CN103476487A - Method for producing water-impermeable ceramic separation membrane, and ceramic separation membrane obtained by method for producing water-impermeable ceramic separation membrane - Google Patents
Method for producing water-impermeable ceramic separation membrane, and ceramic separation membrane obtained by method for producing water-impermeable ceramic separation membrane Download PDFInfo
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- CN103476487A CN103476487A CN201280017967.XA CN201280017967A CN103476487A CN 103476487 A CN103476487 A CN 103476487A CN 201280017967 A CN201280017967 A CN 201280017967A CN 103476487 A CN103476487 A CN 103476487A
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- ceramic separation
- perforated membrane
- silicon compound
- separation film
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- 238000000926 separation method Methods 0.000 title claims abstract description 148
- 239000000919 ceramic Substances 0.000 title claims abstract description 134
- 239000012528 membrane Substances 0.000 title claims abstract description 124
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 76
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 78
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 63
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 49
- 238000009835 boiling Methods 0.000 claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 95
- 238000000034 method Methods 0.000 claims description 81
- 239000011148 porous material Substances 0.000 claims description 51
- 239000000758 substrate Substances 0.000 claims description 45
- 239000006185 dispersion Substances 0.000 claims description 38
- 239000011737 fluorine Substances 0.000 claims description 26
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 238000004458 analytical method Methods 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- -1 silanes organic compounds Chemical class 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 150000001721 carbon Chemical group 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000004611 spectroscopical analysis Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 48
- 238000010438 heat treatment Methods 0.000 abstract description 18
- 230000035699 permeability Effects 0.000 abstract description 17
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 29
- 239000000463 material Substances 0.000 description 28
- 239000007788 liquid Substances 0.000 description 26
- 239000007789 gas Substances 0.000 description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 20
- 150000003377 silicon compounds Chemical class 0.000 description 19
- 239000002904 solvent Substances 0.000 description 19
- 125000004429 atom Chemical group 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
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- 238000009792 diffusion process Methods 0.000 description 13
- 150000002431 hydrogen Chemical class 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 11
- 229910010293 ceramic material Inorganic materials 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- 239000000395 magnesium oxide Substances 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
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- 239000012298 atmosphere Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 229910010271 silicon carbide Inorganic materials 0.000 description 9
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- 150000001875 compounds Chemical class 0.000 description 8
- 238000003618 dip coating Methods 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 229910052581 Si3N4 Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 5
- 229910017083 AlN Inorganic materials 0.000 description 4
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
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- 229910004298 SiO 2 Inorganic materials 0.000 description 3
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- 238000012937 correction Methods 0.000 description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000002270 dispersing agent Substances 0.000 description 3
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 150000002221 fluorine Chemical class 0.000 description 3
- 229910052863 mullite Inorganic materials 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
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- 238000007789 sealing Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 230000000254 damaging effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001962 electrophoresis Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052839 forsterite Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 238000007603 infrared drying Methods 0.000 description 2
- 229910003471 inorganic composite material Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- LPESKBWMHLKTMU-UHFFFAOYSA-N CP(=O)OCCC(O)=O Chemical compound CP(=O)OCCC(O)=O LPESKBWMHLKTMU-UHFFFAOYSA-N 0.000 description 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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- 229910018540 Si C Inorganic materials 0.000 description 1
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- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
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- 230000006837 decompression Effects 0.000 description 1
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
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- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
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- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 239000004575 stone Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- SVKDNKCAGJVMMY-UHFFFAOYSA-N triethoxy(tetradecyl)silane Chemical compound CCCCCCCCCCCCCC[Si](OCC)(OCC)OCC SVKDNKCAGJVMMY-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0083—Thermal after-treatment
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- 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
- B01D69/04—Tubular membranes
Abstract
Provided is a method for producing a ceramic separation membrane which has a good balance between water impermeability and gas permeability at a high level. This method for producing a ceramic separation membrane comprises: formation of a ceramic porous membrane on the surface of a porous base; application of at least a fluorine atom-containing organosilicon compound over the porous membrane; and a heat treatment of the porous membrane, to which the organosilicon compound has been applied, at a temperature that is not less than the boiling point of the organosilicon compound. Consequently, fluorine atoms derived from the organosilicon compound are left at least on the surface of the porous membrane.
Description
Technical field
The present invention relates to the manufacture method of ceramic separation film of water-impermeable and the ceramic separation film made by this manufacture method.The manufacture method that particularly relates to the pottery gas separation membrane processed of the water-impermeable that water (comprising steam) is separated with gas (such as hydrogen, oxygen, nitrogen etc.).
Wherein, the application advocates the priority of No. 2011-087685, the Japanese patent application that proposes on April 11st, 2011, and the full content of this Japanese publication is quoted in this manual with for referencial use.
Background technology
Diffusion barrier normally has the perforated membrane of a plurality of pores, by the size (aperture) of regulating this pore, can be separated gas or liquid, make with extra care or absorption.Therefore, this diffusion barrier be take industrial circle as representative extensive use in each field.Wherein, this diffusion barrier, because its material can be divided into organic separation membrane and inorganic separating film, has respectively different character.
Organic separation membrane consists of macromolecular material.Therefore there is water-impermeable, such as being suitable for, water (comprising steam) is separated with desirable gas (such as hydrogen, oxygen, nitrogen etc.), to obtain highly purified gas.As an illustration, the diffusion barrier consisted of Kynoar (PVDF), polytetrafluoroethylene (PTFE) is for example disclosed in non-patent literature 1.But the heat resistance of this organic separation membrane and resistance to chemical reagents deficiency, therefore be difficult to use in hot environment or in being exposed to the such environment of various medicines, its purposes is restricted.On the other hand, inorganic separating film is by the inorganic porous materials such as the pottery (aluminium oxide (Al with a plurality of pores
2o
3), silica (SiO
2) etc.) form.This inorganic separating film, by the size (aperture) of controlling this pore, can optionally carry out the separation of compound etc. or absorption etc.In addition, due to heat resistance and the above-mentioned organic separation membrane excellence of resistance to chemical reagents geometric ratio of inorganic separating film, therefore can in various environment, use.But the inorganic separating film consisted of inorganic material is generally hydrophilic, has water permeability, so be difficult to as described organic separation membrane, water be separated with desirable gas.
Therefore, (for example under hot environment or be exposed under the environment of various medicines) separates water diffusion barrier with desirable gas is developed and can be suitable under environment widely in expectation.Therefore, the exploitation of technology of making the ceramic separation film of water-impermeable by the surperficial hydrophobic property to inorganic separating film in recent years progressively makes progress (patent documentation 1～3).For example, disclose in non-patent literature 2 and utilized organochlorosilane the surface of the inorganic separating film that consists of gama-alumina to be modified and the ceramic separation film of the water-impermeable that obtains.
Technical literature formerly
Patent documentation
Patent documentation 1: the flat 02-31824 communique of Japanese Patent Application Publication
Patent documentation 2: Japanese Patent Application Publication 2002-263456 communique
Patent documentation 3: Japanese Patent Application Publication 2006-519095 communique
Non-patent literature
Non-patent literature 1:Mark Stuart.Using Hydrophobic Membranes to Protect Gas Sensors.[online] .Sensors ARTICLE ARCHIVES, May1998.[retrieved on 2010-08-23] .Retrieved from the Internet:<http://archives.sensorsmag.com/articles/0598/gas0598/index.htm >
Non-patent literature 2:Journal of membrane science243 (2004) 125-132
Summary of the invention
As mentioned above, in order to manufacture the ceramic separation film of water-impermeable, the method for utilizing organic compound to be modified the surface of ceramic separation film is general method.But, while utilizing this method to make ceramic separation film, the pore sometimes formed on this ceramic separation film can be stopped up by organic compound.In this case, may cause the gas-premeable of ceramic separation film to descend, reduce as the disposal ability of diffusion barrier.That is, in existing ceramic separation film, water-impermeable and gas-premeable have the relation of balance (trade-off), and the method that has both the ceramic separation film of these two kinds of character with high level of making is developed in expectation.
The present invention completes in view of the above problems, its purpose be to provide a kind of manufacture heat resistance and resistance to chemical reagents excellent and have both the method for the ceramic separation film of water-impermeable and gas-premeable with high level.And the invention provides on the other hand, a kind of ceramic separation film of the water-impermeable made by this manufacture method.
To achieve these goals, the invention provides a kind of method of manufacturing the ceramic separation film (following taking the circumstances into consideration referred to as " ceramic separation film ") of water-impermeable.Manufacture method disclosed herein is characterised in that, comprising: (A) on the surface of porous substrate, form the step of the perforated membrane of pottery system, the perforated membrane of this pottery system has the pore in a plurality of apertures that the gaseous species of regulation is separated; (B) give the step of the organo-silicon compound that at least contain fluorine atom on above-mentioned perforated membrane; (C) step that the temperature more than the boiling point of above-mentioned organo-silicon compound (typically being the temperature be above the boiling point) is heat-treated the perforated membrane of having given organo-silicon compound.And, at least remained on surface of above-mentioned perforated membrane, the fluorine atom from above-mentioned organo-silicon compound is arranged.
In manufacture method disclosed herein, give the organo-silicon compound that at least contain fluorine atom (following taking the circumstances into consideration referred to as " fluorine-containing organic silicon compound ", also only be called " organo-silicon compound " sometimes) on perforated membrane.Fluorine atom from this organo-silicon compound can exist (residual) in the surface of perforated membrane with the state with hydrophobic compound (or characteristic group).Therefore, according to manufacture method disclosed herein, the surface of perforated membrane can be given with suitable hydrophobicity, the ceramic separation film of water-impermeable can be manufactured.And, in manufacture method disclosed herein, the temperature more than the boiling point of these organo-silicon compound is heat-treated the perforated membrane of giving after the fluorine-containing organic silicon compound.Thus, can remove this organo-silicon compound with the degree of not damaging effect of the present invention, the pore that therefore can suppress on perforated membrane is stopped up by organo-silicon compound.Therefore, according to manufacture method disclosed herein, can access the ceramic separation film of the gas-premeable that remains high.
That is,, according to manufacture method disclosed herein, can manufacture with high level and have both and there is the water-impermeable of balance relation and the ceramic separation film of gas-premeable in existing ceramic separation film.
In a kind of preferred embodiment of manufacture method disclosed herein, every 1 molecule of above-mentioned organo-silicon compound has the carbon atom more than 10.And, above-mentioned carbon number (N
c) with respect to above-mentioned number of fluorine atoms (N
f) ratio (N
c/ N
f) be more than 0.5, below 2.And, above-mentioned silicon atom number (N
si) with respect to above-mentioned carbon number (N
c) ratio (N
si/ N
c) be more than 0.01, below 0.2.
Heat-treat by the organo-silicon compound to above-mentioned composition of proportions, can make the fluorine atom of appropriate amount remain at least surface of perforated membrane.Therefore, according to manufacture method disclosed herein, can give the surface of perforated membrane with suitable hydrophobicity, and then can manufacture the ceramic separation film of water-impermeable excellence.
In a preferred embodiment of manufacture method disclosed herein, above-mentioned organo-silicon compound are the silanes organic compounds that contain fluorine-based or perfluor base.
Contain organo-silicon compound fluorine-based or the perfluor base, can suitably on perforated membrane, give fluorine atom.And, because the bonding force of above-claimed cpd and perforated membrane (pottery) is stronger, thus can be after heat treatment the fluorine atom of residual right quantity.
In a preferred embodiment of manufacture method disclosed herein, above-mentioned perforated membrane is aluminium oxide (alumina:Al
2o
3).
Aluminium oxide (alumina) comparatively cheapness and operability excellence in porous material.And, can form the loose structure with the aperture that is suitable for the gas separation, thereby can easily manufacture the ceramic separation film with excellent gas-premeable.Wherein, the chemical stability excellence of Alpha-alumina, have the characteristic that fusing point and mechanical strength are high.Therefore, by using Alpha-alumina, can manufacture the ceramic separation film that can for example, utilize widely in wide in range purposes (industrial circle).
In a preferred embodiment of manufacture method disclosed herein, above-mentioned heat treatment, based on energy dispersion type X ray optical spectroscopy (EDS(is also referred to as EDX): in analysis Energy Dispersive X-Ray Spectrometry), with respect to the aluminium atomicity 100 that forms above-mentioned perforated membrane, above-mentioned fluorine atom residues in the surface of above-mentioned perforated membrane with the ratio more than 1, below 10.
In this case, because the fluorine atom of right quantity residues in the surface of perforated membrane, so can not stop up the pore (being that former state keeps high gas-premeable) of perforated membrane, compared with prior art, can improve the hydrophobicity of this perforated membrane.
In a preferred embodiment of manufacture method disclosed herein, by above-mentioned heat treated Temperature Setting, be (preferably more than 300 ℃) more than 200 ℃.This temperature typically is more than 200 ℃, typically is the low temperature (for example, below 700 ℃) of temperature be not completely removed than organo-silicon compound.
In above-mentioned heat treated temperature, during far below 200 ℃, the organo-silicon compound of giving can not be removed fully, cause sometimes the pore on perforated membrane to stop up.In this case, may cause intrinsic functional (typically being high gas-premeable) of ceramic separation film of acquisition to be reduced.On the other hand, much larger than 700 ℃ the time, organo-silicon compound are gasified totally, and may cause the deleterious of manufacture method disclosed herein.Therefore, by making heat treatment temperature in above-mentioned scope, can suitably from the surface of perforated membrane, remove organo-silicon compound.Therefore, can realize effect of the present invention (that is, make high gas-premeable and water-impermeable and deposit) with high level.More preferably above-mentioned heat treated Temperature Setting is (for example more than 350 ℃, below 650 ℃) more than 350 ℃.In this case, can manufacture and there is better water-impermeable (even for example applying 0.2MPa(2bar) following hydraulic pressure is also waterproof) ceramic separation film.
As on the other hand, the present invention also provides a kind of ceramic separation film of the water-impermeable made by any above-mentioned manufacture method.
The ceramic separation film made by above-mentioned any manufacture method, have both gas-premeable and water-impermeable with high level, broken above-mentioned balance relation.And this diffusion barrier consists of ceramic material, thereby heat resistance and resistance to chemical reagents excellence.Therefore can in wide in range purposes, utilize, for example, be suitable as the gas separation membrane that desirable gas is separated with water (comprising steam).
In a preferred embodiment of the ceramic separation film made by manufacture method disclosed herein, the average pore size obtained based on gas adsorption method is more than 0.3nm, below 100 μ m.
In the average pore size of ceramic separation film, during much smaller than 0.3nm, gas-premeable may reduce.On the other hand, in average pore size, during much larger than 100 μ m, even by manufacture method disclosed herein, the surface of perforated membrane has been given in hydrophobic situation, also may cause water-impermeable to reduce.Therefore, preferably the average pore size of the pore of perforated membrane is set in above-mentioned number range.Wherein, in this manual, except the situation of special instruction, " average pore size " is based on the measured value of the existing known gas adsorption method that uses nitrogen (or argon).In this is measured, pore is illustrated in the perforate of external opening, does not comprise the space (closed pore) of sealing.In addition, in this manual, " porosity (%) " means the pore volume (Vb(cm recorded by said determination
3)) divided by apparent volume (Va(cm
3)) be multiplied by again 100 and the value (Vb/Va * 100(%) calculated).Area S when wherein, apparent volume Va can be by the overlooking of this sample and the integrating of thickness T go out.
The accompanying drawing explanation
Fig. 1 is an illustrative figure who schematically shows the ceramic separation film made by manufacture method of the present invention.
Fig. 2 means the figure of the energy dispersion type X ray spectrum analysis spectrum of sample 1.
Fig. 3 A is the SEM photo in cross section of the Alpha-alumina film of sample 1.
Fig. 3 B means the result of SEM-EDS distributional analysis (mapping) of the distribution of carbon atom in Fig. 3 A (C).
Fig. 3 C means the result of SEM-EDS distributional analysis of the distribution of oxygen atom in Fig. 3 A (O).
Fig. 3 D means the result of the SEM-EDS distributional analysis of the distribution of aluminium atom (Al) in Fig. 3 A.
Fig. 4 means the curve map of permeability of the ceramic separation film of sample 1 and sample 5.
Fig. 5 means the figure of the result that the TG-DTA of sample 1 measures.
The specific embodiment
Below, the preferred embodiment of the present invention is described.Wherein, beyond the item of mentioning especially in this manual and be the necessary item of enforcement of the present invention, can be understood as the design item of the ability technical staff based on the state of the art.The present invention can the technology general knowledge based on the disclosed content of this specification and this area implement.
The structure of<ceramic separation film>
With reference to Fig. 1, an illustration of the ceramic separation film that made by manufacture method disclosed herein is described.Ceramic separation film 20 disclosed herein is water-impermeable, is formed on the surface of porous substrate 10.Below, also ceramic separation film 20 is called together with porous substrate 10 to membrane component 1.This ceramic separation film 20(membrane component 1) there are a plurality of pores with gaseous species aperture of separating that will regulation, for example therefore can be used in from the mixture of water (comprising steam) and gas and separate purpose gas.At this, as the gas of above-mentioned separation purpose, for example can enumerate hydrogen (H
2), nitrogen (N
2), oxygen (O
2) etc.
As the material of the perforated membrane that forms ceramic separation film 20, can from existing known ceramic material, suitably select.For example, can use aluminium oxide (alumina:Al
2o
3), zirconia (zirconia:ZrO
2), magnesia (magnesia:MgO), silica (silica:SiO
2), titanium oxide (titania:TiO
2), cerium oxide (ceria:CeO
2), yittrium oxide (yttria:Y
2o
3), barium titanate (BaTiO
3) etc. oxide material; Cordierite (2MgO2Al
2o
35SiO
2), mullite (3Al
2o
32SiO
2), forsterite (2MgOSiO
2), steatite (MgOSiO
2), sialon (Sialon, Si
3n
4al
2o
3), zircon (ZrO
2siO
2), ferrite (ferrite) (M
2oFe
2o
3) etc. the combined oxidation composition material; Silicon nitride (silicon nitride:Si
3n
4), the nitride-based materials such as aluminium nitride (aluminum nitride:AlN); The carbon compound materials such as carborundum (Silicon Carbide:SiC); The hydroxide composition materials such as hydroxyapatite; The element class materials such as carbon (C), silicon (Si); Perhaps contain their two or more inorganic composite materials etc.Can also use natural minerals (clay, clay mineral, grog, silica sand, pottery stone, feldspar, white sand) or blast-furnace slag, flying dust etc.
Wherein, be preferably selected from aluminium oxide (α ?alumina, γ ?alumina), one kind or two or more in zirconium dioxide (zirconia), titanium oxide (titania), magnesia (magnesia), silica (silica), mullite, cordierite, carborundum (Silicon Carbide) and silicon nitride (silicon nitride), more preferably using the ceramic powders that aluminium oxide or silica forms as main body.Wherein, said " as main body " means that 50 overall quality % of ceramic powders above (preferably 75 quality % above, more preferably 80 quality %～100 quality %) are aluminium oxide or silica here.
For example, in porous material, aluminium oxide (alumina) is cheapness and operability excellence comparatively.And, can easily form the loose structure with the aperture that is suitable for the gas separation, therefore can easily manufacture the ceramic separation film with excellent gas-premeable.And, in above-mentioned aluminium oxide, particularly preferably use Alpha-alumina.Alpha-alumina has aspect chemical to be stablized and fusing point and the high characteristic of mechanical strength.Therefore, by using Alpha-alumina, can manufacture the ceramic separation film that can for example, utilize in wide in range purposes (industrial circle).
As mentioned above, ceramic separation film 20 has a plurality of pores of the size that the gaseous species of regulation is separated.The aperture of this pore (average pore size) is not particularly limited, and for example can set the molecular diameter that makes it be greater than the molecular diameter of the gas (forming the molecule of gas) as separate object and be less than other molecules.Like this, by controlling ceramic separation film 20(, typically be the perforated membrane that forms this ceramic separation film) average pore size, can only make the gaseous species (separate object) of regulation pass through.For example,, from containing hydrogen (H
2) mixture in separate in the situation of this hydrogen (molecular diameter: 0.289nm left and right), more than preferably the average pore size of perforated membrane being set as to 0.3nm, below 100 μ m (preferably the above 100nm of 0.3nm following, more preferably below the above 1nm of 0.3nm).By making average pore size in above-mentioned scope, can realize effect of the present invention (that is, high gas-premeable and water-impermeable deposit) with high level.
In addition, the porosity of ceramic separation film 20 also is not particularly limited, can be according to the appropriate changes such as gaseous species as separate object.For example, while stating hydrogen in separation, preferably by the porosity of perforated membrane, be set as more than 10%, (preferably more than 20% below 60%, more preferably more than 30% below 50%) below 75%.In the situation that there is the porosity in this number range, owing to thering is suitable water-impermeable and gas-premeable preferably.
The shape of ceramic separation film 20 is not particularly limited, and can adopt various shapes according to the shape of the membrane component (ceramic separation film) of purpose and the shape of porous substrate described later.For example, can enumerate tubulose (cylindric), all lateral vertical of cylinder ground is flattened to flat tubulose (hollow flat shape), dull and stereotyped (thin plate) shape, the hollow box shape obtained or there is the cylindric etc. of honeycomb structure.Wherein, the membrane component 1 of the structure shown in Fig. 1 is tubulose, in the mode of the outer peripheral face 10a that covers porous substrate 10, forms ceramic separation film 20.
The thickness of this ceramic separation film 20 is not particularly limited, and can be for example (typically be the above 10 μ m of 10nm are following, preferably the above 5 μ m of 50nm are following, more preferably the above 3 μ m of 100nm are following) below 10 μ m.Ceramic separation film 20 with thickness of above-mentioned number range has suitable water-impermeable and gas-premeable, so preferably.
The surface of ceramic separation film disclosed herein (perforated membrane) 20 exists the fluorine atom from the fluorine-containing organic silicon compound.At this, " surface of ceramic separation film (perforated membrane) " be not only refer to ceramic separation film (perforated membrane) the part of protruding most (, the longest part of length on thickness direction), refer to the zone of the inside (the particularly near surface zone of the inside of ceramic separation film (perforated membrane)) that comprises ceramic separation film (perforated membrane).
Above-mentioned fluorine atom, from the fluorine-containing organic silicon compound, can be present in the state with hydrophobic compound (or characteristic group) surface of ceramic separation film.So, by this fluorine atom (compound that contains fluorine atom or characteristic group), give the surface of ceramic separation film with hydrophobicity.This fluorine atom is so long as from organo-silicon compound, just be not particularly limited, such as being present in the surface of ceramic separation film with the compound by above-mentioned organo-silicon compound thermal decomposition is generated or with the state that forms characteristic group that ceramic metallic atom be combined etc.
The number of fluorine atoms that is present in the surface of ceramic separation film, with respect to the pottery that forms above-mentioned ceramic separation film, contained metallic atom (being the Al atom when aluminium oxide) is several 100, is preferably more than 0.1 (for example more than 0.1 below 100, preferably more than 1 below 50, more preferably more than 1 below 10).If with respect to pottery, contained metallic atom is several 100 as mentioned above, fluorine atom at least exists with the ratio more than 0.1, just can give the surface of ceramic separation film with hydrophobicity.Wherein, above-mentioned atomicity can have known energy dispersion type X ray optical spectroscopy (EDS:Energy Dispersive X-Ray Spectrometry) now by use, for example scanning electron microscope (SEM:Scanning Electron Microscope)-EDS is resolved (analysis) and determines.In this case, typically, for the characteristic X-ray intensity of standard of comparison material and determination object thing and the relative intensity obtained, enforcement relates to atomic number effect correction (Z), absorbs the correction of revising (A) and these three factors of fluorescence excitation correction (F), carries out quantitative (the ZAF corrected Calculation method) of atom.In this manual, also can adopt and carry out the value that this modification calculates.
In addition, on the surface of ceramic separation film, except above-mentioned fluorine atom, can also there be carbon atom (C), oxygen atom (O), silicon atom (Si) etc.With respect to pottery, contained metallic atom is several 100, and carbon number can be for example (preferably more than 400 below 500, more preferably 450 ± 25) more than 300, below 600.In addition, with respect to pottery, contained metallic atom is several 100, and oxygen atomicity can be for example (preferably more than 100 below 250, more preferably 175 ± 25) more than 50, below 300.And contained metallic atom is several 100 with respect to pottery, the silicon atom numerical example for example, as be (more than 0.1 below 100, preferably more than 1 below 50) more than 0.1.There is the ceramic separation film on the surface formed with above-mentioned ratio, can bring into play excellent hydrophobicity, so preferably.
As porous substrate 10, can from existing known inorganic substrate, suitably select according to purposes, can be typically pottery or metal.More specifically, can use aluminium oxide (alumina:Al
2o
3), zirconia (zirconia:ZrO
2), magnesia (magnesia:MgO), silica (silica, silica: SiO
2), titanium oxide (titania:TiO
2), cerium oxide (ceria:CeO
2), yittrium oxide (yttria:Y
2o
3), barium titanate (BaTiO
3) etc. oxide material; Cordierite (2MgO2Al
2o
35SiO
2), mullite (3Al
2o
32SiO
2), forsterite (2MgOSiO
2), steatite (MgOSiO
2), sialon (Si
3n
4al
2o
3), zircon (ZrO
2siO
2), ferrite (M
2oFe
2o
3) etc. the combined oxidation composition material; Silicon nitride (silicon nitride:Si
3n
4), the nitride-based material such as aluminium nitride (aluminum nitride:AlN); The carbon compound materials such as carborundum (Silicon Carbide:SiC); The hydroxide composition materials such as hydroxyapatite; The element class materials such as carbon (C), silicon (Si); Perhaps contain their two or more inorganic composite materials etc.; , as metal materials such as the illustrative ceramic material of the material of perforated membrane 20 or aluminium (Al), iron (Fe) etc., more preferably use ceramic material (typically being aluminium oxide, for example Alpha-alumina).
For example, and more preferably porous substrate 10 pottery of the same race by the pottery with forming above-mentioned ceramic separation film (perforated membrane) 20 forms (using ceramic powder of the same race to make).In this case, porous substrate 10 improves with the zygosity of the interface of ceramic separation film 20, can access the membrane component 1 that durability is more excellent.
The size of the pore (through hole) formed in porous substrate 10, be preferably greater than the pore formed in above-mentioned ceramic separation film 20.More specifically, can make average pore size for 0.1 μ m for example is above, 10 μ m following (preferably the above 1 μ m of 0.1 μ m following, more preferably 0.5 μ m ± 0.3 μ m) left and right.During much smaller than 0.1 μ m, be difficult to the characteristic (for example gas separating property) of performance as ceramic separation film in the average pore size of porous substrate.On the other hand, in above-mentioned average pore size, during much larger than 100 μ m, mechanical strength may be not enough.Therefore, the average pore size of preferred porous substrate is in above-mentioned scope.In addition, due to same reason, the porosity of porous substrate can for for example more than 10%, (preferably more than 20% below 60%, more preferably more than 30% below 50%) below 75% left and right.
The shape of porous substrate 10 can adopt various shapes according to the shape of the membrane component (ceramic separation film) of purpose.For example, can enumerate tubulose (cylindric), all lateral vertical of cylinder ground is flattened to flat tubulose (hollow flat shape), dull and stereotyped (thin plate) shape, the hollow box shape obtained or there is the cylindric etc. of honeycomb structure.Wherein, in the membrane component 1 of structure shown in Fig. 1, use the porous substrate 10 of tubulose.
The porous substrate 10 of desired shape can be used commercially available product, can be also the base material adopted such as existing known forming technique (mould molding, cold isostatic compaction (cold isostatic pressing), extrusion molding, injection moulding, cast molding, extrusion forming etc.) or burning techniques manufacture.For example, when using ceramic material as the material of porous substrate, at first make pulverous inorganic porous material (ceramic material) and adhesive be evenly dispersed in solvent, thereby prepare the dispersion liquid of pulp-like (comprising paste, ink-like).Wherein, the dispersion liquid of this pulp-like can contain the additives such as dispersant or surfactant as required.Then, use above-mentioned forming technique, the dispersion liquid of pulp-like is shaped to the shape of expection.Then, by this formed body with typically for the additive of acceleration of sintering (for example, for Al
2o
3for MgO, SiO
2, or for Si
3n
4for Y
2o
3, Al
2o
3, MgO etc.) fired together, made its sintering and manufactured.
Typically being of above-mentioned inorganic porous material Powdered (granular), its particle diameter is not particularly limited.Can be for example (preferably 0.5 μ m above, more preferably more than 1 μ m), 50 μ m following (preferably 10 μ m are following, more preferably 5 μ m are following) more than 0.1 μ m.The material that meets above-mentioned scope can form densification and the more excellent porous substrate of durability.Wherein, in this manual, particle diameter means: in the size distribution of the volume reference recorded at the particle size distribution by based on laser diffraction-light scattering method, be equivalent to the average grain diameter (meso-position radius) of accumulation 50% from the particulate side.
The manufacture method of the ceramic separation film of<water-impermeable>
Then, the method (following taking the circumstances into consideration referred to as " manufacture method ") of the ceramic separation film of manufacturing this water-impermeable described.
Manufacture method disclosed herein is characterised in that, comprising: (A) on the surface of porous substrate, form the step had the perforated membrane of the pottery system of a plurality of pores in the aperture of the gaseous species of regulation separation; (B) give the fluorine-containing organic silicon compound on above-mentioned perforated membrane; (C) step that the temperature more than the boiling point of these organo-silicon compound is heat-treated the perforated membrane of having given above-mentioned organo-silicon compound.And, in manufacture method disclosed herein, at least remained on surface of above-mentioned perforated membrane, the fluorine atom from the fluorine-containing organic silicon compound is arranged.And only otherwise break away from purpose of the present invention, the operation beyond above-mentioned operation etc. can suitably be determined with reference to various benchmark.
A. the formation of perforated membrane
In manufacture method disclosed herein, at first, on the surface of porous substrate, form perforated membrane (ceramic separation film).The method that forms perforated membrane can adopt the whole bag of tricks used in existing known film forming technology.As the method, such as can enumerate dip coating, spin-coating method, scrape the skill in using a kitchen knife in cookery, screen painting method, sol-gel process, electrophoresis, spraying process etc.
When adopting dip coating as the formation method of perforated membrane, at first, preparation will form ceramic material (typically being Powdered) homodisperse dispersion liquid in solvent of perforated membrane.Then, the porous substrate that will have desirable shape floods certain hour in this dispersion liquid, afterwards this porous substrate is mentioned from dispersion liquid with certain speed.Wherein, during the porous substrate dipping, by the temperature by this dispersion liquid (and viscosity), keep constant, can form film with good repeatability.In addition, the dipping of porous substrate and mention and can vertically carry out with respect to the liquid level of dispersion liquid.In this method, the concentration by regulating the ceramic material (powder) in dispersion liquid and porous substrate mention speed etc., can control the thickness of perforated membrane.
As ceramic material, typically use the material of Powdered (granular).The particle diameter of this material is not particularly limited, typically can be for being less than the particle diameter as the material of above-mentioned porous substrate.Can be for example (preferably 0.1 μ m above, more preferably more than 0.5 μ m), 30 μ m following (preferably 7 μ m are following, more preferably 5 μ m are following) more than 0.01 μ m.Meet the material of above-mentioned scope, densification and mechanical strength are high, can form the perforated membrane that durability is more excellent.
As dispersion solvent, be not particularly limited, can use one kind or two or more in the solvent that can make above-mentioned ceramic material suitably disperse.This dispersion solvent can be used any one of mineral-type solvent, organic solvent.As the mineral-type dispersion solvent, the mixed solvent that preferred water or the water of take are main body.As the solvent beyond the water that forms this mixed solvent, for example, can suitably select can with the mixed uniformly organic solvent of water (lower alcohol, lower ketones etc.) in one kind or two or more.In addition, as the organic dispersion solvent, such as enumerating ether solvent, esters solvent, ketones solvent etc.The containing ratio of the solvent in this dispersion liquid is not particularly limited, and is preferably the above 50 quality % of 1 overall quality % of dispersion liquid following (typically being the above 35 quality % of 5 quality % following).
Other compositions (additives such as tackifier or dispersant) that can also add adhesive or can add arbitrarily in above-mentioned dispersion solvent as required.Adhesive or additive etc. are not particularly limited, and can in the manufacture of perforated membrane, from existing known material, suitably select.For example, as this adhesive, can enumerate the cellulose or derivatives thereofs such as CMC, hydroxyethylcellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, carboxymethyl cellulose, carboxyethyl cellulose, carboxyethyl methylphosphinate cellulose, cellulose, ethyl cellulose, methylcellulose, ethylhydroxyethylcellulose; Polyvinyl alcohol, modified polyvinylalcohol; Polytetrafluoroethylene (PTFE) etc.The containing ratio of adhesive etc. is not particularly limited, can be for more than 2 overall quality % of dispersion liquid, below 20 quality %.
As porous substrate, suitable choice for use in the material that can illustrate from above-mentioned " structure of ceramic separation film " according to purposes.
Then, after the dispersion liquid that is attached to this porous substrate surface being removed to (typically by drying, making its volatilization), carry out the suitable processing of firing, can form perforated membrane on the surface of porous substrate thus.
The removing of dispersion liquid can suitably be used existing known method (such as natural drying, heat drying, forced air drying, low humidity air-dry dry, vacuum drying, infrared drying, far infrared drying, utilize the drying of electron ray etc.).Particularly, for example can be at baking temperature below 200 ℃ (typically be more than 80 ℃ below 150 ℃, preferably more than 100 ℃ below 150 ℃) heat drying stipulated time (for example 0.5 hour～5 hours).
The condition of firing processing is not particularly limited, and for example firing temperature can be set as more than 1000 ℃ to (typically be more than 1000 ℃ below 2000 ℃, for example more than 1000 ℃ below 1500 ℃), will be set as the firing time more than 0.1 hour (typically be more than 0.5 hour below 10 hours, for example more than 1 hour below 5 hours) or more than 24 hours.Firing atmosphere is not particularly limited, for example can under oxidizing atmosphere, (typically be in atmosphere) or non-oxidizing atmosphere under (typically be nitrogen (N
2) or the atmosphere of the inactive gas such as argon (Ar) under) etc.And this is fired and can carry out fixing temperature is disposable, also can carry out stage by stage in different temperature.For example, can be warming up to 700 ℃～800 ℃ left and right, after this temperature is fired (maintenance) about 0.1 hour～0.5 hour, be warming up to 1000 ℃～1500 ℃ left and right, fire (maintenance) about 1 hour～5 hours.
B. organo-silicon compound gives
In manufacture method disclosed herein, then, on the surface of above-mentioned perforated membrane 20, give the fluorine-containing organic silicon compound.
The fluorine-containing organic silicon compound is the compound that at least contains fluorine atom (F), silicon atom (Si) and carbon atom (C) as used herein.Contain the silicon organic compound of (preferably basic framework (main chain) contains silicon) in structure, owing to for example, at high temperature (typically be more than 200 ℃, more than 300 ℃ below 600 ℃), issuing the heat-dissipating decomposition reaction, can be suitable for forming Si-Si key, Si-N key, the such key of Si-C key on the surface of above-mentioned perforated membrane.Therefore, can suitably fluorine atom contained in organo-silicon compound be added to the surface of perforated membrane.And, because the bonding force of above-claimed cpd and perforated membrane (pottery) is stronger, so, after heat treatment, can make fluorine atom suitably residual on this porous material surface.
The fluorine-containing organic silicon compound, can directly be used commercially available product as used herein, also can for example use the compound (typically making its polymerization) that contains above-mentioned constituting atom synthetic.Wherein, preferably use in every unimolecule the fluorine-containing organic silicon compound that contains carbon atom (C) more than 10 (for example more than 10 below 50, preferably more than 10 below 30, more preferably 20 ± 5).And, contain fluorine atom (F) more than 10 (for example more than 10 below 50, preferably more than 10 below 40, more preferably 25 ± 10) in preferred every unimolecule.And, contain silicon atom (Si) more than 1 (for example more than 1 below 50, typically be more than 1 below 10) in preferred every unimolecule.
Number of fluorine atoms (the N of above-mentioned fluorine-containing organic silicon compound
f) and carbon number (N
c) ratio (N
c/ N
f) can be (preferably more than 0.5 below 1.5, more preferably more than 0.5 below 1) more than 0.5, below 2.And, carbon number (N
c) and silicon atom number (N
si) ratio (N
si/ N
c) can be (preferably more than 0.01 below 0.08, more preferably 0.05 ± 0.02) more than 0.01, below 0.2.Heat-treat by the organo-silicon compound to above-mentioned composition of proportions, can make the fluorine atom of appropriate amount residue at least surperficial of perforated membrane.Therefore, by above-mentioned manufacture method, the surface of perforated membrane can be given with suitable hydrophobicity, the ceramic separation film of water-impermeable excellence can be manufactured.
Above-mentioned fluorine-containing organic silicon compound can be the silanes organic compound that contains fluorine-based or perfluor base.When using the silanes organic compound as organo-silicon compound, can suitably add fluorine atom on the surface of perforated membrane.And, because the bonding force of above-claimed cpd and perforated membrane (pottery) is stronger, so fluorine atom that can residual right quantity after heat treatment.
As the silanes organic compound, preferably there is the side chain that contains 1 above fluorine atom, more preferably there is the side chain (for example perfluor base) that contains 2 above fluorine atoms.As this silanes organic compound, for example, can enumerate 1H, 1H, 2H, 2H-perfluor dodecyl triethoxysilane (PFDTES:perfluorododecyl-1H, 1H, 2H, 2H-triethoxysilane:C
18h
19o
3f
21si), 1H, 1H, 2H, 2H-perfluor myristyl triethoxysilane (perfluorotetradecyl-1H, 1H, 2H, 2H-triethoxysilane:C
20h
19o
3f
25si), 1H, 1H, 2H, 2H-perfluoro hexyl trimethoxy silane, 1H, 1H, 2H, 2H-perfluoro capryl trimethoxy silane, 1H, 1H, 2H, 2H-perfluor decyl triethoxysilane, 3,3,3-trifluoro propyl trimethoxy silane etc.
In addition, the fluorine-containing organic silicon compound can be also the type siloxane organic compound.More preferably this type siloxane organic compound has the side chain that contains at least one fluorine atom, as the concrete example of type siloxane organic compound, can enumerate the polysiloxanes of perfluor polysiloxanes (perfluoropolysiloxane) etc.
The boiling point of fluorine-containing organic silicon compound is not particularly limited, and can be for example (preferably more than 100 ℃ below 300 ℃, more preferably more than 150 ℃ below 250 ℃) more than 100 ℃, below 400 ℃.The organo-silicon compound of boiling point in above-mentioned number range, in heat treatment described later, can be by suitably thermal decomposition of organo-silicon compound, thereby preferably use.Wherein, organo-silicon compound can be the states of the mixture that contains organic compound as described above as used herein.
As the method for giving the fluorine-containing organic silicon compound, can adopt existing known the whole bag of tricks, be not particularly limited.As such method, such as can adopt dip coating, spin-coating method, scrape the skill in using a kitchen knife in cookery, screen painting method, sol-gel process, electrophoresis, spraying process etc., wherein preferably adopt dip coating.Pass through the method, not only can on the surface of this perforated membrane, (part of protruding most) suitably give organo-silicon compound, and also can suitably give organo-silicon compound in pore, (typically being near the zone of inwall split shed section of this pore).
For example, when adopting dip coating as adding method, at first prepare to make above-mentioned organo-silicon compound be dispersed in the dispersion liquid in solvent.As solvent, for example can suitably use the solvent of record in above-mentioned " formation of perforated membrane ".And, in the limit that does not make effect of the present invention significantly worsen, can suitably add other compositions (additives such as adhesive, tackifier or dispersant) that can add arbitrarily.Then, the porous substrate that will be formed with perforated membrane for example, is mentioned with certain speed this porous substrate flood certain hour (typically be several minutes～tens of minutes, 1 minute～20 minutes) in this dispersion liquid after from dispersion liquid.During the porous substrate dipping, keep constant by the temperature by this dispersion liquid (and viscosity), can give organo-silicon compound with good repeatability.In addition, above-mentioned dipping and mention and can vertically carry out with respect to the liquid level of dispersion liquid.And, can be suitably and with operation that can facilitating impregnation (operations such as, decompression or heating) at this.And, remove (typically by heat drying, making its volatilization) by the dispersion solvent that will be attached to porous film surface, can give organo-silicon compound on the surface of perforated membrane.The method of removing of dispersion liquid can be same with above-mentioned " formation of perforated membrane ".
Wherein, in dip coating, by the concentration of regulating the organo-silicon compound in dispersion liquid or the speed of mentioning, dipping number of times etc., can control the amount (thickness) of the organo-silicon compound of giving.The higher amount of giving of every 1 time of the concentration of general its solution is more, and it is fewer to mention the lower amount of giving of every 1 time of speed.And dipping number of times and the substantially proportional relation of the amount of giving, can be by the amount of giving of every 1 time and the always amount of giving of estimation of amassing of dipping number of times.This amount of giving is not particularly limited, and for example can give the thickness that makes this organo-silicon compound layer is that 1nm is above, 1000nm following (preferably the above 100nm of 1nm is following, more preferably the above 50nm of 1nm is following) left and right.Thus, for the organo-silicon compound of bringing into play hydrophobic appropriate amount, be imparted into perforated membrane, after heat treatment, also can make the fluorine atom of right quantity residue on perforated membrane.Wherein, this thickness for example can be determined by the cross section that utilizes general electron microscope (typically being transmission electron microscope) to observe perforated membrane.
C. heat treatment
In manufacture method disclosed herein, then, the temperature that (typically is the temperature be above the boiling point) more than the boiling point of organo-silicon compound is heat-treated the perforated membrane of having given organo-silicon compound.Thus, can in the limit of not damaging effect of the present invention, remove this organo-silicon compound.The pore that therefore, can suppress on perforated membrane is stopped up by organo-silicon compound.
Above-mentioned heat treated temperature is carried out with the temperature (temperature that boiling point is above) of the boiling point of the fluorine-containing organic silicon compound higher than above-mentioned use.Therefore, such as can be according to the appropriate changes such as kind (boiling point) of the organo-silicon compound of giving.This heat treated temperature typically can be set as more than 200 ℃, preferably more than 250 ℃, more preferably more than 300 ℃.And, for example can be set as below 700 ℃, preferably below 650 ℃, more preferably below 600 ℃.In this case, can suitably organo-silicon compound be removed from the surface of perforated membrane.
And, by the above-mentioned heat treated temperature of further raising, the surface that can give perforated membrane is with gas-premeable more suitably.For example, using 1H, 1H, 2H, 2H-perfluor dodecyl triethoxysilane is during as organo-silicon compound, for example, by by above-mentioned heat treated Temperature Setting being more than 350 ℃ (more than 350 ℃ below 650 ℃, preferably more than 400 ℃ below 500 ℃), can manufacture the ceramic separation film of water-impermeable excellence.Particularly, in 350 ℃ of situations of heat-treating, can obtain at hydraulic pressure 0.2MPa(2bar) can prevent the ceramic separation film seen through of sealing when following.In addition, in 450 ℃ of situations of heat-treating, can obtain at hydraulic pressure 0.4MPa(4bar) can prevent the ceramic separation film seen through of sealing when following.That is,, according to manufacture method disclosed herein, can manufacture with high level and have both and there is the water-impermeable of balance relation and the ceramic separation film of gas-premeable in existing ceramic separation film.
The heat treated time can be according to the appropriate changes such as kind of the organo-silicon compound of giving on perforated membrane, for example can be set as more than 0.5 hour, below 3 hours (preferably more than 0.5 hour, below 2 hours).Preferably after reaching the heat treatment temperature of preferred settings, keep more than 0.1 hour (typically be more than 0.1 hour below 3 hours, for example more than 0.5 hour below 2 hours).Thus, organo-silicon compound suitably can be removed from the surface of perforated membrane.
In manufacture method disclosed herein, the remained on surface of above-mentioned perforated membrane has the fluorine atom from the fluorine-containing organic silicon compound.More specifically, the atom that organo-silicon compound contain carbon (C), oxygen (O), fluorine (F), silicon (Si) etc.And, when this fluorine-containing organic silicon compound is decomposed due to heat treatment, the part of above-mentioned atom is combination again after decomposition, form the little compound (or characteristic group) of molecular weight when being imparted to porous film surface, can remain in the surface of perforated membrane.Thus, can be at the residual fluorine atom had from organo-silicon compound in the surface (the near surface zone that comprises ceramic separation film inside) of perforated membrane (ceramic separation film).At this, has given from the state of the fluorine compounds of organo-silicon compound with from the state of the Ceramic bond of the characteristic group that contains fluorine atom of organo-silicon compound and ceramic separation film on the surface that " fluorine atom from organo-silicon compound is residual " is included in ceramic separation film.
In addition, in manufacture method disclosed herein, due to the thermal decomposition of organo-silicon compound, make fluorine atom residue in the surface of ceramic separation film.Above-mentioned organo-silicon compound contain silicon atom (Si).This silicon atom (Si) and the ceramic separation film formed by pottery to engage compatibility good, by this silicon atom (Si), fluorine atom (F) easily is imparted into the surface of ceramic separation film.
The number of fluorine atoms that is present in the surface of ceramic separation film, with respect to the pottery that forms above-mentioned ceramic separation film, contained metallic atom is several 100, is preferably more than 0.1 (for example more than 0.1 below 100, preferably more than 1 below 50, more preferably more than 1 below 10).Like this, if contained metallic atom is several 100 with respect to pottery, there is the fluorine atom of the ratio more than at least 0.1, just can give the surface of ceramic separation film with hydrophobicity.
For example, when perforated membrane (ceramic separation film) is aluminium oxide, remain in the number of fluorine atoms on the surface of perforated membrane (ceramic separation film), mean with the assay value based on energy dispersion type X ray spectrum analysis, with respect to aluminium oxide (Al
2o
3) contained Al atom 100, be preferably more than 0.1 (for example more than 0.1 below 100, preferably more than 1 below 50).If so that at least 0.1 ratio is residual fluorine atom arranged with respect to Al atom 100, just can give the surface of ceramic separation film with hydrophobicity.If, further with respect to Al atom 100, fluorine atom residues in the surface of ceramic separation film with 1 ratio, just can give the surface of ceramic separation film with suitable hydrophobicity.
In manufacture method disclosed herein, with the temperature more than the boiling point of organo-silicon compound, the perforated membrane of having given organo-silicon compound is heat-treated.Thus, can make to residue in from the fluorine atom of organo-silicon compound the surface of above-mentioned perforated membrane.By making fluorine atom residue in this porous film surface, can manufacture to have (hydrophobic) ceramic separation film of water-impermeable.In further manufacture method disclosed herein, the temperature more than the boiling point of organo-silicon compound is heat-treated the ceramic separation film of having given organo-silicon compound.Thus, organo-silicon compound are removed from ceramic separation film.The pore that therefore, can suppress ceramic separation film is stopped up by organo-silicon compound.Therefore, the ceramic separation film made by this manufacture method has high gas-premeable.
That is,, according to manufacture method disclosed herein, can manufacture with high level and have both and there is the water-impermeable of balance relation and the ceramic separation film of gas-premeable in existing ceramic separation film.
The use of<ceramic separation film>
The ceramic separation film made by above-mentioned manufacture method can be used with various purposes.For example, this ceramic separation film can be used in the diffusion barrier (for example, hydrogen separation membrane, oxygen separation membrane, nitrogen diffusion barrier etc.) that the gaseous species of water (comprising steam) and regulation is separated.
Below, with reference to Fig. 1, the situation for the ceramic separation film that will be made by manufacture method disclosed herein as hydrogen separation membrane describes.This hydrogen separation membrane is with from hydrogen (H
2) separating hydrogen gas is that purpose is used in the mixture that mixes of G&W.Particularly, at first, said mixture (water (comprising steam) and hydrogen) is contacted with ceramic separation film (hydrogen separation membrane) 20, for example, with the pressure (0.2MPa(2bar) of regulation following) pressurization.At this, the surface of above-mentioned ceramic separation film 20 has been endowed hydrophobicity, and this diffusion barrier has water-impermeable.Therefore, even under the state of pressurization, water does not see through ceramic separation film 20 yet.In addition, because this ceramic separation film 20 has maintained high gas-premeable, so hydrogen sees through ceramic separation film 20.Therefore, this hydrogen flows into porous substrate 10 sides (being the inboard of tubulose).Like this, ceramic separation film disclosed herein (hydrogen separation membrane) 20 can suitably only be isolated hydrogen from the mixture of hydrogen G&W.
<embodiment>
Below, embodiments of the invention are described.In this embodiment, prepare to change 5 kinds of membrane components that manufacturing conditions obtains.Wherein, below the embodiment of explanation is not intended to limit the present invention.
(sample 1)
At first, will be dispersed in decentralized medium (water) as the alumina powder (Alpha-alumina, particle diameter 3 μ m) of inorganic porous material the alumina fluid dispersion of preparation pulp-like together with adhesive (ethyl cellulose base polymer).Then, utilize extrusion molding, the dispersion liquid of pulp-like is shaped to the formed body of tubulose.By under air atmosphere, this formed body being fired to (1500 ℃, 2 hours), manufacture the porous substrate of tubulose.The porosity of this porous substrate is 40%, average pore size is 0.7 μ m.
Then, form on the surface of above-mentioned porous substrate the ceramic separation film (Alpha-alumina film) formed by Alpha-alumina.Particularly, will be dispersed in decentralized medium (water) as the alumina powder (Alpha-alumina, particle diameter 1 μ m) of porous material the alumina fluid dispersion of preparation pulp-like together with adhesive (polyvinyl alcohol adhesive).Then, adopt dip coating, at the outer peripheral face of the porous substrate of above-mentioned tubulose, give above-mentioned Alpha-alumina dispersion liquid.After making solvent seasoning, fired (1200 ℃, 2 hours) under air atmosphere, thereby formed the ceramic separation film (Alpha-alumina film) of thickness 100 μ m on the surface of porous substrate.The porosity of this Alpha-alumina film is 39%, average pore size is 65nm.
Then, the fluorine-containing organic silicon compound is imparted to the surface of above-mentioned Alpha-alumina film.In the present embodiment, as above-mentioned organo-silicon compound, use perfluor dodecyl triethoxysilane (2H, 2H-triethoxysilane, be designated hereinafter simply as " PFDTES " for perfluorododecyl-1H, 1H).Adopt dip coating, this PFDTES is imparted to the surface of Alpha-alumina film with thickness 50nm.Then, under oxygen atmosphere, the Alpha-alumina film of having given PFDTES is heat-treated to (350 ℃, 1 hour), thereby remove PFDTES from the surface of Alpha-alumina film.The membrane component that will possess the ceramic separation film that such operation makes is called sample 1.
Below, the manufacturing conditions of sample 2～5 is described.Wherein, in the making of following sample, for the step that there is no special instruction, carry out the step same with above-mentioned sample 1.
(sample 2)
In sample 2, by above-mentioned heat treated Temperature Setting, it is 400 ℃.
(sample 3)
In sample 3, as ceramic separation film, form the Alpha-alumina film of average pore size 4nm.(sample 4)
In sample 4, give decyl trimethoxy silane (decyltrimethoxysilane, be designated hereinafter simply as " DTMS ") on the surface of Alpha-alumina film.And, at this, by above-mentioned heat treated Temperature Setting, be 450 ℃.
(sample 5)
In sample 5, do not give any material on the surface of Alpha-alumina film, implement heat treatment (350 ℃, 1 hour) after forming this Alpha-alumina film.
The formation of above-mentioned each sample is summarized in to table 1.
[table 1]
(parsing on ceramic separation film surface)
At this, at first, observe the cross section of the ceramic separation film (the Alpha-alumina film after heat treatment) of sample 1 by SEM.The photo obtained is shown in to Fig. 3 A.Then, in this limits vision, carry out energy dispersion type X ray spectrum analysis (SEM-EDS analysis), carry out the quantitative and qualitative analysis of element.
The analysis result of SEM-EDS is shown in to Fig. 2.Fig. 2 means the figure of the energy dispersion type X ray spectrum analysis spectrum of sample 1.In this spectrogram, the longitudinal axis means counting, and transverse axis means the intensity of X ray.The results verification of this analysis is to the peak of carbon (C), oxygen (O), fluorine (F), aluminium (Al), silicon (Si).That is, the Alpha-alumina film of known sample 1 after heat treatment exists (remaining) each above-mentioned atom.And, according to having carried out the assay value that ZAF revises, on the surface of Alpha-alumina film, with respect to 100 aluminium atoms, have 4 fluorine atoms.So, for the distribution of the element of clear above-mentioned confirmation, for carbon (C), oxygen (O) and each element of aluminium (Al), carried out the SEM-EDS distributional analysis.
What will obtain by this distributional analysis the results are shown in Fig. 3 B～Fig. 3 D.Fig. 3 B means the result of SEM-EDS distributional analysis of the distribution of the carbon atom (C) in the cross section of Alpha-alumina film.Fig. 3 C means the result of SEM-EDS distributional analysis of the distribution of the oxygen atom (O) in the cross section of Alpha-alumina film.Fig. 3 D means the result of SEM-EDS distributional analysis of the distribution of the aluminium atom (Al) in the cross section of Alpha-alumina film.As shown in Figure 3 B, the result of being analyzed from SEM-EDS, carbon atom (C) does not almost detect in the inside of Alpha-alumina film (typically being the zone of the inside more than surperficial 5 μ of distance), that is, on surface and inner near surface zone, do not exist.Can think that thus the carbon atom detected comes from the organo-silicon compound on the surface that is imparted to the Alpha-alumina film (PFDTES).On the other hand, known as shown in Fig. 3 C and Fig. 3 D, oxygen atom (O) and aluminium atom (Al) are present in the inside of Alpha-alumina film in a large number.Can think that thus oxygen atom (O) and aluminium atom (Al) come from the aluminium oxide that forms ceramic separation film (Alpha-alumina film).
By above can think exist the material (residual after heat treatment) come from through heat treated organo-silicon compound on the surface of ceramic separation film.That is, can think that fluorine (F) and the silicon (Si) of having confirmed its existence in Fig. 2 are the atoms that comes from organo-silicon compound, with above-mentioned carbon, similarly be present in the surface (residual after heat treatment) of ceramic separation film.
(mensuration of water contact angle)
Then, for the hydrophobicity of assess sample 1 and sample 5, measure " water contact angle ".When measuring " water contact angle ", take JIS R3257(1999) measured as benchmark.Particularly, drip the water of 1 μ L on the surface of Alpha-alumina film, the angle θ that the surface of the tangent line of the water droplet of dropping and subjects is, as " water contact angle θ ", adopts θ/2 methods to measure water contact angle θ.
The result of said determination, the water contact angle θ on the surface of the Alpha-alumina film of sample 1 is more than 120 °.And the water contact angle θ on the surface of the Alpha-alumina film of sample 5 is below 50 °.Like this, be greater than the water contact angle θ of sample 5 by the water contact angle θ of sample 1, known sample 1 is difficult to soak (hydrophobicity is high) than sample 5.
(evaluation of water permeability)
Then, measure the water permeability of each sample.Particularly, each sample is cut to the circle into diameter 30mm, be fixed on support.Under the state of the Alpha-alumina film side contacts that makes water and each sample, to the direction of porous substrate, water is pressurizeed.Then, will periodically improve the water applied pressure, the pressure when water penetrates into the porous substrate side is measured as " authorized pressure ".The authorized pressure of each sample (MPa) is shown in to this hurdle of table 1.
As shown in table 1, in sample 1,4, until apply 0.2MPa(2bar) above pressure, water does not all penetrate into the porous substrate side.That is, known sample the 1, the 4th, do not see through the water-impermeable film of water during hydraulic pressure below 0.2MPa.On the other hand, in the sample 5 of not giving organo-silicon compound, even do not exert pressure, water also penetrates into the porous substrate side.That is, the known diffusion barrier only consisted of Alpha-alumina does not have water-impermeable.In addition, sample 2,3, even apply 0.4MPa(4bar) above pressure, water does not penetrate into the porous substrate side yet.Can think thus in the sample 3 that average pore size at the pore that heat treated temperature is elevated to the sample 2 of 400 ° and Alpha-alumina film is 4nm, give more excellent water-impermeable.
(selecting the evaluation of permeability)
Then, the selection permeability of sample 1 and 5 is estimated.At this, use nitrogen (N
2), distilled water, absolute ethyl alcohol (99.5%, Wako Pure Chemical Industries, Ltd. produce), toluene (99.5%, Wako Pure Chemical Industries, Ltd. produce), adopt the method identical with above-mentioned " evaluation of water permeability ", selected the evaluation of permeability.This evaluation result is shown in to Fig. 4.Wherein, the transverse axis of Fig. 4 means that, to mixture applied pressure (bar), the longitudinal axis means the transit dose (mol/m of each material
2.s.Pa).And, in Fig. 4, the transit dose of the icon representation sample 1 that full coat is black, the transit dose of hollow icon representation sample 5.
As shown in Figure 4, the nitrogen (N of comparative sample 1 and sample 5
2) transit dose, sample 1 and sample 5 both, nitrogen (N
2) all suitably see through the N of sample 1 and sample 5
2the gas permeability is equal extent.
Water (the H of comparative sample 1 and sample 5
2o) transit dose, see through water under the state of exerting pressure in sample 5, even and apply the pressure about 2bar in sample 1, do not make water see through yet.That is, known sample 1 has excellent water-impermeable.
The permeability of the ethanol of comparative sample 1 and sample 5 (Ethanol) under the state of pressure low (below 1.2bar), sees through ethanol, and in sample 1, could not make ethanol see through in sample 5.So, when pressure strengthens (more than 1.2bar), the permeability to ethanol also appears in sample 1, the permeability of known appearance and sample 5 same trend.
The transit dose of the toluene of comparative sample 1 and sample 5 (Toulene), sample 1 and sample 5 all have the permeability of same trend.That is, 5 pairs of toluene of known sample 1 and sample all have excellent permeability.
As mentioned above, sample 5 all sees through the contained whole material of mixture.With respect to this, in sample 1, there is the impermeability to water under the pressurized conditions below 2bar, and there is the impermeability to ethanol under the pressurized conditions below 1.2bar.That is, can think that sample 1 has the impermeability of water (according to pressurized conditions, also comprising ethanol) and has other materials (N
2gas, ethanol, toluene) permeability, there is the selection permeability.Therefore the ceramic separation film of known sample 1 can be suitable for separating the mixture from containing water or ethanol (particularly water) material of regulation.
(TG-DTA evaluation)
In addition, for the variation of confirming that organo-silicon compound produce due to heat treatment, carry out differential thermogravimetric amount and measure (TG-DTA:Thermo Gravimeter-Differential Thermal Analysis) simultaneously.At this, the device " Thermoplus " that uses Co., Ltd. Neo-Confucianism to manufacture, given the sample of PFDTES for the sample 1(of above-mentioned making on the surface of perforated membrane) measured.Particularly, under air atmosphere, with 5.0 ℃/min of programming rate, from room temperature, be warming up to 600 ℃, confirm exothermic peak temperature and weight change.Measurement result is shown in to Fig. 5.
As shown in Figure 5, in sample 1 near 250 ℃ (254.1 ℃) confirmed obvious weight and reduced.Afterwards, near 250 ℃～550 ℃, observe the minimizing of the weight of following exothermic peak, when surpassing about 600 ℃, almost can't see weight change.Therefore, while in manufacture method disclosed herein, using PFDTES as organo-silicon compound, for example, by by heat treated Temperature Setting being more than 200 ℃, below 700 ℃ (typically be more than 250 ℃ below 600 ℃, more than 300 ℃ below 600 ℃), can give suitable gas-premeable and water-impermeable to perforated membrane.
Utilizability on industry
In the diffusion barrier of the water-impermeable made by manufacture method disclosed herein, with high level, have both gas-premeable and water-impermeable.Therefore, can be suitable for use as the gas separation membrane for example desirable gas separated with water (comprising steam).And, because this diffusion barrier consists of pottery, so heat resistance and resistance to chemical reagents excellence can be applied in various fields.
Symbol description
1 membrane component
10 porous substrates
20 ceramic separation films (perforated membrane)
Claims (8)
1. the manufacture method of the ceramic separation film of a water-impermeable, is characterized in that, comprising:
Form the step of the perforated membrane of pottery system on the surface of porous substrate, the perforated membrane of described pottery system has a plurality of pores in the aperture that the gaseous species of regulation is separated;
Give the step of the organo-silicon compound that at least contain fluorine atom on described perforated membrane; With
The step that temperature more than the boiling point of described organo-silicon compound is heat-treated the perforated membrane of having given described organo-silicon compound,
At least remained on surface at described perforated membrane has the fluorine atom from described organo-silicon compound.
2. manufacture method as claimed in claim 1 is characterized in that:
Every 1 molecule of described organo-silicon compound has the carbon atom more than 10,
Described carbon number (N
c) with respect to described number of fluorine atoms (N
f) ratio (N
c/ N
f) be more than 0.5, below 2,
Described silicon atom number (N
si) with respect to described carbon number (N
c) ratio (N
si/ N
c) be more than 0.01, below 0.2.
3. manufacture method as claimed in claim 1 or 2 is characterized in that:
Described organo-silicon compound are the silanes organic compounds that contain fluorine-based or perfluor base.
4. manufacture method as described as any one in claim 1～3 is characterized in that:
Described perforated membrane is aluminium oxide.
5. manufacture method as claimed in claim 4 is characterized in that:
In the analysis based on energy dispersion type X ray optical spectroscopy, with respect to the aluminium atomicity 100 that forms described perforated membrane, described fluorine atom residues in the surface of described perforated membrane with the ratio more than 1, below 10.
6. manufacture method as described as any one in claim 1～5 is characterized in that:
By described heat treated Temperature Setting, be more than 200 ℃, below 700 ℃.
7. the ceramic separation film of the water-impermeable made by the described manufacture method of any one in claim 1～6.
8. ceramic separation film as claimed in claim 7 is characterized in that:
The average pore size obtained based on gas adsorption method is more than 0.3nm, below 100 μ m.
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| JP2011-087685 | 2011-04-11 | ||
| PCT/JP2012/058981 WO2012141033A1 (en) | 2011-04-11 | 2012-04-02 | Method for producing water-impermeable ceramic separation membrane, and ceramic separation membrane obtained by method for producing water-impermeable ceramic separation membrane |
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| CN112135708A (en) * | 2018-04-06 | 2020-12-25 | 株式会社则武 | High-porosity CBN ceramic grinding stone with homogeneous structure |
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| EP3001819B1 (en) * | 2013-03-14 | 2021-06-23 | ZeoMem Sweden AB | A method for producing a crystalline film of zeolite and/or zeolite like crystals on a porous substrate |
| WO2016117360A1 (en) * | 2015-01-22 | 2016-07-28 | 富士フイルム株式会社 | Acidic gas separation module |
| JP7065492B2 (en) * | 2017-09-06 | 2022-05-12 | 国立大学法人 名古屋工業大学 | Separation membrane |
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| JPH06170188A (en) * | 1992-12-10 | 1994-06-21 | Tokyo Gas Co Ltd | Gas separation membrane and production thereof |
| JP2002220225A (en) * | 2000-11-27 | 2002-08-09 | Toray Ind Inc | Zeolite membrane, method for treating zeolite membrane, aluminium electrolytic capacitor, and separating method |
| JP3686937B2 (en) * | 2001-08-15 | 2005-08-24 | 独立行政法人産業技術総合研究所 | Pervaporation separation membrane with high selectivity separation function |
| JP5045948B2 (en) * | 2008-12-24 | 2012-10-10 | 独立行政法人産業技術総合研究所 | Pervaporation separation membrane and method for producing the same |
| JP5718831B2 (en) * | 2012-01-19 | 2015-05-13 | 株式会社ノリタケカンパニーリミテド | Alkali-resistant inorganic porous material and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112135708A (en) * | 2018-04-06 | 2020-12-25 | 株式会社则武 | High-porosity CBN ceramic grinding stone with homogeneous structure |
| CN112135708B (en) * | 2018-04-06 | 2023-03-14 | 株式会社则武 | High-porosity CBN ceramic grinding stone with homogeneous structure |
| CN109868158A (en) * | 2019-02-28 | 2019-06-11 | 北京三聚环保新材料股份有限公司 | A kind of ceramic membrane and its method of modifying, filter and filtration system |
| CN109868158B (en) * | 2019-02-28 | 2024-04-02 | 北京海新能源科技股份有限公司 | Ceramic membrane, modification method thereof, filter comprising ceramic membrane and filter system comprising ceramic membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012141033A1 (en) | 2012-10-18 |
| JPWO2012141033A1 (en) | 2014-07-28 |
| JP5925190B2 (en) | 2016-05-25 |
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