。
また、多孔質支持体に膜状に析出されるチタノシリケート型ゼオライト結晶層の厚さは０．１〜５００μｍ、さらに０．５〜１００μｍとすることが好適である。
A titanosilicate type zeolite is a compound obtained by substituting a part of Si that forms a crystal lattice of crystalline SiO 2 (silicalite) having a zeolite structure with Ti. Hydrogen peroxide is used as an oxidizing agent. It is known as an oxidation catalyst for various organic compounds. When Ti atoms are introduced into the crystal lattice, an absorption peak due to a Ti—O—Si bond is observed in the vicinity of 960 cm −1 in the infrared absorption spectrum, and a tetracoordinate Ti is present in the vicinity of 210 nm in the ultraviolet / visible absorption spectrum. Absorption based on is observed. By these measurements, substitution of Ti atoms can be confirmed.
Further, the thickness of the titanosilicate type zeolite crystal layer deposited on the porous support in the form of a film is preferably 0.1 to 500 μm, more preferably 0.5 to 100 μm.
ここで、本実施の形態に係る混合分離膜製造方法について図１を参照しながら説明する。図１は本実施の形態に係る混合分離膜製造方法を示す工程図である。
まず、ステップＳ１では構造規定剤と水とケイ素源を混合させる。本実施の形態に係る混合分離膜製造方法では、構造規定剤として水酸化テトラアルキルアンモニウムなど、ケイ素源としてテトラアルキルオルトシリケートやコロイダルシリカ（シリカゲルやゾル）などが考えられる。水は蒸留水であることが望ましい。
次にステップＳ２ではステップＳ１で混合したケイ素源、構造規定剤及び水を室温で攪拌する。さらに、ステップＳ３では、チタン源としてテトラアルキルオルトチタネートやハロゲン化チタン化合物などを添加し、過酸化水素も添加する。その後ステップＳ４ではこれらの混合物を室温で撹拌する。このようにして得られる原料ゾルあるいはゲルを調製した後、ステップＳ５では多孔質支持体を浸漬し、所定温度で所定時間、水熱合成を行い、その後、構造規定剤を除去するために焼成を行う。所定温度と所定時間の具体的な値については後述する。
なお、本実施の形態においては、ステップＳ１乃至ステップＳ４までをそれぞれ工程として分けたが、これらステップ間の時間は短く、出発原料としてケイ素源、構造規定剤、水、チタン源、過酸化水素を室温にて混合し、原料ゾルあるいはゲルを調製するようにしてもよい。
Here, the mixed separation membrane manufacturing method according to the present embodiment will be described with reference to FIG. FIG. 1 is a process diagram showing a mixed separation membrane manufacturing method according to the present embodiment.
First, in step S1, a structure directing agent, water, and a silicon source are mixed. In the mixed separation membrane manufacturing method according to the present embodiment, tetraalkylammonium hydroxide or the like can be used as the structure-directing agent, and tetraalkylorthosilicate or colloidal silica (silica gel or sol) can be used as the silicon source. The water is preferably distilled water.
Next, in step S2, the silicon source, structure directing agent and water mixed in step S1 are stirred at room temperature. Further, in step S3, tetraalkyl orthotitanate or a titanium halide compound is added as a titanium source, and hydrogen peroxide is also added. Thereafter, in step S4, the mixture is stirred at room temperature. After preparing the raw material sol or gel thus obtained, in step S5, the porous support is immersed, hydrothermal synthesis is performed at a predetermined temperature for a predetermined time, and then baking is performed to remove the structure directing agent. Do. Specific values of the predetermined temperature and the predetermined time will be described later.
In this embodiment, steps S1 to S4 are divided as processes, but the time between these steps is short, and silicon source, structure directing agent, water, titanium source, hydrogen peroxide are used as starting materials. The raw material sol or gel may be prepared by mixing at room temperature.
ここで、ケイ素源として用いるテトラアルキルオルトシリケートは、特に限定する物ではないが、例えばテトラメチルオルトシリケート、テトラエチルオルトシリケート、テトラプロピルオルトシリケート、テトラブチルオルトシリケート、テトラペンチルオルトシリケート、テトラヘキシルオルトシリケート、テトラヘプチルオルトシリケート、テトラオクチルオルトシリケート、トリメチルエチルシリケート、ジメチルエチルシリケート、メチルトリエチルシリケート、ジメチルプロピルシリケート等があげられる。これらの内入手の容易さからテトラエチルオルトシリケートが好ましく用いられる。 Here, the tetraalkylorthosilicate used as the silicon source is not particularly limited, but for example, tetramethylorthosilicate, tetraethylorthosilicate, tetrapropylorthosilicate, tetrabutylorthosilicate, tetrapentylorthosilicate, tetrahexylorthosilicate. Tetraheptyl orthosilicate, tetraoctyl orthosilicate, trimethylethyl silicate, dimethylethyl silicate, methyltriethyl silicate, dimethylpropyl silicate and the like. Of these, tetraethylorthosilicate is preferably used because of its easy availability.
チタン源として用いるテトラアルキルオルトチタネートは、特に限定する物ではないが、例えばテトラメチルオルトチタネート、テトラエチルオルトチタネート、テトラプロピルオルトチタネート、テトラブチルオルトチタネート、テトラオクチルオルトチタネート、トリメチルエチルチタネート、ジメチルジエチルチタネート、メチルトリエチルチタネート、ジメチルジプロピルチタネート等があげられる。これらの内入手の容易さからテトラエチルオルトチタネートやテトラブチルオルトチタネートが好ましく用いられる。 The tetraalkyl orthotitanate used as the titanium source is not particularly limited. For example, tetramethyl orthotitanate, tetraethyl orthotitanate, tetrapropyl orthotitanate, tetrabutyl orthotitanate, tetraoctyl orthotitanate, trimethylethyl titanate, dimethyl diethyl titanate Methyl triethyl titanate, dimethyl dipropyl titanate, and the like. Of these, tetraethyl orthotitanate and tetrabutyl orthotitanate are preferably used because of their easy availability.
構造規定剤として用いる水酸化テトラアルキルアンモニウムは、特に限定する物ではないが、例えば水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、テトラプロピルアンモニウム、水酸化テトラブチルアンモニウム等があげられ、入手の容易さからテトラプロピルアンモニウムが好ましく用いられる。 The tetraalkylammonium hydroxide used as the structure directing agent is not particularly limited, and examples thereof include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and the like, and are easily available. To tetrapropylammonium is preferably used.
多孔質支持体を原料ゲルに浸漬する際に支持体上に種結晶を担持させておくことによりチタノシリケート型ゼオライトの結晶を支持体上に効率よく析出させることが出来る。すなわち、チタノシリケート型ゼオライトの結晶化時間が短縮でき好都合である。種結晶としては、平均粒径が５００μｍ以下、特に０．５〜５０μｍの結晶が多孔質支持体上に保持しやすく好適である。この種結晶の多孔質支持体への担持量は１〜５００ｍｇ／ｃｍ２、特に１０〜６０ｍｇ／ｃｍ２ が好ましい。 When the porous support is immersed in the raw material gel, the seed crystal is supported on the support, whereby the titanosilicate zeolite crystals can be efficiently precipitated on the support. That is, it is convenient because the crystallization time of the titanosilicate zeolite can be shortened. As the seed crystal, a crystal having an average particle diameter of 500 μm or less, particularly 0.5 to 50 μm is preferable because it is easy to hold on the porous support. The amount of the seed crystal supported on the porous support is preferably 1 to 500 mg / cm 2 , particularly preferably 10 to 60 mg / cm 2 .
多孔質支持体上に種結晶を担持させるには、種結晶の粉末を溶媒、好ましくは水中に分散させ、これを多孔質支持体上にコートするのが好ましいが、多孔質支持体製造時に原料の一部としてＴ型ゼオライトの粉末を混入させてもよい。 In order to support the seed crystal on the porous support, it is preferable to disperse the seed crystal powder in a solvent, preferably water, and coat this on the porous support. T-type zeolite powder may be mixed as part of the above.
このようにして多孔質支持体の表面にチタノシリケート型ゼオライト結晶層の厚さが前述のとおり、０．１〜５００μｍ、好ましくは０．５〜１００μｍとなるように析出させることにより、本実施の形態に係る好適な混合物分離膜を得ることができる。 In this manner, the titanosilicate type zeolite crystal layer is deposited on the surface of the porous support so that the thickness thereof is 0.1 to 500 μm, preferably 0.5 to 100 μm, as described above. A suitable mixture separation membrane according to the embodiment can be obtained.
本発明において、多孔質支持体上にチタノシリケート型ゼオライト結晶層を膜状に析出させた分離膜を合成する際の反応原料の仕込み組成比は、ＳｉＯ２ ／ＴｉＯ２ ＝５〜５００、Ｈ２Ｏ ／ＳｉＯ２ ＝１０〜３００、ＲＮ＋／ＳｉＯ２＝０．０５〜１．０（ＲＮ＋は水酸化テトラアルキルアンモニウムを表す。）、となるように調整することが好ましい。さらに好ましくは、ＳｉＯ２ ／ＴｉＯ２ ＝２０〜３００、Ｈ２Ｏ ／ＳｉＯ２ ＝２０〜２００、ＲＮ＋／ＳｉＯ２＝０．１〜０．８である。 In the present invention, the composition ratio of the reaction raw materials when synthesizing a separation membrane in which a titanosilicate type zeolite crystal layer is deposited in the form of a membrane on a porous support is SiO 2 / TiO 2 = 5 to 500, H 2 O / SiO 2 = 10 to 300, RN + / SiO 2 = 0.05 to 1.0 (RN + represents tetraalkylammonium hydroxide) is preferably adjusted. More preferably, SiO 2 / TiO 2 = 20~300 , H 2 O / SiO 2 = 20~200, an RN + / SiO 2 = 0.1~0.8.
本発明において、水熱合成法により多孔質支持体上にチタノシリケート型ゼオライト結晶層を膜状に析出させた分離膜を合成する際の合成温度は１００〜２２０℃、好ましくは１５０〜２００℃であり、合成時間は１０〜１５０時間、好ましくは１６〜３０時間である。前記合成温度、合成時間にて反応を１回行うことにより、高い分離性能を有する多孔質支持体上にチタノシリケート型ゼオライト結晶層を膜状に析出させた分離膜を合成できる。この際、圧力は自圧或いは加圧下のいずれかの方法で行うことが出来るが、通常は自圧下で行える。系の攪拌は必ずしも行う必要はなく、静置状態でも製膜化は十分進行する。 In the present invention, the synthesis temperature when synthesizing a separation membrane in which a titanosilicate type zeolite crystal layer is deposited on a porous support by a hydrothermal synthesis method is 100 to 220 ° C, preferably 150 to 200 ° C. The synthesis time is 10 to 150 hours, preferably 16 to 30 hours. By performing the reaction once at the synthesis temperature and synthesis time, a separation membrane in which a titanosilicate type zeolite crystal layer is deposited in the form of a membrane on a porous support having high separation performance can be synthesized. At this time, the pressure can be performed by either self-pressure or under pressure, but usually it can be performed under self-pressure. It is not always necessary to stir the system, and film formation proceeds sufficiently even in a stationary state.
このように水熱合成した膜は水で十分に洗浄後、焼成を行う。焼成処理の温度は３００〜７００℃であり、好ましくは４００〜６００℃である。焼成時間は、特に限定されないが、１〜５０時間、好ましくは５〜２０時間焼成処理を行うことにより、本発明の多孔質支持体上にチタノシリケート型ゼオライト結晶層を膜状に析出させた分離膜を製造することが出来る。 The film hydrothermally synthesized in this way is sufficiently washed with water and then fired. The temperature of baking processing is 300-700 degreeC, Preferably it is 400-600 degreeC. The calcining time is not particularly limited, but the titanosilicate zeolite crystal layer was deposited in the form of a film on the porous support of the present invention by performing a calcining treatment for 1 to 50 hours, preferably 5 to 20 hours. A separation membrane can be manufactured.
本実施の形態に係る混合物分離膜の分離対象は、気体では、ヘリウム、水素、二酸化炭素、酸素、窒素やメタン、エタン、プロパン、ｎ−ブタン、ｉ−ブタンのようなＣ１〜Ｃ４の炭化水素ガスなどをあげることができ、液体としては、水、メタノール、エタノール、プロパノール等のアルコール類、アセトン、メチルエチルケトン等のケトン類、四塩化炭素、トリクロロエチレン等のハロゲン化炭化水素のごとき有機液体をあげることができる。本発明において分離の対象とする気体混合物とは上記ガス状化合物を２種類もしくはそれ以上含む混合物、液体混合物とは上記液状化合物を２種類もしくはそれ以上含む混合物である。 The separation target of the mixture separation membrane according to the present embodiment is a C1-C4 hydrocarbon such as helium, hydrogen, carbon dioxide, oxygen, nitrogen, methane, ethane, propane, n-butane, and i-butane in the case of gas. Examples of liquids include water, alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, and organic liquids such as halogenated hydrocarbons such as carbon tetrachloride and trichloroethylene. Can do. In the present invention, the gas mixture to be separated is a mixture containing two or more of the gaseous compounds, and the liquid mixture is a mixture containing two or more of the liquid compounds.
以下に実施例をあげて本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。これらの実施例は、チタン源であるテトラブチルオルトチタネートの量、水熱合成の温度と時間をパラメータとしてチタノシリケート型ゼオライト膜を合成するものであり、その後、その膜の分離性能について試験を実施した。また、比較例１は実施例１においてチタンを含まないものとするほかは全く条件を同じくして合成されたＭＦＩ型シリカライト膜である。 The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples. In these examples, a titanosilicate type zeolite membrane was synthesized using the amount of tetrabutyl orthotitanate as a titanium source, the temperature and time of hydrothermal synthesis as parameters, and then the separation performance of the membrane was tested. Carried out. Comparative Example 1 is an MFI type silicalite membrane synthesized under the same conditions as in Example 1 except that titanium is not included.
実施例１（合成例１）
出発原料としてテトラエチルオルトシリケート（アルドリッチ社製９８％）２２．１ｇ、テトラブチルオルトチタネート（和光純薬製９５％）０．３７ｇ、水酸化テトラプロピルアンモニウム（東京化成社製２０％）１６．０ｇ、水２１１．５ｇ、過酸化水素水（和光純薬製３０％）１ｍｌを用いて調整した原料ゲル（ＳｉＯ２ ：ＴｉＯ２ ：ＲＮ＋：Ｈ２Ｏ ＝１：０．０１：０．１７：１２０）を、テフロン（登録商標）内筒を備えたステンレス製耐圧反応管に仕込み、多孔質ムライト製支持体（長さ１０ｃｍ、平均孔径約１ミクロン）をこの中に浸漬し、温度２００℃で２４時間水熱合成を行った。前記反応終了後、表面に膜が析出した前記支持体を取り出し、水中で洗浄した後、５００℃で１０時間焼成した。
Example 1 (Synthesis Example 1)
As starting materials, tetraethylorthosilicate (98% manufactured by Aldrich) 22.1 g, tetrabutyl orthotitanate (95% manufactured by Wako Pure Chemical Industries) 0.37 g, tetrapropylammonium hydroxide (20% manufactured by Tokyo Chemical Industry Co., Ltd.) 16.0 g, Raw material gel (SiO 2 : TiO 2 : RN + : H 2 O = 1: 0.01: 0.17: 120 prepared using 211.5 g of water and 1 ml of hydrogen peroxide water (30% manufactured by Wako Pure Chemical Industries, Ltd.) ) In a pressure resistant reaction tube made of stainless steel equipped with a Teflon (registered trademark) inner cylinder, and a porous mullite support (length: 10 cm, average pore diameter: about 1 micron) is immersed in the tube and heated at a temperature of 200 ° C. for 24 hours. Time hydrothermal synthesis was performed. After completion of the reaction, the support having a film deposited on the surface was taken out, washed in water, and then baked at 500 ° C. for 10 hours.
比較例１
比較例として、チタン源を含まないＭＦＩ型シリカライト膜を以下のようにして調製した。出発原料としてテトラエチルオルトシリケート（アルドリッチ社製９８％）２２．１ｇ、水酸化テトラプロピルアンモニウム（東京化成社製２０％）１６．０ｇ、水２１１．５ｇを用いて調整した原料ゲル（ＳｉＯ２ ：ＲＮ＋：Ｈ２Ｏ ＝１：０．１７：１２０）を、テフロン（登録商標）内筒をそなえたステンレス製耐圧反応管に仕込み、多孔質ムライト製支持体（長さ１０ｃｍ、平均孔径約１ミクロン）を、この中に浸漬し、温度２００℃で２４時間水熱合成を行った。前記反応終了後、表面に膜が析出した前記支持体を取り出し水中で洗浄した後、５００℃で１０時間焼成した。
Comparative Example 1
As a comparative example, an MFI type silicalite film not containing a titanium source was prepared as follows. Raw material gel (SiO 2 : RN) prepared using 22.1 g of tetraethylorthosilicate (98% made by Aldrich), 16.0 g of tetrapropylammonium hydroxide (20% made by Tokyo Kasei Co., Ltd.) and 211.5 g of water as starting materials. + : H 2 O = 1: 0.17: 120) was charged into a stainless steel pressure-resistant reaction tube having a Teflon (registered trademark) inner cylinder, and a porous mullite support (length 10 cm, average pore diameter of about 1 micron) ) Was immersed in this, and hydrothermal synthesis was performed at a temperature of 200 ° C. for 24 hours. After completion of the reaction, the support having a film deposited on the surface was taken out, washed in water, and then baked at 500 ° C. for 10 hours.
実施例１で得られた多孔質支持体上にチタノシリケート型ゼオライト結晶層を析出させた分離膜のＸ線回折を行った結果について図２を参照しながら説明する。
図２に示されるのはいずれもＸ線回折測定図であり、（１）はチタノシリケート型ゼオライトの結晶粉末、（２）は、実施例１で調製した多孔質支持体上に析出させたチタノシリケート型ゼオライト膜、（３）は比較例１で調製した多孔質支持体上に析出させたＭＦＩ型シリカライト膜、（４）は多孔質支持体のものである。測定図の横軸は２theta（θ）、すなわち入射角の２倍値を度(degree)で示すもので、縦軸はＸ線回折強度を示すものである。
図２において、（１）と（２）のＸ線回折図のピークパターンはよく一致しており、また、比較例１で調製したチタン源を含まないＭＦＩ型シリカライト膜のピークパターンとも良く一致している。しかし、いずれも（４）とは一致していない。したがって、いずれもゼオライトの結晶構造を示しており、今回の実施例におけるチタノシリケート型の混合物分離膜においても適切にチタノシリケート型ゼオライト結晶層が析出していることが確認された。
The results of X-ray diffraction of the separation membrane in which the titanosilicate zeolite crystal layer was deposited on the porous support obtained in Example 1 will be described with reference to FIG.
2 are X-ray diffraction measurement diagrams. (1) is a crystal powder of titanosilicate type zeolite, and (2) is deposited on the porous support prepared in Example 1. The titanosilicate type zeolite membrane, (3) is the MFI type silicalite membrane deposited on the porous support prepared in Comparative Example 1, and (4) is that of the porous support. The horizontal axis of the measurement diagram represents 2 theta (θ), that is, a value that represents twice the incident angle in degrees, and the vertical axis represents the X-ray diffraction intensity.
In FIG. 2, the peak patterns of the X-ray diffraction patterns of (1) and (2) are in good agreement, and the peak pattern of the MFI type silicalite film not containing the titanium source prepared in Comparative Example 1 is also good. I'm doing it. However, none of them agrees with (4). Therefore, all showed the crystal structure of zeolite, and it was confirmed that the titanosilicate type zeolite crystal layer was appropriately deposited also in the titanosilicate type mixture separation membrane in the present example.
次に図３を参照しながら、本実施例のチタノシリケート型ゼオライト膜と比較例のＭＦＩ型ゼオライト膜について赤外線吸収スペクトルの測定結果について説明する。図３の（１）は本実施例に係るチタノシリケート型ゼオライト膜の赤外線吸収スペクトル測定結果を示し、（２）はＭＦＩ型ゼオライト膜の赤外線吸収スペクトル測定結果を示す図である。図３における横軸は１ｃｍ当りの波数を示しており縦軸はTransmission（透過率）を示すものである。
図３の本実施例に係る（１）では９６０ｃｍ−１付近にＴｉ−Ｏ−Ｓｉ結合に起因する吸収ピークが観測されている。
Next, measurement results of infrared absorption spectra of the titanosilicate zeolite membrane of this example and the MFI zeolite membrane of the comparative example will be described with reference to FIG. (1) of FIG. 3 shows the infrared absorption spectrum measurement result of the titanosilicate type zeolite membrane according to this example, and (2) shows the infrared absorption spectrum measurement result of the MFI type zeolite membrane. The horizontal axis in FIG. 3 indicates the wave number per 1 cm, and the vertical axis indicates the transmission (transmittance).
In (1) according to this example of FIG. 3, an absorption peak due to the Ti—O—Si bond is observed in the vicinity of 960 cm −1 .
更に、図４は本実施例に係るチタノシリケート型ゼオライト膜に対して紫外・可視領域の拡散反射スペクトルを測定した結果を示す図である。図４において、横軸は拡散反射スペクトルの波長を示し、縦軸は吸光度を示す。この図４では、
２１０ｎｍ付近に４配位Ｔｉに基づく吸収が観測された。
図３，４に示された結果によりＭＦＩ型骨格におけるＴｉ原子の置換が確認でき、多孔質支持体表面にチタノシリケート型ゼオライト結晶層が生成していることが確認された。
Further, FIG. 4 is a diagram showing the results of measuring the diffuse reflection spectrum in the ultraviolet / visible region for the titanosilicate zeolite membrane according to this example. In FIG. 4, the horizontal axis indicates the wavelength of the diffuse reflection spectrum, and the vertical axis indicates the absorbance. In this FIG.
Absorption based on tetracoordinated Ti was observed near 210 nm.
The results shown in FIGS. 3 and 4 confirmed the substitution of Ti atoms in the MFI type skeleton, and confirmed that a titanosilicate type zeolite crystal layer was formed on the surface of the porous support.
また、図５（ａ）は、この実施例１で得られた混合物分離膜の表面を走査型電子顕微鏡で撮影した写真を示すものであり、（ｂ）は同じく断面を撮影した写真である。図５（ａ），（ｂ）から、多孔質支持体上に緻密にＭＦＩ型のチタノシリケート型ゼオライトが析出しているのが確認された。 Moreover, Fig.5 (a) shows the photograph which image | photographed the surface of the mixture separation membrane obtained in this Example 1 with the scanning electron microscope, (b) is the photograph which image | photographed the cross section similarly. 5 (a) and 5 (b), it was confirmed that MFI type titanosilicate type zeolite was densely deposited on the porous support.
実施例２（合成例２）
出発原料としてテトラエチルオルトシリケート（アルドリッチ社製９８％）２２．１ｇ、テトラブチルオルトチタネート（和光純薬製９５％）０．３７ｇ、水酸化テトラプロピルアンモニウム（東京化成社製２０％）１６．０ｇ、水２１１．５ｇ、過酸化水素水（和光純薬製３０％）１ｍｌを用いて調整した原料ゲル（ＳｉＯ２ ：ＴｉＯ２ ：ＲＮ＋：Ｈ２Ｏ ＝１：０．０１：０．１７：１２０）を、テフロン（登録商標）内筒を備えたステンレス製耐圧反応管に仕込み、多孔質ムライト製支持体（長さ１０ｃｍ、平均孔径約１ミクロン）をこの中に浸漬し、温度２００℃で１２時間水熱合成を行った。前記反応終了後、表面に膜が析出した前記支持体を取り出し、水中で洗浄した後、５００℃で１０時間焼成した。
Example 2 (Synthesis Example 2)
As starting materials, tetraethylorthosilicate (98% manufactured by Aldrich) 22.1 g, tetrabutyl orthotitanate (95% manufactured by Wako Pure Chemical Industries) 0.37 g, tetrapropylammonium hydroxide (20% manufactured by Tokyo Chemical Industry Co., Ltd.) 16.0 g, Raw material gel (SiO 2 : TiO 2 : RN + : H 2 O = 1: 0.01: 0.17: 120 prepared using 211.5 g of water and 1 ml of hydrogen peroxide water (30% manufactured by Wako Pure Chemical Industries, Ltd.) ) In a stainless steel pressure-resistant reaction tube equipped with a Teflon (registered trademark) inner cylinder, and a porous mullite support (length: 10 cm, average pore diameter: about 1 micron) is immersed in the tube. Time hydrothermal synthesis was performed. After completion of the reaction, the support having a film deposited on the surface was taken out, washed in water, and then baked at 500 ° C. for 10 hours.
実施例３（合成例３）
出発原料としてテトラエチルオルトシリケート（アルドリッチ社製９８％）２２．１ｇ、テトラブチルオルトチタネート（和光純薬製９５％）０．３７ｇ、水酸化テトラプロピルアンモニウム（東京化成社製２０％）１６．０ｇ、水２１１．５ｇ、過酸化水素水（和光純薬製３０％）１ｍｌを用いて調整した原料ゲル（ＳｉＯ２ ：ＴｉＯ２ ：ＲＮ＋：Ｈ２Ｏ ＝１：０．０１：０．１７：１２０）を、テフロン（登録商標）内筒を備えたステンレス製耐圧反応管に仕込み、多孔質ムライト製支持体（長さ１０ｃｍ、平均孔径約１ミクロン）をこの中に浸漬し、温度２００℃で１６時間水熱合成を行った。前記反応終了後、表面に膜が析出した前記支持体を取り出し、水中で洗浄した後、５００℃で１０時間焼成した。
Example 3 (Synthesis Example 3)
As starting materials, tetraethylorthosilicate (98% manufactured by Aldrich) 22.1 g, tetrabutyl orthotitanate (95% manufactured by Wako Pure Chemical Industries) 0.37 g, tetrapropylammonium hydroxide (20% manufactured by Tokyo Chemical Industry Co., Ltd.) 16.0 g, Raw material gel (SiO 2 : TiO 2 : RN + : H 2 O = 1: 0.01: 0.17: 120 prepared using 211.5 g of water and 1 ml of hydrogen peroxide water (30% manufactured by Wako Pure Chemical Industries, Ltd.) ) In a stainless steel pressure-resistant reaction tube equipped with a Teflon (registered trademark) inner cylinder, and a porous mullite support (length: 10 cm, average pore diameter: about 1 micron) is dipped in this, Time hydrothermal synthesis was performed. After completion of the reaction, the support having a film deposited on the surface was taken out, washed in water, and then baked at 500 ° C. for 10 hours.
実施例４（合成例４）
出発原料としてテトラエチルオルトシリケート（アルドリッチ社製９８％）２２．１ｇ、テトラブチルオルトチタネート（和光純薬製９５％）０．３７ｇ、水酸化テトラプロピルアンモニウム（東京化成社製２０％）１６．０ｇ、水２１１．５ｇ、過酸化水素水（和光純薬製３０％）１ｍｌを用いて調整した原料ゲル（ＳｉＯ２ ：ＴｉＯ２ ：ＲＮ＋：Ｈ２Ｏ ＝１：０．０１：０．１７：１２０）を、テフロン（登録商標）内筒を備えたステンレス製耐圧反応管に仕込み、多孔質ムライト製支持体（長さ１０ｃｍ、平均孔径約１ミクロン）をこの中に浸漬し、温度２００℃で２０時間水熱合成を行った。前記反応終了後、表面に膜が析出した前記支持体を取り出し、水中で洗浄した後、５００℃で１０時間焼成した。
Example 4 (Synthesis Example 4)
As starting materials, tetraethylorthosilicate (98% manufactured by Aldrich) 22.1 g, tetrabutyl orthotitanate (95% manufactured by Wako Pure Chemical Industries) 0.37 g, tetrapropylammonium hydroxide (20% manufactured by Tokyo Chemical Industry Co., Ltd.) 16.0 g, Raw material gel (SiO 2 : TiO 2 : RN + : H 2 O = 1: 0.01: 0.17: 120 prepared using 211.5 g of water and 1 ml of hydrogen peroxide water (30% manufactured by Wako Pure Chemical Industries, Ltd.) ) In a stainless steel pressure-resistant reaction tube equipped with a Teflon (registered trademark) inner cylinder, and a porous mullite support (length: 10 cm, average pore diameter: about 1 micron) is immersed in the tube. Time hydrothermal synthesis was performed. After completion of the reaction, the support having a film deposited on the surface was taken out, washed in water, and then baked at 500 ° C. for 10 hours.
実施例５（合成例５）
出発原料としてテトラエチルオルトシリケート（アルドリッチ社製９８％）２２．１ｇ、テトラブチルオルトチタネート（和光純薬製９５％）０．３７ｇ、水酸化テトラプロピルアンモニウム（東京化成社製２０％）１６．０ｇ、水２１１．５ｇ、過酸化水素水（和光純薬製３０％）１ｍｌを用いて調整した原料ゲル（ＳｉＯ２ ：ＴｉＯ２ ：ＲＮ＋：Ｈ２Ｏ ＝１：０．０１：０．１７：１２０）を、テフロン（登録商標）内筒を備えたステンレス製耐圧反応管に仕込み、多孔質ムライト製支持体（長さ１０ｃｍ、平均孔径約１ミクロン）をこの中に浸漬し、温度２００℃で４０時間水熱合成を行った。前記反応終了後、表面に膜が析出した前記支持体を取り出し、水中で洗浄した後、５００℃で１０時間焼成した。
Example 5 (Synthesis Example 5)
As starting materials, tetraethylorthosilicate (98% manufactured by Aldrich) 22.1 g, tetrabutyl orthotitanate (95% manufactured by Wako Pure Chemical Industries) 0.37 g, tetrapropylammonium hydroxide (20% manufactured by Tokyo Chemical Industry Co., Ltd.) 16.0 g, Raw material gel (SiO 2 : TiO 2 : RN + : H 2 O = 1: 0.01: 0.17: 120 prepared using 211.5 g of water and 1 ml of hydrogen peroxide water (30% manufactured by Wako Pure Chemical Industries, Ltd.) ) In a stainless steel pressure-resistant reaction tube equipped with a Teflon (registered trademark) inner cylinder, and a porous mullite support (length: 10 cm, average pore diameter: about 1 micron) is immersed in the tube. Time hydrothermal synthesis was performed. After completion of the reaction, the support having a film deposited on the surface was taken out, washed in water, and then baked at 500 ° C. for 10 hours.
実施例６（合成例６）
出発原料としてテトラエチルオルトシリケート（アルドリッチ社製９８％）２２．１ｇ、テトラブチルオルトチタネート（和光純薬製９５％）０．１９ｇ、水酸化テトラプロピルアンモニウム（東京化成社製２０％）１６．０ｇ、水２１１．５ｇ、過酸化水素水（和光純薬製３０％）１ｍｌを用いて調整した原料ゲル（ＳｉＯ２ ：ＴｉＯ２ ：ＲＮ＋：Ｈ２Ｏ ＝１：０．００５：０．１７：１２０）を、テフロン（登録商標）内筒を備えたステンレス製耐圧反応管に仕込み、多孔質ムライト製支持体（長さ１０ｃｍ、平均孔径約１ミクロン）をこの中に浸漬し、温度２００℃で２４時間水熱合成を行った。前記反応終了後、表面に膜が析出した前記支持体を取り出し、水中で洗浄した後、５００℃で１０時間焼成した。
Example 6 (Synthesis Example 6)
As starting materials, tetraethylorthosilicate (98% manufactured by Aldrich) 22.1 g, tetrabutyl orthotitanate (95% manufactured by Wako Pure Chemical Industries) 0.19 g, tetrapropylammonium hydroxide (20% manufactured by Tokyo Chemical Industry Co., Ltd.) 16.0 g, Raw material gel (SiO 2 : TiO 2 : RN + : H 2 O = 1: 0.005: 0.17: 120 prepared using 211.5 g of water and 1 ml of hydrogen peroxide water (30% manufactured by Wako Pure Chemical Industries, Ltd.) ) In a pressure resistant reaction tube made of stainless steel equipped with a Teflon (registered trademark) inner cylinder, and a porous mullite support (length: 10 cm, average pore diameter: about 1 micron) is immersed in the tube and heated at a temperature of 200 ° C. for 24 hours. Time hydrothermal synthesis was performed. After completion of the reaction, the support having a film deposited on the surface was taken out, washed in water, and then baked at 500 ° C. for 10 hours.
実施例７（合成例７）
出発原料としてテトラエチルオルトシリケート（アルドリッチ社製９８％）２２．１ｇ、テトラブチルオルトチタネート（和光純薬製９５％）０．７８ｇ、水酸化テトラプロピルアンモニウム（東京化成社製２０％）１６．０ｇ、水２１１．５ｇ、過酸化水素水（和光純薬製３０％）１ｍｌを用いて調整した原料ゲル（ＳｉＯ２ ：ＴｉＯ２ ：ＲＮ＋：Ｈ２Ｏ ＝１：０．０２：０．１７：１２０）を、テフロン（登録商標）内筒を備えたステンレス製耐圧反応管に仕込み、多孔質ムライト製支持体（長さ１０ｃｍ、平均孔径約１ミクロン）をこの中に浸漬し、温度２００℃で２０時間水熱合成を行った。前記反応終了後、表面に膜が析出した前記支持体を取り出し、水中で洗浄した後、５００℃で１０時間焼成した。
Example 7 (Synthesis Example 7)
As starting materials, tetraethylorthosilicate (Aldrich 98%) 22.1 g, tetrabutylorthotitanate (Wako Pure Chemicals 95%) 0.78 g, tetrapropylammonium hydroxide (Tokyo Kasei 20%) 16.0 g, Raw material gel (SiO 2 : TiO 2 : RN + : H 2 O = 1: 0.02: 0.17: 120 prepared using 211.5 g of water and 1 ml of hydrogen peroxide solution (30% manufactured by Wako Pure Chemical Industries, Ltd.) ) In a stainless steel pressure-resistant reaction tube equipped with a Teflon (registered trademark) inner cylinder, and a porous mullite support (length: 10 cm, average pore diameter: about 1 micron) is immersed in the tube. Time hydrothermal synthesis was performed. After completion of the reaction, the support having a film deposited on the surface was taken out, washed in water, and then baked at 500 ° C. for 10 hours.
実施例８（合成例８）
出発原料としてテトラエチルオルトシリケート（アルドリッチ社製９８％）２２．１ｇ、テトラブチルオルトチタネート（和光純薬製９５％）１．１１ｇ、水酸化テトラプロピルアンモニウム（東京化成社製２０％）１６．０ｇ、水２１１．５ｇ、過酸化水素水（和光純薬製３０％）１ｍｌを用いて調整した原料ゲル（ＳｉＯ２ ：ＴｉＯ２ ：ＲＮ＋：Ｈ２Ｏ ＝１：０．０３：０．１７：１２０）を、テフロン（登録商標）内筒を備えたステンレス製耐圧反応管に仕込み、多孔質ムライト製支持体（長さ１０ｃｍ、平均孔径約１ミクロン）をこの中に浸漬し、温度２００℃で２４時間水熱合成を行った。前記反応終了後、表面に膜が析出した前記支持体を取り出し、水中で洗浄した後、５００℃で１０時間焼成した。
Example 8 (Synthesis Example 8)
As starting materials, tetraethylorthosilicate (Aldrich 98%) 22.1 g, tetrabutylorthotitanate (Wako Pure Chemicals 95%) 1.11 g, tetrapropylammonium hydroxide (Tokyo Kasei 20%) 16.0 g, Raw material gel (SiO 2 : TiO 2 : RN + : H 2 O = 1: 0.03: 0.17: 120 prepared using 211.5 g of water and 1 ml of hydrogen peroxide solution (30% manufactured by Wako Pure Chemical Industries, Ltd.) ) In a pressure resistant reaction tube made of stainless steel equipped with a Teflon (registered trademark) inner cylinder, and a porous mullite support (length: 10 cm, average pore diameter: about 1 micron) is immersed in the tube and heated at a temperature of 200 ° C. for 24 hours. Time hydrothermal synthesis was performed. After completion of the reaction, the support having a film deposited on the surface was taken out, washed in water, and then baked at 500 ° C. for 10 hours.
実施例９（合成例９）
出発原料としてテトラエチルオルトシリケート（アルドリッチ社製９８％）２２．１ｇ、テトラブチルオルトチタネート（和光純薬製９５％）０．７８ｇ、水酸化テトラプロピルアンモニウム（東京化成社製２０％）１６．０ｇ、水２１１．５ｇ、過酸化水素水（和光純薬製３０％）１ｍｌを用いて調整した原料ゲル（ＳｉＯ２ ：ＴｉＯ２ ：ＲＮ＋：Ｈ２Ｏ ＝１：０．０２：０．１７：１２０）を、テフロン（登録商標）内筒を備えたステンレス製耐圧反応管に仕込み、多孔質ムライト製支持体（長さ１０ｃｍ、平均孔径約１ミクロン）をこの中に浸漬し、温度１７０℃で４８時間水熱合成を行った。前記反応終了後、表面に膜が析出した前記支持体を取り出し、水中で洗浄した後、５００℃で１０時間焼成した。
Example 9 (Synthesis Example 9)
As starting materials, tetraethylorthosilicate (Aldrich 98%) 22.1 g, tetrabutylorthotitanate (Wako Pure Chemicals 95%) 0.78 g, tetrapropylammonium hydroxide (Tokyo Kasei 20%) 16.0 g, Raw material gel (SiO 2 : TiO 2 : RN + : H 2 O = 1: 0.02: 0.17: 120 prepared using 211.5 g of water and 1 ml of hydrogen peroxide solution (30% manufactured by Wako Pure Chemical Industries, Ltd.) ) In a pressure resistant reaction tube made of stainless steel equipped with a Teflon (registered trademark) inner cylinder, a porous mullite support (length: 10 cm, average pore diameter: about 1 micron) is immersed in this, and the temperature is set to 48 at a temperature of 170 ° C. Time hydrothermal synthesis was performed. After completion of the reaction, the support having a film deposited on the surface was taken out, washed in water, and then baked at 500 ° C. for 10 hours.
実施例１０（合成例１０）
出発原料としてテトラエチルオルトシリケート（アルドリッチ社製９８％）８０．３ｇ、テトラブチルオルトチタネート（和光純薬製９５％）３．８６ｇ、水酸化テトラプロピルアンモニウム（東京化成社製２０％）１３４．５ｇ、水８１．３ｇ、過酸化水素水（和光純薬製３０％）１ｍｌを用いて調整した原料ゲル（ＳｉＯ２ ：ＴｉＯ２ ：ＲＮ＋：Ｈ２Ｏ ＝１：０．０３：０．３５：２８）を、テフロン（登録商標）内筒を備えたステンレス製耐圧反応管に仕込み、多孔質ムライト製支持体（長さ１０ｃｍ、平均孔径約１ミクロン）をこの中に浸漬し、温度１７５℃で４８時間水熱合成を行った。前記反応終了後、表面に膜が析出した前記支持体を取り出し、水中で洗浄した後、５００℃で１０時間焼成した。
Example 10 (Synthesis Example 10)
As starting materials, tetraethylorthosilicate (Aldrich 98%) 80.3 g, tetrabutylorthotitanate (Wako Pure Chemicals 95%) 3.86 g, tetrapropylammonium hydroxide (Tokyo Kasei 20%) 134.5 g, Raw material gel (SiO 2 : TiO 2 : RN + : H 2 O = 1: 0.03: 0.35: 28) prepared using 81.3 g of water and 1 ml of hydrogen peroxide water (30% manufactured by Wako Pure Chemical Industries, Ltd.) ) In a stainless steel pressure-resistant reaction tube equipped with a Teflon (registered trademark) inner cylinder, and a porous mullite support (length: 10 cm, average pore diameter: about 1 micron) is immersed in the tube. Time hydrothermal synthesis was performed. After completion of the reaction, the support having a film deposited on the surface was taken out, washed in water, and then baked at 500 ° C. for 10 hours.
実施例１１（合成例１１）
出発原料としてテトラエチルオルトシリケート（アルドリッチ社製９８％）２２．１ｇ、テトラブチルオルトチタネート（和光純薬製９５％）０．７８ｇ、水酸化テトラプロピルアンモニウム（東京化成社製２０％）１６．０ｇ、水２１１．５ｇ、過酸化水素水（和光純薬製３０％）１ｍｌを用いて調整した原料ゲル（ＳｉＯ２ ：ＴｉＯ２ ：ＲＮ＋：Ｈ２Ｏ ＝１：０．０２：０．１７：１２０）を、テフロン（登録商標）内筒を備えたステンレス製耐圧反応管に仕込み、多孔質ムライト製支持体（長さ１０ｃｍ、平均孔径約１ミクロン）をこの中に浸漬し、温度１７０℃で１２０時間水熱合成を行った。前記反応終了後、表面に膜が析出した前記支持体を取り出し、水中で洗浄した後、５００℃で１０時間焼成した。
Example 11 (Synthesis Example 11)
As starting materials, tetraethylorthosilicate (Aldrich 98%) 22.1 g, tetrabutylorthotitanate (Wako Pure Chemicals 95%) 0.78 g, tetrapropylammonium hydroxide (Tokyo Kasei 20%) 16.0 g, Raw material gel (SiO 2 : TiO 2 : RN + : H 2 O = 1: 0.02: 0.17: 120 prepared using 211.5 g of water and 1 ml of hydrogen peroxide solution (30% manufactured by Wako Pure Chemical Industries, Ltd.) ) In a stainless steel pressure-resistant reaction tube equipped with a Teflon (registered trademark) inner cylinder, and a porous mullite support (length: 10 cm, average pore diameter: about 1 micron) is immersed in the tube. Time hydrothermal synthesis was performed. After completion of the reaction, the support having a film deposited on the surface was taken out, washed in water, and then baked at 500 ° C. for 10 hours.
実施例１２（合成例１２）
出発原料としてテトラエチルオルトシリケート（アルドリッチ社製９８％）２２．１ｇ、テトラブチルオルトチタネート（和光純薬製９５％）０．７８ｇ、水酸化テトラプロピルアンモニウム（東京化成社製２０％）１６．０ｇ、水２１１．５ｇ、過酸化水素水（和光純薬製３０％）１ｍｌを用いて調整した原料ゲル（ＳｉＯ２ ：ＴｉＯ２ ：ＲＮ＋：Ｈ２Ｏ ＝１：０．０２：０．１７：１２０）を、テフロン（登録商標）内筒を備えたステンレス製耐圧反応管に仕込み、多孔質ムライト製支持体（長さ１０ｃｍ、平均孔径約１ミクロン）をこの中に浸漬し、温度１８０℃で７２時間水熱合成を行った。前記反応終了後、表面に膜が析出した前記支持体を取り出し、水中で洗浄した後、５００℃で１０時間焼成した。
Example 12 (Synthesis Example 12)
As starting materials, tetraethylorthosilicate (Aldrich 98%) 22.1 g, tetrabutylorthotitanate (Wako Pure Chemicals 95%) 0.78 g, tetrapropylammonium hydroxide (Tokyo Kasei 20%) 16.0 g, Raw material gel (SiO 2 : TiO 2 : RN + : H 2 O = 1: 0.02: 0.17: 120 prepared using 211.5 g of water and 1 ml of hydrogen peroxide solution (30% manufactured by Wako Pure Chemical Industries, Ltd.) ) In a stainless steel pressure-resistant reaction tube equipped with a Teflon (registered trademark) inner cylinder, and a porous mullite support (length: 10 cm, average pore diameter: about 1 micron) is immersed in the tube. Time hydrothermal synthesis was performed. After completion of the reaction, the support having a film deposited on the surface was taken out, washed in water, and then baked at 500 ° C. for 10 hours.
実施例１３（合成例１３）
出発原料としてテトラエチルオルトシリケート（アルドリッチ社製９８％）２２．１ｇ、テトラブチルオルトチタネート（和光純薬製９５％）０．７８ｇ、水酸化テトラプロピルアンモニウム（東京化成社製２０％）１６．０ｇ、水２１１．５ｇ、過酸化水素水（和光純薬製３０％）１ｍｌを用いて調整した原料ゲル（ＳｉＯ２ ：ＴｉＯ２ ：ＲＮ＋：Ｈ２Ｏ ＝１：０．０２：０．１７：１２０）を、テフロン（登録商標）内筒を備えたステンレス製耐圧反応管に仕込み、多孔質ムライト製支持体（長さ１０ｃｍ、平均孔径約１ミクロン）をこの中に浸漬し、温度１９０℃で４０時間水熱合成を行った。前記反応終了後、表面に膜が析出した前記支持体を取り出し、水中で洗浄した後、５００℃で１０時間焼成した。
Example 13 (Synthesis Example 13)
As starting materials, tetraethylorthosilicate (Aldrich 98%) 22.1 g, tetrabutylorthotitanate (Wako Pure Chemicals 95%) 0.78 g, tetrapropylammonium hydroxide (Tokyo Kasei 20%) 16.0 g, Raw material gel (SiO 2 : TiO 2 : RN + : H 2 O = 1: 0.02: 0.17: 120 prepared using 211.5 g of water and 1 ml of hydrogen peroxide solution (30% manufactured by Wako Pure Chemical Industries, Ltd.) ) In a pressure resistant reaction tube made of stainless steel equipped with a Teflon (registered trademark) inner cylinder, a porous mullite support (length: 10 cm, average pore diameter: about 1 micron) is immersed in this, and a temperature of 190 ° C. is 40. Time hydrothermal synthesis was performed. After completion of the reaction, the support having a film deposited on the surface was taken out, washed in water, and then baked at 500 ° C. for 10 hours.
実施例１４（合成例１４）
出発原料としてテトラエチルオルトシリケート（アルドリッチ社製９８％）２２．１ｇ、テトラブチルオルトチタネート（和光純薬製９５％）０．７８ｇ、水酸化テトラプロピルアンモニウム（東京化成社製２０％）１６．０ｇ、水２１１．５ｇ、過酸化水素水（和光純薬製３０％）１ｍｌを用いて調整した原料ゲル（ＳｉＯ２ ：ＴｉＯ２ ：ＲＮ＋：Ｈ２Ｏ ＝１：０．０２：０．１７：１２０）を、テフロン（登録商標）内筒を備えたステンレス製耐圧反応管に仕込み、多孔質ムライト製支持体（長さ１０ｃｍ、平均孔径約１ミクロン）をこの中に浸漬し、温度２１０℃で２０時間水熱合成を行った。前記反応終了後、表面に膜が析出した前記支持体を取り出し、水中で洗浄した後、５００℃で１０時間焼成した。
Example 14 (Synthesis Example 14)
As starting materials, tetraethylorthosilicate (Aldrich 98%) 22.1 g, tetrabutylorthotitanate (Wako Pure Chemicals 95%) 0.78 g, tetrapropylammonium hydroxide (Tokyo Kasei 20%) 16.0 g, Raw material gel (SiO 2 : TiO 2 : RN + : H 2 O = 1: 0.02: 0.17: 120 prepared using 211.5 g of water and 1 ml of hydrogen peroxide solution (30% manufactured by Wako Pure Chemical Industries, Ltd.) ) In a pressure resistant reaction tube made of stainless steel equipped with a Teflon (registered trademark) inner cylinder, a porous mullite support (length: 10 cm, average pore diameter: about 1 micron) is immersed in the tube, and the temperature is 210 ° C. Time hydrothermal synthesis was performed. After completion of the reaction, the support having a film deposited on the surface was taken out, washed in water, and then baked at 500 ° C. for 10 hours.
実施例１５（合成例１５）
出発原料としてテトラエチルオルトシリケート（アルドリッチ社製９８％）２２．１ｇ、テトラブチルオルトチタネート（和光純薬製９５％）０．７８ｇ、水酸化テトラプロピルアンモニウム（東京化成社製２０％）１６．０ｇ、水７３．８ｇ、過酸化水素水（和光純薬製３０％）１ｍｌを用いて調整した原料ゲル（ＳｉＯ２ ：ＴｉＯ２ ：ＲＮ＋：Ｈ２Ｏ ＝１：０．０２：０．１７：４０）を、テフロン（登録商標）内筒を備えたステンレス製耐圧反応管に仕込み、多孔質ムライト製支持体（長さ１０ｃｍ、平均孔径約１ミクロン）をこの中に浸漬し、温度２００℃で２４時間水熱合成を行った。前記反応終了後、表面に膜が析出した前記支持体を取り出し、水中で洗浄した後、５００℃で１０時間焼成した。
Example 15 (Synthesis Example 15)
As starting materials, tetraethylorthosilicate (Aldrich 98%) 22.1 g, tetrabutylorthotitanate (Wako Pure Chemicals 95%) 0.78 g, tetrapropylammonium hydroxide (Tokyo Kasei 20%) 16.0 g, Raw material gel (SiO 2 : TiO 2 : RN + : H 2 O = 1: 0.02: 0.17: 40 prepared using 73.8 g of water and 1 ml of hydrogen peroxide water (30% manufactured by Wako Pure Chemical Industries, Ltd.) ) In a pressure resistant reaction tube made of stainless steel equipped with a Teflon (registered trademark) inner cylinder, and a porous mullite support (length: 10 cm, average pore diameter: about 1 micron) is immersed in the tube and heated at a temperature of 200 ° C. for 24 hours. Time hydrothermal synthesis was performed. After completion of the reaction, the support having a film deposited on the surface was taken out, washed in water, and then baked at 500 ° C. for 10 hours.
実施例１６（合成例１６）
出発原料としてテトラエチルオルトシリケート（アルドリッチ社製９８％）２２．１ｇ、テトラブチルオルトチタネート（和光純薬製９５％）０．７８ｇ、水酸化テトラプロピルアンモニウム（東京化成社製２０％）１６．０ｇ、水２６４．４ｇ、過酸化水素水（和光純薬製３０％）１ｍｌを用いて調整した原料ゲル（ＳｉＯ２ ：ＴｉＯ２ ：ＲＮ＋：Ｈ２Ｏ ＝１：０．０２：０．１７：１５０）を、テフロン（登録商標）内筒を備えたステンレス製耐圧反応管に仕込み、多孔質ムライト製支持体（長さ１０ｃｍ、平均孔径約１ミクロン）をこの中に浸漬し、温度２００℃で２４時間水熱合成を行った。前記反応終了後、表面に膜が析出した前記支持体を取り出し、水中で洗浄した後、５００℃で１０時間焼成した。
Example 16 (Synthesis Example 16)
As starting materials, tetraethylorthosilicate (Aldrich 98%) 22.1 g, tetrabutylorthotitanate (Wako Pure Chemicals 95%) 0.78 g, tetrapropylammonium hydroxide (Tokyo Kasei 20%) 16.0 g, Raw material gel (SiO 2 : TiO 2 : RN + : H 2 O = 1: 0.02: 0.17: 150 prepared using 264.4 g of water and 1 ml of hydrogen peroxide water (30% manufactured by Wako Pure Chemical Industries, Ltd.) ) In a pressure resistant reaction tube made of stainless steel equipped with a Teflon (registered trademark) inner cylinder, and a porous mullite support (length: 10 cm, average pore diameter: about 1 micron) is immersed in the tube and heated at a temperature of 200 ° C. for 24 hours. Time hydrothermal synthesis was performed. After completion of the reaction, the support having a film deposited on the surface was taken out, washed in water, and then baked at 500 ° C. for 10 hours.
実施例１７（使用例１）
実施例７で作製した膜について、マスフローメータ（ＳＴＥＣ社製、ＳＥＦ−７３３０Ｍ）を用いて、作製した膜のヘリウム、水素、二酸化炭素、酸素、窒素、メタン、ｎ−ブタン、およびｉ−ブタンガスの透過速度を５０℃で測定した。また、各気体の透過速度の比を以って分離係数とした結果、気体透過速度はそれぞれ２４０、６００、１９００、５９０、５７０、１６００、２１０、１．８×１０−６（ｃｍ３（ＳＴＰ）／ｃｍ２ｓｃｍＨｇ）となり、分子径の大きいｉ−ブタンが他のガスに比べて透過速度が非常に小さくなり、本発明の膜は分子ふるい能を有している。
Example 17 (Use Example 1)
About the film produced in Example 7, using a mass flow meter (manufactured by STEC, SEF-7330M), helium, hydrogen, carbon dioxide, oxygen, nitrogen, methane, n-butane, and i-butane gas of the produced film were used. The permeation rate was measured at 50 ° C. Moreover, as a result of using the ratio of the permeation rate of each gas as the separation factor, the gas permeation rates were 240, 600, 1900, 590, 570, 1600, 210, 1.8 × 10 −6 (cm 3 (STP ) / Cm 2 scmHg), i-butane having a large molecular diameter has a very low permeation rate compared to other gases, and the film of the present invention has molecular sieving ability.
上記結果より、本実施例における混合物分離膜は、分子径の大きいｉ−ブタンと分子径の小さいヘリウム、水素、二酸化炭素、酸素、窒素、メタン、ｎ−ブタンを効率よく分離できることが明らかとなった。 From the above results, it is clear that the mixture separation membrane in this example can efficiently separate i-butane having a large molecular diameter and helium, hydrogen, carbon dioxide, oxygen, nitrogen, methane, and n-butane having a small molecular diameter. It was.
実施例１８〜３３（使用例２〜１７）
実施例１〜１６で得られた分離膜を用いて、浸透気化（パーベーパレーション）法によりエタノール/水（５/９５ｗｔ％）混合溶液からエタノールを選択的に透過させる実験を７５℃でおこなった。
Examples 18 to 33 (Use Examples 2 to 17)
Using the separation membranes obtained in Examples 1 to 16, experiments were conducted at 75 ° C. to selectively permeate ethanol from an ethanol / water (5/95 wt%) mixed solution by the pervaporation method. .
比較例２
同様に、比較例１で得られたＭＦＩ型シリカライト膜を用いて、浸透気化（パーベーパレーション）法によりエタノール/水（５/９５ｗｔ％）混合溶液からエタノールを選択的に透過させる実験を７５℃でおこなった。
Comparative Example 2
Similarly, 75 experiments for selectively permeating ethanol from an ethanol / water (5/95 wt%) mixed solution by the pervaporation method using the MFI type silicalite membrane obtained in Comparative Example 1 were conducted. Performed at ℃.
測定に使用した装置の概略図を図６に示す。図６おいて、符号１は実施例１〜１６及び比較例１で調製したゼオライト分離膜である。このゼオライト分離膜１は、中空円筒形でありガラス容器９内に貯留された供給液２内に浸漬されている。供給液２は、エタノール/水（５／９５ｗｔ％）混合溶液であり、撹拌子４とスターラー５の作用によって攪拌される。ガラス容器９はさらに恒温槽６内に浸漬されており、温度調節装置７によって温度を一定に維持している。
ゼオライト分離膜１の上端部にはシリコンチューブ３が接続されており、このシリコンチューブ３はコールドトラップ１１を介して真空ポンプ１２を備える真空ライン１５に接続されている。
従って、ゼオライト分離膜１の内部は減圧されており、供給液２のうちゼオライト分離膜１を透過気化した蒸気はシリコンチューブ３を介してコールドトラップ１１に捕集されて液化する。
なお、ゼオライト分離膜１の底部から供給液２が侵入しないように栓１０によって塞いでいる。また、真空ライン１５の真空度は真空計１４によって測定されている。Ｎ２ガス１３は、真空ライン１５を常圧に戻すリーク時に封入される。空気を吸入すると水蒸気が混入するため、Ｎ２ガス１３を用いるものである。
A schematic diagram of the apparatus used for the measurement is shown in FIG. In FIG. 6, reference numeral 1 denotes a zeolite separation membrane prepared in Examples 1 to 16 and Comparative Example 1. The zeolite separation membrane 1 has a hollow cylindrical shape and is immersed in a supply liquid 2 stored in a glass container 9. The supply liquid 2 is an ethanol / water (5/95 wt%) mixed solution, and is stirred by the action of the stirring bar 4 and the stirrer 5. The glass container 9 is further immersed in the thermostatic bath 6, and the temperature is maintained constant by the temperature control device 7.
A silicon tube 3 is connected to the upper end of the zeolite separation membrane 1, and the silicon tube 3 is connected to a vacuum line 15 including a vacuum pump 12 via a cold trap 11.
Accordingly, the inside of the zeolite separation membrane 1 is decompressed, and the vapor permeated through the zeolite separation membrane 1 in the supply liquid 2 is collected in the cold trap 11 via the silicon tube 3 and liquefied.
The feed liquid 2 is blocked by a plug 10 so as not to enter from the bottom of the zeolite separation membrane 1. The degree of vacuum of the vacuum line 15 is measured by a vacuum gauge 14. The N 2 gas 13 is enclosed at the time of a leak that returns the vacuum line 15 to normal pressure. Since water vapor is mixed when air is inhaled, N 2 gas 13 is used.
供給液２とコールドトラップ１１で捕集された透過物の組成はガスクロマトグラフにより測定し、膜の透過性能は単位面積、単位時間あたりの全透過量Ｑ（ｋｇ／ｍ２ｈ）と下記式で定義する分離係数αにより評価した。 The composition of the permeate collected by the supply liquid 2 and the cold trap 11 is measured by gas chromatography, and the permeation performance of the membrane is expressed in terms of unit area, total permeation amount Q (kg / m 2 h) per unit time and the following formula. It was evaluated by the separation factor α defined.
（式中、ＦＡ、ＦＢはそれぞれ供給液中の液体Ａ、Ｂの平均濃度（ｗｔ％）であり、ＰＡ、ＰＢはそれぞれ透過物中のＡ、Ｂの平均濃度（ｗｔ％）である。） (In the formula, F A and F B are the average concentrations (wt%) of the liquids A and B in the supply liquid, respectively, and P A and P B are the average concentrations (wt%) of A and B in the permeate, respectively. .)
実施例１〜１６で調製した分離膜、及び比較例１で調製したＭＦＩ型シリカライト膜の、処理温度７５℃におけるエタノール/水（５/９５ｗｔ％）混合溶液中のエタノールに対する全透過量Ｑ（ｋｇ／ｍ２ｈ）及び分離係数αを表１に示す。 The total permeation amount Q for ethanol in the ethanol / water (5/95 wt%) mixed solution of the separation membranes prepared in Examples 1 to 16 and the MFI type silicalite membrane prepared in Comparative Example 1 at a treatment temperature of 75 ° C. kg / m 2 h) and the separation factor α are shown in Table 1.
表１において、比較例２として示したＭＦＩ型シリカライト膜による分離性能は、全透過量Ｑが１．６で分離係数αが４２である。これに対して実施例１８から実施例３３として示したチタノシリケート型ゼオライト膜による分離性能は、様々な値が示されている。
今回の実験で分離係数αが大きい場合には、水とエタノールに対してより高い分離能を備えていると言えるが、その際には相対的に全透過量Ｑが小さいという傾向がある。実施例１８乃至３３では、比較例２のＱとαに対していずれも上回る値を有する結果は得られなかった。
しかしながら、実施例１８乃至３３で比較してみると、分離係数αが１であるもの、すなわち分離膜として機能していないものを除くと、優劣が見受けられる。例えば、最も大きな分離係数αを示した実施例２４の結果では、全透過量Ｑもこれらの実施例の中で２番目に大きな値を示している。
最も大きな全透過量Ｑを有する実施例２０では、分離係数αが６６と実施例２４の１２７の半数程度となっているため、今回の実施例の中では実施例２４の結果から実施例７で調製された膜が最も分離性能に優れているということが理解される。
また、実施例１８乃至３３を比較例２と比較した場合、分離係数αが１であるものを除けば、いずれも分離係数αは大きくなっており、本実施の形態に係る混合物分離膜は高いエタノール選択透過性を示し、エタノール/水混合液を効率よく分離できることが確認された。
また、これらの実施例から本実施の形態に係る混合物分離膜の製造方法においても、優れた分離性能を備えた混合物分離膜を提供することができるという効果を確認することができた。
In Table 1, the separation performance of the MFI type silicalite membrane shown as Comparative Example 2 is that the total permeation amount Q is 1.6 and the separation factor α is 42. On the other hand, various values are shown for the separation performance of the titanosilicate zeolite membranes shown as Examples 18 to 33.
In this experiment, when the separation factor α is large, it can be said that the water and ethanol have higher separation ability, but in this case, the total permeation amount Q tends to be relatively small. In Examples 18 to 33, a result having values exceeding both Q and α of Comparative Example 2 was not obtained.
However, when comparing Examples 18 to 33, superiority or inferiority is observed except for those having a separation coefficient α of 1, that is, those not functioning as a separation membrane. For example, in the results of Example 24 showing the largest separation coefficient α, the total transmission amount Q also shows the second largest value in these examples.
In the example 20 having the largest total permeation amount Q, the separation coefficient α is 66, which is about half of 127 of the example 24. Therefore, in this example, the result of the example 24 is used in the example 7. It is understood that the prepared membrane has the best separation performance.
In addition, when Examples 18 to 33 are compared with Comparative Example 2, except that the separation factor α is 1, the separation factor α is high, and the mixture separation membrane according to the present embodiment is high. It was confirmed that ethanol selective permeability was exhibited and the ethanol / water mixture could be separated efficiently.
Moreover, in the manufacturing method of the mixture separation membrane which concerns on this Embodiment from these Examples, the effect that the mixture separation membrane provided with the outstanding separation performance was able to be provided has been confirmed.
本発明に係る混合物分離膜の製造方法は、多種多様の気体混合物あるいは液体混合物の分離に利用できる。さらに、チタンの触媒作用とこの混合物分離膜の作用の両方を利用して、触媒反応前の反応物から触媒反応後の生成物を分離することが可能であるので、単に複数の種類の混合物を分離するだけでなく、触媒反応生成物を抽出するような化学反応システムなどにも利用可能である。 The method for producing a mixture separation membrane according to the present invention can be used for separation of a wide variety of gas mixtures or liquid mixtures. Furthermore, it is possible to separate the product after the catalytic reaction from the reaction product before the catalytic reaction by utilizing both the catalytic action of titanium and the action of the mixture separation membrane. It can be used not only for separation but also for a chemical reaction system for extracting a catalytic reaction product.
１…ゼオライト分離膜 ２…供給液 ３…シリコンチューブ ４…撹拌子 ５…スターラー ６…恒温槽 ７…温度調節装置 ８…冷却管 ９…ガラス容器 １０…栓 １１…コールドトラップ １２…真空ポンプ １３…Ｎ２ガス １４…真空計 １５…真空ライン DESCRIPTION OF SYMBOLS 1 ... Zeolite separation membrane 2 ... Supply liquid 3 ... Silicon tube 4 ... Stirrer 5 ... Stirrer 6 ... Constant temperature bath 7 ... Temperature control device 8 ... Cooling tube 9 ... Glass container 10 ... Plug 11 ... Cold trap 12 ... Vacuum pump 13 ... N 2 gas 14 ... Vacuum gauge 15 ... Vacuum line
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| JP7090278B2 (en) * | 2018-03-07 | 2022-06-24 | 日立造船株式会社 | CHA type titanosilicate separation membrane and its manufacturing method, and gas separation method |
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| KR20180085066A (en) | 2014-07-18 | 2018-07-25 | 토소가부시키가이샤 | Composition including silicotitanate having sitinakite structure, and production method for same |
| US10343136B2 (en) | 2014-07-18 | 2019-07-09 | Tosoh Corporation | Composition including silicotitanate having sitinakite structure, and production method for same |
| EP3556729A1 (en) | 2014-07-18 | 2019-10-23 | Tosoh Corporation | Use of a composition comprising silicotitanate having sitinakite structure and niobium |
| US11471855B2 (en) | 2014-07-18 | 2022-10-18 | Tosoh Corporation | Adsorption method for at least one of cesium and strontium employing silicotitanate having sitinakite structure |
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