JP5718831B2 - Alkali-resistant inorganic porous material and method for producing the same - Google Patents
Alkali-resistant inorganic porous material and method for producing the same Download PDFInfo
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- 239000011148 porous material Substances 0.000 title claims description 144
- 238000004519 manufacturing process Methods 0.000 title claims description 45
- 239000003513 alkali Substances 0.000 title claims description 22
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 61
- 238000000926 separation method Methods 0.000 claims description 45
- 239000012528 membrane Substances 0.000 claims description 39
- 125000001153 fluoro group Chemical group F* 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 125000004429 atom Chemical group 0.000 claims description 25
- 229910052731 fluorine Inorganic materials 0.000 claims description 24
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 12
- 239000011737 fluorine Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 6
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 claims description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052753 mercury Inorganic materials 0.000 claims description 6
- 150000003377 silicon compounds Chemical class 0.000 claims description 6
- -1 perfluoro group Chemical group 0.000 claims description 5
- 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 claims description 4
- 229910052863 mullite Inorganic materials 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 description 28
- 238000010335 hydrothermal treatment Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 18
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000012670 alkaline solution Substances 0.000 description 11
- 230000008859 change Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000395 magnesium oxide Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 238000007654 immersion Methods 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 229910010271 silicon carbide Inorganic materials 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000012937 correction Methods 0.000 description 4
- 230000003292 diminished effect Effects 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 238000003618 dip coating Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910018540 Si C Inorganic materials 0.000 description 2
- 229910007991 Si-N Inorganic materials 0.000 description 2
- 229910008045 Si-Si Inorganic materials 0.000 description 2
- 229910006294 Si—N Inorganic materials 0.000 description 2
- 229910006411 Si—Si Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 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 2
- 238000010304 firing Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- UVENODJFBHXOMX-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-pentacosafluorododecyl-tris(1,1,2,2,2-pentafluoroethoxy)silane Chemical compound FC(F)(F)C(F)(F)O[Si](OC(F)(F)C(F)(F)F)(OC(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UVENODJFBHXOMX-UHFFFAOYSA-N 0.000 description 1
- 208000010392 Bone Fractures Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010010214 Compression fracture Diseases 0.000 description 1
- 206010017076 Fracture Diseases 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920003174 cellulose-based polymer Polymers 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
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- KWEUJTRPCBXYLS-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-henicosafluorododecyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F KWEUJTRPCBXYLS-UHFFFAOYSA-N 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Description
本発明は、耐アルカリ性の無機多孔質体に関する。詳しくは、従来に比べ化学的安定性（典型的には耐腐食性、例えば耐アルカリ性）が向上した無機多孔質体の製造方法に関する。 The present invention relates to an alkali-resistant inorganic porous material. More specifically, the present invention relates to a method for producing an inorganic porous body having improved chemical stability (typically corrosion resistance, for example, alkali resistance) as compared with the prior art.
多孔質体は、その内部に三次元的に連なった気孔を備えた構造であり、通常の固体とは異なる性質を有する。例えば、該多孔質体は広い比表面積を有することから、触媒やその支持体（担体）として有用である。また気孔の大きさ（孔径）を制御することにより、液体やガス等を分離、精製、又は吸着することもできる。このため、工業的に幅広い分野で利用されている。なかでも、無機材料で構成される無機多孔質体は、耐熱性、耐久性、耐薬品性等に優れることから、例えば、高温環境下におけるガス分離に応用されている。 The porous body has a structure having pores that are three-dimensionally connected therein, and has a property different from that of a normal solid. For example, since the porous body has a wide specific surface area, it is useful as a catalyst or a support (support) thereof. Further, by controlling the size (pore diameter) of the pores, liquid, gas, etc. can be separated, purified, or adsorbed. For this reason, it is used in a wide range of industrial fields. Especially, since the inorganic porous body comprised with an inorganic material is excellent in heat resistance, durability, chemical resistance, etc., it is applied to the gas separation in a high temperature environment, for example.
上記応用例の一つとして、比較的大きな孔径を有する支持体（無機多孔質体）の上に、所望の孔径を有する分離膜（多孔質膜）を備えた分離膜エレメントがある。該分離膜エレメントの製造方法としては、典型的には、目的とする分離膜の原料成分を含む溶液中に支持体を浸漬し、アルカリ水熱処理（水熱合成とも言う。）することにより、該支持体表面に分離膜を形成する方法が挙げられる。かかる方法によれば、支持体の表面上のみならず、該支持体表面下の気孔内にも分離膜を形成し得るため、分離能の向上に有効である。上記アルカリ水熱処理に関する先行技術としては、特許文献１〜３が挙げられる。 As one of the application examples, there is a separation membrane element including a separation membrane (porous membrane) having a desired pore diameter on a support (inorganic porous body) having a relatively large pore diameter. As a method for producing the separation membrane element, typically, the support is immersed in a solution containing the raw material components of the target separation membrane, and subjected to alkaline hydrothermal treatment (also referred to as hydrothermal synthesis), thereby producing the separation membrane element. The method of forming a separation membrane on the support surface is mentioned. According to such a method, the separation membrane can be formed not only on the surface of the support but also in the pores below the surface of the support, which is effective in improving the separation performance. Patent documents 1-3 are mentioned as prior art about the above-mentioned alkaline hydrothermal treatment.
上述の通り無機多孔質体は耐薬品性に優れ、幅広い分野で使用されている。しかし、例えば上記アルカリ水熱処理のような強アルカリ環境下（例えばＰＨ試験紙による試験でＰＨが１１以上の環境下）では、アルカリによって該多孔質体の表面が腐食される虞がある。このため、合成時および／または使用時にアルカリ性の物質と接触し得る場合、耐アルカリ性（耐腐食性）をより向上させることが望まれている。 As described above, the inorganic porous body has excellent chemical resistance and is used in a wide range of fields. However, the surface of the porous body may be corroded by alkali in a strongly alkaline environment such as the alkaline hydrothermal treatment (for example, in an environment where PH is 11 or more in a test using a PH test paper). For this reason, when it can contact an alkaline substance at the time of a synthesis | combination and / or use, it is desired to improve alkali resistance (corrosion resistance) more.
本発明は、かかる課題を鑑みてなされたものであり、その目的とするところは、化学的安定性（典型的には耐腐食性、例えば耐アルカリ性）が従来に比べ向上した無機多孔質体を製造する方法を提供することである。また、本発明は、他の側面として、かかる製造方法によって得られた無機多孔質体を提供する。 The present invention has been made in view of such problems, and an object of the present invention is to provide an inorganic porous body having improved chemical stability (typically corrosion resistance, for example, alkali resistance) as compared with the prior art. It is to provide a method of manufacturing. Moreover, this invention provides the inorganic porous body obtained by this manufacturing method as another side surface.
上記目的を実現するべく、本発明によって、耐アルカリ性の無機多孔質体を製造する方法であって：無機多孔質材の表面に、少なくともフッ素原子を含む有機ケイ素化合物を付与すること；および上記有機ケイ素化合物が付与された上記無機多孔質材を、上記有機ケイ素化合物の沸点以上の温度で、上記無機多孔質材の少なくとも一部の表面に上記有機ケイ素化合物由来のフッ素原子が残存するよう熱処理すること；を包含する、無機多孔質体の製造方法が提供される。
ここで開示される製造方法では、無機多孔質材の表面に、上記フッ素含有有機ケイ素化合物が付与されている。このため、該多孔質材の化学的安定性および／または疎水性が従来に比べ向上している。したがって、例えば強アルカリ溶液中における該多孔質材の耐アルカリ性（耐腐食性）を向上し得る。また、ここで開示される製造方法では、上記フッ素含有有機ケイ素化合物を付与した後に熱処理を施すことにより、該有機ケイ素化合物を本発明の効果が損なわれない程度に除去している。このため多孔質材の気孔が好適に保たれており、例えば該多孔質材を支持体に用いた分離膜エレメントでは、高い分離能（例えば、ガス透過性）を発揮することができる。
In order to achieve the above object, according to the present invention, there is provided a method for producing an alkali-resistant inorganic porous material comprising: providing an organic silicon compound containing at least fluorine atoms on the surface of an inorganic porous material; The inorganic porous material provided with the silicon compound is heat-treated at a temperature equal to or higher than the boiling point of the organic silicon compound so that fluorine atoms derived from the organic silicon compound remain on at least a part of the surface of the inorganic porous material. A method for producing an inorganic porous body is provided.
In the production method disclosed here, the fluorine-containing organosilicon compound is applied to the surface of the inorganic porous material. For this reason, the chemical stability and / or hydrophobicity of the porous material is improved as compared with the prior art. Therefore, for example, the alkali resistance (corrosion resistance) of the porous material in a strong alkali solution can be improved. Further, in the production method disclosed herein, the organosilicon compound is removed to such an extent that the effects of the present invention are not impaired by applying the heat treatment after the fluorine-containing organosilicon compound is applied. For this reason, the pores of the porous material are suitably maintained. For example, in a separation membrane element using the porous material as a support, high separation ability (for example, gas permeability) can be exhibited.
また、ここで開示される製造方法の好ましい一態様では、上記無機多孔質材として、水銀圧入法に基づく平均孔径が０．４μｍ以上１００μｍ以下のものを用いる。
無機多孔質材の気孔径が０．４μｍを大幅に下回る場合、多孔質材としての特性（例えばガス分離能）を発揮することが難しくなる。一方、上記気孔径が１００μｍを大幅に上回る場合、機械的強度が低下したり、本発明の効果が薄れたり（典型的には、該多孔質体表面上に存在する気孔の内壁のうち、開口部近傍の領域における化学的安定性の不足）する虞がある。よって、無機多孔質体の気孔径は上記範囲内にあることが好ましい。
In a preferred embodiment of the production method disclosed herein, an inorganic porous material having an average pore diameter of 0.4 μm or more and 100 μm or less based on a mercury intrusion method is used.
When the pore diameter of the inorganic porous material is significantly less than 0.4 μm, it becomes difficult to exhibit characteristics (for example, gas separation ability) as the porous material. On the other hand, when the pore diameter is significantly larger than 100 μm, the mechanical strength is lowered or the effect of the present invention is diminished (typically, of the inner walls of the pores existing on the surface of the porous body, There is a risk that the chemical stability in the region near the portion is insufficient). Therefore, the pore size of the inorganic porous body is preferably within the above range.
また、ここで開示される製造方法の好ましい一態様では、上記無機多孔質材として、アルミナ、ジルコニア、チタニア、マグネシア、シリカ、炭化ケイ素、窒化ケイ素および無機複合酸化物からなる群から選択される１種または２種以上を含んでいる。
上記化合物は、典型的にはセラミックの材料として知られており、無機多孔質材のなかでも化学的安定性に優れ、強い機械的強度を有している。このため、より幅広い用途で利用することができる。
In a preferred embodiment of the production method disclosed herein, the inorganic porous material is selected from the group consisting of alumina, zirconia, titania, magnesia, silica, silicon carbide, silicon nitride, and inorganic composite oxide. Contains seeds or two or more.
The above compound is typically known as a ceramic material, and has excellent chemical stability and strong mechanical strength among inorganic porous materials. For this reason, it can utilize for a wider use.
また、ここで開示される製造方法の好ましい一態様では、上記熱処理は、走査型電子顕微鏡―エネルギー分散型Ｘ線分光法に基づく分析で、無機多孔質材を構成する金属原子１００原子数に対し、上記フッ素原子が０．１原子数以上１００原子数以下の割合で残存するように行う。
上記組成比率で構成された無機多孔質材では、該多孔質材の表面にフッ素含有有機ケイ素化合物由来のフッ素原子が好適に残存している。このため該多孔質材の気孔を塞ぐことなく（即ち本来の性能を保ったまま）、該多孔質体の化学的安定性を従来に比べ向上させることができる。
Further, in a preferred embodiment of the production method disclosed herein, the heat treatment is performed on the basis of 100 atomic number of metal atoms constituting the inorganic porous material by analysis based on scanning electron microscope-energy dispersive X-ray spectroscopy. The fluorine atoms remain at a ratio of 0.1 to 100 atoms.
In the inorganic porous material having the above composition ratio, fluorine atoms derived from the fluorine-containing organosilicon compound are suitably left on the surface of the porous material. For this reason, the chemical stability of the porous body can be improved as compared with the prior art without blocking the pores of the porous material (that is, while maintaining the original performance).
また、ここで開示される製造方法の好ましい一態様では、上記有機ケイ素化合物は、少なくともパーフルオロ基を含んでいる。
パーフルオロ基を有する有機ケイ素化合物は、フッ素原子をより好適に無機多孔質材の表面に付加することができる。また、上記結合は比較的結合力が強いため、熱処理後においても好適な数のフッ素原子を残存させることができる。このため、該多孔質材の表面に好適に化学的安定性を付与することができる。
In a preferred embodiment of the production method disclosed herein, the organosilicon compound contains at least a perfluoro group.
The organosilicon compound having a perfluoro group can add a fluorine atom to the surface of the inorganic porous material more preferably. Further, since the bond has a relatively strong bonding force, a suitable number of fluorine atoms can remain even after the heat treatment. For this reason, chemical stability can be suitably imparted to the surface of the porous material.
また、ここで開示される製造方法の好ましい一態様では、上記熱処理の温度を、２００℃以上４００℃以下（例えば３００℃）に設定する。
熱処理の温度が２００℃を大幅に下回った場合、付与した有機ケイ素化合物が十分に除去されず、無機多孔質材の気孔が塞がれてしまうため、分離、精製など本来の機能性が低下する虞がある。一方、４００℃を大幅に上回った場合は、有機ケイ素化合物が完全に気化してしまい、ここで開示される製造方法の効果が薄れる虞がある。このため、熱処理温度を上記範囲とすることで、該多孔質材の気孔を塞ぐことなく、より好適に本発明の効果（即ち、化学的安定性）を発揮することができる。
In a preferred embodiment of the production method disclosed herein, the temperature of the heat treatment is set to 200 ° C. or higher and 400 ° C. or lower (for example, 300 ° C.).
When the temperature of the heat treatment is significantly lower than 200 ° C., the provided organosilicon compound is not sufficiently removed and the pores of the inorganic porous material are blocked, so that the original functionality such as separation and purification is lowered. There is a fear. On the other hand, when the temperature is significantly higher than 400 ° C., the organosilicon compound is completely vaporized, and the effect of the production method disclosed herein may be diminished. For this reason, the effect (namely, chemical stability) of this invention can be exhibited more suitably, without plugging the hole of this porous material by making heat processing temperature into the said range.
また、本発明は、ここで開示されるいずれかの製造方法によって得られた無機多孔質体を提供する。
ここで開示されるいずれかの製造方法によって得られる無機多孔質体は、化学的安定性（典型的には耐腐食性、例えば耐アルカリ性）がより一層向上している。よって合成時および／または使用時に腐食性物質（典型的には強酸性物質、強アルカリ性物質、有機溶剤等）と接触し得る場合（例えば、強アルカリ環境下となり得る場合）に好適に用いることができる。
Moreover, this invention provides the inorganic porous body obtained by one of the manufacturing methods disclosed here.
The inorganic porous body obtained by any of the production methods disclosed herein has further improved chemical stability (typically corrosion resistance, for example, alkali resistance). Therefore, it is preferably used when it can come into contact with a corrosive substance (typically a strong acidic substance, a strong alkaline substance, an organic solvent, etc.) during synthesis and / or use (for example, when it can be in a strong alkaline environment). it can.
また、ここで開示される製造方法によって得られる無機多孔質体の好ましい一態様では、水銀圧入法に基づく平均孔径が０．４μｍ以上１００μｍ以下である。
上記範囲を満たす無機多孔質材料は、比較的気孔径が大きいため、例えば後述するガス分離膜の支持体として好適に用いることができる。
In a preferred embodiment of the inorganic porous material obtained by the production method disclosed herein, the average pore diameter based on the mercury intrusion method is 0.4 μm or more and 100 μm or less.
Since the inorganic porous material satisfying the above range has a relatively large pore diameter, for example, it can be suitably used as a support for a gas separation membrane described later.
以下、本発明の好適な実施形態を説明する。なお、本明細書において特に言及している事項以外の事柄であって本発明の実施に必要な事柄は、当該分野における従来技術に基づく当業者の設計事項として把握され得る。本発明は、本明細書に開示されている内容と当該分野における技術常識とに基づいて実施することができる。 Hereinafter, preferred embodiments of the present invention will be described. Note that matters other than matters specifically mentioned in the present specification and necessary for the implementation of the present invention can be grasped as design matters of those skilled in the art based on the prior art in this field. The present invention can be carried out based on the contents disclosed in this specification and common technical knowledge in the field.
なお、本明細書において「気孔径（単に、孔径という場合もある。）」とは、特に断りがない場合、一般的な水銀圧入法測定に基いて得られる値を指す。なお、かかる測定において、気孔は、外部に開かれた開孔を意味し、閉じられた空間（閉孔）は含まない。水銀圧入法による測定には、例えば株式会社島津製作所製のオートポアＩＩＩ９４１０を用いることができる。また本明細書において、「気孔率（％）」とは、上記測定により得られる気孔容積（Ｖｂ（ｃｍ３））を、見かけの体積（Ｖａ（ｃｍ３））で除して１００を掛けることにより、算出した値を意味する。さらに本明細書において、粒径とはレーザー回折・光散乱法に基づく粒度分布測定により測定した体積基準の粒度分布において微粒子側からの累積５０％に相当する平均粒径（メジアン径）を示す。 In the present specification, “pore diameter (sometimes simply referred to as pore diameter)” refers to a value obtained based on a general mercury intrusion measurement unless otherwise specified. In this measurement, the pore means an opening opened to the outside, and does not include a closed space (closed hole). For the measurement by the mercury intrusion method, for example, Autopore III 9410 manufactured by Shimadzu Corporation can be used. In this specification, “porosity (%)” is obtained by dividing the pore volume (Vb (cm 3 )) obtained by the above measurement by the apparent volume (Va (cm 3 )) and multiplying by 100. Means the calculated value. Further, in this specification, the particle diameter means an average particle diameter (median diameter) corresponding to 50% cumulative from the fine particle side in a volume-based particle size distribution measured by particle size distribution measurement based on a laser diffraction / light scattering method.
ここで開示される製造方法は、まず無機多孔質材を用意すること、該多孔質材の表面に、フッ素原子を含む有機ケイ素化合物を付与すること、有機ケイ素化合物を付与した多孔質材を熱処理することを包含する。そして、上記熱処理後に、有機ケイ素化合物由来のフッ素原子が多孔質体の表面に残存していることを特徴とする。このため、他の構成成分の内容や組成等については、本発明の目的を逸脱しない限りにおいて種々の基準に照らして決定することができる。 The production method disclosed herein includes first preparing an inorganic porous material, applying an organosilicon compound containing a fluorine atom to the surface of the porous material, and heat-treating the porous material provided with the organosilicon compound. To include. And after the said heat processing, the fluorine atom derived from an organosilicon compound remains on the surface of a porous body, It is characterized by the above-mentioned. For this reason, the content and composition of other components can be determined in light of various standards without departing from the object of the present invention.
＜無機多孔質材の用意＞
ここで開示される製造方法では、先ず無機多孔質材を用意する。該無機多孔質材としては、従来公知の種々のものから特に制限なく、用途に応じて適宜選択することができる。例えば、酸化アルミニウム（アルミナ：Ａｌ２Ｏ３）、二酸化ジルコニウム（ジルコニア：ＺｒＯ２）、酸化マグネシウム（マグネシア：ＭｇＯ）、酸化ケイ素（シリカ：ＳｉＯ２）、酸化チタン（チタニア：ＴｉＯ２）、酸化セリウム（セリア：ＣｅＯ２）、酸化イットリウム（イットリア：Ｙ２Ｏ３）、チタン酸バリウム（ＢａＴｉＯ３）等の酸化物系材料や、コーディエライト（２ＭｇＯ・２Ａｌ２Ｏ３・５ＳｉＯ２）、ムライト（３Ａｌ２Ｏ３・２ＳｉＯ２）、フォルステライト（２ＭｇＯ・ＳｉＯ２）、ステアタイト（ＭｇＯ・ＳｉＯ２）、サイアロン（Ｓｉ３Ｎ４・Ａｌ２Ｏ３）、ジルコン（ＺｒＯ２・ＳｉＯ２）、フェライト（Ｍ２Ｏ・Ｆｅ２Ｏ３）等の複合酸化物系材料、窒化ケイ素（シリコンナイトライド：Ｓｉ３Ｎ４）、窒化アルミニウム（アルミナイトライド：ＡｌＮ）等の窒化物系材料、炭化ケイ素（シリコンカーバイド：ＳｉＣ）等の炭化物系材料、ハイドロキシアパタイト等の水酸化物系材料、炭素（Ｃ）、ケイ素（Ｓｉ）、アルミニウム（Ａｌ）、鉄（Ｆｅ）等の元素系材料、もしくはこれらを一種以上含む無機複合材料が挙げられる。また、天然鉱物（粘土、粘土鉱物、シャモット、ケイ砂、陶石、長石、シラス）や、高炉スラグ、フライアッシュ等を用いることもできる。
ここで開示される製造方法における好ましい一態様では、上記無機多孔質材は、セラミック材料として好適に用いられる、酸化アルミニウム（α‐アルミナ、γ‐アルミナ）、二酸化ジルコニウム（ジルコニア）、酸化チタン（チタニア）、酸化マグネシウム（マグネシア）、酸化ケイ素（シリカ）、ムライト、コーディエライト、炭化ケイ素（シリコンカーバイド）および窒化ケイ素（シリコンナイトライド）からなる群から選択される１種または２種以上を含んでいる。これらのセラミック材料を含む場合、より一層化学的安定性に優れ、強い機械的強度を有しているため、工業的に幅広い用途で用いることができる。
<Preparation of inorganic porous material>
In the manufacturing method disclosed here, first, an inorganic porous material is prepared. The inorganic porous material is appropriately selected depending on the intended use without any particular limitation from various conventionally known materials. For example, aluminum oxide (alumina: Al 2 O 3 ), zirconium dioxide (zirconia: ZrO 2 ), magnesium oxide (magnesia: MgO), silicon oxide (silica: SiO 2 ), titanium oxide (titania: TiO 2 ), cerium oxide (Ceria: CeO 2 ), yttrium oxide (yttria: Y 2 O 3 ), oxide materials such as barium titanate (BaTiO 3 ), cordierite (2MgO · 2Al 2 O 3 · 5SiO 2 ), mullite ( 3Al 2 O 3 · 2SiO 2) , forsterite (2MgO · SiO 2), steatite (MgO · SiO 2), sialon (Si 3 N 4 · Al 2 O 3), zirconium (ZrO 2 · SiO 2), ferrite (M 2 O · Fe 2 O 3) composite oxide material such as silicon nitride (Shi Con nitride: Si 3 N 4), aluminum nitride (aluminum nitride: AlN) nitride material such as silicon carbide (silicon carbide: SiC) carbide-based material such as a hydroxide-based material, such as hydroxyapatite, Examples thereof include elemental materials such as carbon (C), silicon (Si), aluminum (Al), and iron (Fe), or inorganic composite materials containing one or more of these. Natural minerals (clay, clay mineral, chamotte, quartz sand, porcelain stone, feldspar, shirasu), blast furnace slag, fly ash, and the like can also be used.
In a preferred embodiment of the production method disclosed herein, the inorganic porous material is preferably used as a ceramic material, such as aluminum oxide (α-alumina, γ-alumina), zirconium dioxide (zirconia), titanium oxide (titania). ), Magnesium oxide (magnesia), silicon oxide (silica), mullite, cordierite, silicon carbide (silicon carbide) and silicon nitride (silicon nitride). Yes. When these ceramic materials are included, they are further excellent in chemical stability and have strong mechanical strength, so that they can be used in a wide range of industrial applications.
ここで用いる多孔質材の気孔径としては、特に限定されないが、例えば、サブミクロン以上（例えば０．１μｍ以上、好ましくは１μｍ以上）であって、１００μｍ以下（好ましくは５０μｍ以下、例えば３０μｍ以下）とすることができる。無機多孔質材の気孔径が０．１μｍを大幅に下回る場合、多孔質材としての特性（例えばガス分離能）を発揮することが難しくなる。一方、上記気孔径が１００μｍを大幅に上回る場合、機械的強度が不足したり、本発明の効果が薄れたり（典型的には、該気孔の開口部付近における化学的安定性の不足）する虞がある。よって、無機多孔質材の気孔径は、上記範囲内にあることが好ましい。 The pore diameter of the porous material used here is not particularly limited, but is, for example, submicron or more (for example, 0.1 μm or more, preferably 1 μm or more) and 100 μm or less (preferably 50 μm or less, for example, 30 μm or less). It can be. When the pore diameter of the inorganic porous material is significantly less than 0.1 μm, it becomes difficult to exhibit characteristics (for example, gas separation ability) as the porous material. On the other hand, when the pore diameter is significantly larger than 100 μm, the mechanical strength may be insufficient, or the effect of the present invention may be diminished (typically, the chemical stability in the vicinity of the opening of the pore is insufficient). There is. Therefore, the pore diameter of the inorganic porous material is preferably within the above range.
ここで用いる無機多孔質材は、用途に応じた種々の形状をとり得る。例えば、平板（薄板）状、中空箱型状、チューブ状（円筒状）、あるいは円筒の周側面を垂直に押し潰したフラットチューブラ−状（中空扁平状）、ハニカム構造を有した円柱状などが挙げられるが、形状やサイズ、厚み等は特に限定されない。例えば、ハニカム構造のような複雑な構造の場合は、ここで開示される製造方法を用いることにより後述する分離膜の形成をより簡便なものにし得るため特に好適である。また、例えば、分離膜エレメントの支持体として用いる場合は、ガス分離モジュールとしての改質器等リアクタに適用しやすいため、チューブ状のものを好適に用いることができる。
所望する形状は、従来行われている公知の成形技法（金型成形、冷間静水圧成形、押出成形、射出成形、鋳込み成形、プレス成形等）や焼成技法を用いて製造することができる。かかる手法としては、例えば、先ず粉末状の上記無機多孔質材と、バインダ（例えば、セルロース系ポリマー）とを分散溶媒（水や有機溶剤）中に分散させることによって、スラリー状（ペースト状、インク状を含む。）の分散液を調製する。なお、該スラリー状の分散液には、必要に応じて分散剤や界面活性剤等の添加剤を含み得る。次に、上述した公知の成形技法を用いてスラリー状の分散液を所望の形状に成形する。そして、該成形体と、焼結を促進するための添加剤（例えばＡｌ２Ｏ３に対するＭｇＯ、ＳｉＯ２や、Ｓｉ３Ｎ４に対するＹ２Ｏ３、Ａｌ２Ｏ３、ＭｇＯ等）とを焼成し、焼結することによって製造することができる。
The inorganic porous material used here can take various shapes depending on the application. For example, a flat (thin plate) shape, a hollow box shape, a tube shape (cylindrical shape), a flat tubular shape (hollow flat shape) in which the peripheral side surface of the cylinder is vertically crushed, a cylindrical shape having a honeycomb structure, etc. The shape, size, thickness and the like are not particularly limited. For example, in the case of a complicated structure such as a honeycomb structure, the formation of the separation membrane described later can be made simpler by using the manufacturing method disclosed herein, which is particularly preferable. In addition, for example, when used as a support for a separation membrane element, it is easy to apply to a reactor such as a reformer as a gas separation module.
The desired shape can be produced by using conventionally known molding techniques (mold molding, cold isostatic pressing, extrusion molding, injection molding, casting molding, press molding, etc.) and firing techniques. As such a technique, for example, first, the powdery inorganic porous material and a binder (for example, a cellulose-based polymer) are first dispersed in a dispersion solvent (water or an organic solvent) to form a slurry (paste, ink). A dispersion is prepared. The slurry-like dispersion may contain additives such as a dispersant and a surfactant as necessary. Next, the slurry-like dispersion is formed into a desired shape using the above-described known forming technique. Then, baking and shaped body, additives for accelerating the sintering (MgO for example Al 2 O 3, SiO 2 or, Si 3 N 4 for Y 2 O 3, Al 2 O 3, MgO , etc.) and the And can be manufactured by sintering.
＜有機ケイ素化合物の付与＞
ここで開示される製造方法では、次に、上記無機多孔質材の表面に、フッ素原子を含む有機ケイ素化合物を付与する。即ち、ここで用いられる有機ケイ素化合物は、少なくともフッ素原子（Ｆ）と、ケイ素原子（Ｓｉ）と炭素原子（Ｃ）とを含む化合物である。構造にケイ素を含む（好ましくは、基本骨格（主鎖）にケイ素を含む）有機化合物は、高温（典型的には１００℃以上、例えば２００℃以上４００℃以下）で熱分解反応することにより、上記無機多孔質材の表面にＳｉ−Ｓｉ結合、Ｓｉ−Ｎ結合、Ｓｉ−Ｃ結合のような結合を好適に生じ得る。このため、有機ケイ素化合物中に含まれるフッ素原子を、好適に無機多孔質材の表面に付加することができる。また上記結合は、比較的結合力が強いため、熱処理後においても該多孔質材表面にフッ素原子を好適に残存させることができる。
<Granting organosilicon compound>
In the production method disclosed herein, next, an organosilicon compound containing fluorine atoms is applied to the surface of the inorganic porous material. That is, the organosilicon compound used here is a compound containing at least a fluorine atom (F), a silicon atom (Si), and a carbon atom (C). An organic compound containing silicon in the structure (preferably containing silicon in the basic skeleton (main chain)) undergoes a thermal decomposition reaction at a high temperature (typically 100 ° C. or higher, for example, 200 ° C. or higher and 400 ° C. or lower). Bonds such as Si—Si bonds, Si—N bonds, and Si—C bonds can be suitably generated on the surface of the inorganic porous material. For this reason, the fluorine atom contained in the organosilicon compound can be suitably added to the surface of the inorganic porous material. Further, since the bond has a relatively strong bonding force, fluorine atoms can be suitably left on the surface of the porous material even after heat treatment.
ここで用いる上記有機ケイ素化合物としては、例えばフッ素原子（ＭＦ）と炭素原子（ＭＣ）との存在比（ＭＣ／ＭＦ）が、０．５以上２以下（好ましくは０．５以上１．５以下、より好ましくは０．５以上１以下）のものが好ましく、また炭素原子（ＭＣ）に対するケイ素原子（ＭＳｉ）の原子数の比の値（ＭＳｉ／ＭＣ）は、０．０１以上０．２以下（好ましくは０．０１以上０．０８以下、より好ましくは０．０５±０．０２）であるとよい。さらに、該有機ケイ素化合物の構造としては、フッ素原子を１つ以上含んだ側鎖を有していることが好ましく、フッ素原子を２つ以上含んだ側鎖（例えばパーフルオロ基）を有していることがより好ましい。かかる有機ケイ素化合物としては、具体的には、１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロドデシルトリエトキシシラン（ＰＦＤＴＥＳ：ｐｅｒｆｌｕｏｒｏｄｏｄｅｃｙｌ−１Ｈ，１Ｈ，２Ｈ，２Ｈ−ｔｒｉｅｔｈｏｘｙｓｉｌａｎｅ：Ｃ１８Ｈ１９Ｏ３Ｆ２１Ｓｉ）や、１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロテトラデシルトリエトキシシラン（ｐｅｒｆｌｕｏｒｏｔｅｔｒａｄｅｃｙｌ−１Ｈ，１Ｈ，２Ｈ，２Ｈ−ｔｒｉｅｔｈｏｘｙｓｉｌａｎｅ：Ｃ２０Ｈ１９Ｏ３Ｆ２５Ｓｉ）等のシラン系有機化合物や、パーフルオロポリシロキサン（ｐｅｒｆｌｕｏｒｏｐｏｌｙｓｉｌｏｘａｎｅ）等のシロキサン系有機化合物が挙げられる。なお、ここで「有機ケイ素化合物」とは、上述のような化合物のみならず、かかる化合物を含んだ混合物の状態をも包含する。 As the organosilicon compound used here, for example, the abundance ratio (M C / M F ) between a fluorine atom (M F ) and a carbon atom (M C ) is 0.5 or more and 2 or less (preferably 0.5 or more). 1.5 or less, more preferably 0.5 or more and 1 or less), and the ratio of the number of silicon atoms (M Si ) to carbon atoms (M C ) (M Si / M C ) is It may be 0.01 or more and 0.2 or less (preferably 0.01 or more and 0.08 or less, more preferably 0.05 ± 0.02). Further, the structure of the organosilicon compound preferably has a side chain containing one or more fluorine atoms, and has a side chain containing two or more fluorine atoms (for example, a perfluoro group). More preferably. As such an organosilicon compound, specifically, 1H, 1H, 2H, 2H-perfluorododecyltriethoxysilane (PFDTES: perfluorododecyl-1H, 1H, 2H, 2H-triethoxysilane: C 18 H 19 O 3 F 21 Si ) and, IH, IH, 2H, 2H-perfluoro-tetradecyl triethoxysilane (perfluorotetradecyl-1H, 1H, 2H , 2H-triethoxysilane: and C 20 H 19 O 3 F 25 Si) silane such as organic compounds, par Examples thereof include siloxane-based organic compounds such as fluoropolysiloxane (perfluoropolysiloxane). Here, the “organosilicon compound” includes not only the above-described compounds but also a mixture state containing such compounds.
上記有機ケイ素化合物の沸点は、特に限定されないが、例えば、１００℃以上５００℃以下（典型的には１５０℃以上４５０℃以下、好ましくは２００℃〜４００℃）のものを好適に用いることができる。沸点が上記範囲にある有機ケイ素化合物は、後述する熱処理において、無機多孔質材の表面に有機ケイ素化合物をより好適に付与することができる。 Although the boiling point of the organosilicon compound is not particularly limited, for example, those having a temperature of 100 ° C. to 500 ° C. (typically 150 ° C. to 450 ° C., preferably 200 ° C. to 400 ° C.) can be suitably used. . The organosilicon compound having a boiling point in the above range can more suitably impart the organosilicon compound to the surface of the inorganic porous material in the heat treatment described below.
上記有機ケイ素化合物を無機多孔質材の表面に付与する方法としては、従来公知の種々の方法を用いることができる。かかる方法としては、例えば、ディップコーティング法、スピンコーティング法、ドクターブレード法、スクリーン印刷法、ゾル―ゲル法、電気泳動法、スプレー法等が挙げられる。ここで用いられる無機多孔質材のように表面が平滑でない場合は、例えば、ディップコーティング法を用いることができる。上記手法によれば、該多孔質材の最表面上（即ち、最も凸な）のみならず、気孔内（典型的には該気孔の内壁のうち開口部近傍の領域）にも好適に有機ケイ素化合物を付与し得る。このため、該多孔質材の化学的安定性をより向上させることができる。かかる手法としては、具体的には、先ず上記有機ケイ素化合物を溶媒中に分散させた分散液を用意する。次に、付与の被対象物としての無機多孔質材を、該分散液中に浸漬させ、一定時間（典型的には数分〜数十分、例えば１分〜２０分）放置した後、引き上げる。そして、該多孔質材の表面に付着した分散溶媒を除去した（典型的には乾燥により揮発させた）後に、後述する熱処理を行うことにより、有機ケイ素化合物を付与することができる。なお、上記有機ケイ素化合物の付与、乾燥および焼成は、必要に応じて一部の操作またはこれら一連の操作を複数回繰り返して行うことができる。 As a method for applying the organosilicon compound to the surface of the inorganic porous material, various conventionally known methods can be used. Examples of such a method include a dip coating method, a spin coating method, a doctor blade method, a screen printing method, a sol-gel method, an electrophoresis method, and a spray method. When the surface is not smooth like the inorganic porous material used here, for example, a dip coating method can be used. According to the above method, not only on the outermost surface of the porous material (that is, the most convex), but also in the pores (typically, the region near the opening of the inner wall of the pore). Compounds can be provided. For this reason, the chemical stability of the porous material can be further improved. Specifically, as such a technique, firstly, a dispersion liquid in which the organosilicon compound is dispersed in a solvent is prepared. Next, the inorganic porous material as the object to be applied is immersed in the dispersion, left for a certain period of time (typically several minutes to several tens of minutes, for example, 1 minute to 20 minutes), and then pulled up. . And after removing the dispersion | distribution solvent adhering to the surface of this porous material (typically making it volatilize by drying), an organosilicon compound can be provided by performing the heat processing mentioned later. The application, drying and firing of the organosilicon compound can be carried out by repeating a part of the operation or a series of these operations as needed.
また、ディップコーティング法では、分散液の粘度や有機ケイ素化合物の濃度、ディップ回数等を調整することによって、付与する有機ケイ素化合物の厚みを制御することができる。有機ケイ素化合物を付与する厚みは、特に限定されないが、例えば、凡そ０．１ｎｍ〜１０００ｎｍ（好ましくは凡そ０．５ｎｍ〜１００ｎｍ、より好ましくは凡そ０．５ｎｍ〜５０ｎｍ）程度とすることができる。これによって、好適な量の有機ケイ素化合物が付与されるため、有機多孔質体の化学的安定性を向上させることができる。なお、かかる厚みは例えば一般的な電子顕微鏡（典型的には透過型電子顕微鏡）によって、観察し得る。 In the dip coating method, the thickness of the organosilicon compound to be applied can be controlled by adjusting the viscosity of the dispersion, the concentration of the organosilicon compound, the number of dip, and the like. The thickness to which the organosilicon compound is applied is not particularly limited, but can be, for example, about 0.1 nm to 1000 nm (preferably about 0.5 nm to 100 nm, more preferably about 0.5 nm to 50 nm). As a result, a suitable amount of the organosilicon compound is provided, so that the chemical stability of the organic porous body can be improved. The thickness can be observed, for example, with a general electron microscope (typically a transmission electron microscope).
＜熱処理＞
そして、上記有機ケイ素化合物を付与した多孔質材を、少なくとも有機ケイ素化合物の沸点よりも高い温度で熱処理する。ここで開示される製造方法では、上記熱処理後に、有機ケイ素化合物由来のフッ素原子（もしくは官能基）が、無機多孔質体の少なくとも一部の表面に残存している。このため、該多孔質材の化学的安定性および／または疎水性が従来に比べ向上している。したがって、例えば強アルカリ溶液中における該多孔質材の耐腐食性を向上し得る。また、ここで開示される製造方法では、上記フッ素含有有機ケイ素化合物を付与した後に熱処理を施すことにより、該有機ケイ素化合物を本発明の効果が損なわれない程度に除去している。このため、多孔質材の気孔が好適に保たれており、例えば、該多孔質材を支持体に用いた分離膜エレメントでは、高い分離能（例えば、ガス透過性）を発揮することができる。
<Heat treatment>
And the porous material which provided the said organosilicon compound is heat-processed at the temperature higher than the boiling point of an organosilicon compound at least. In the production method disclosed herein, after the heat treatment, fluorine atoms (or functional groups) derived from the organosilicon compound remain on at least a part of the surface of the inorganic porous body. For this reason, the chemical stability and / or hydrophobicity of the porous material is improved as compared with the prior art. Therefore, for example, the corrosion resistance of the porous material in a strong alkaline solution can be improved. Further, in the production method disclosed herein, the organosilicon compound is removed to such an extent that the effects of the present invention are not impaired by applying the heat treatment after the fluorine-containing organosilicon compound is applied. For this reason, the pores of the porous material are suitably maintained. For example, in a separation membrane element using the porous material as a support, high separation ability (for example, gas permeability) can be exhibited.
かかる熱処理では、フッ素原子を含む有機ケイ素化合物が、炭素原子（Ｃ）、酸素原子（Ｏ）、フッ素原子（Ｆ）、ケイ素原子（Ｓｉ）等に分解される。これら原子の一部は、分解後に再び結合し、上記付与に用いた有機ケイ素化合物よりも分子量の小さい化合物（もしくは官能基）として多孔質膜の表面に付与され得る。この際、有機化合物にケイ素原子（Ｓｉ）が含まれていることで、上記無機多孔質材の表面にＳｉ−Ｓｉ結合、Ｓｉ−Ｎ結合、Ｓｉ−Ｃ結合のような結合を好適に生じ得る。このため、かかるケイ素原子（Ｓｉ）を介して、有機ケイ素化合物中に含まれるフッ素原子を、好適に無機多孔質材の表面に付加することができる。また上記結合は、比較的結合力が強いため、熱処理後においてもフッ素原子を好適に残存させることができる。 In such heat treatment, the organosilicon compound containing fluorine atoms is decomposed into carbon atoms (C), oxygen atoms (O), fluorine atoms (F), silicon atoms (Si), and the like. Some of these atoms can be recombined after decomposition and applied to the surface of the porous membrane as a compound (or functional group) having a molecular weight smaller than that of the organosilicon compound used for the above application. At this time, since the organic compound contains silicon atoms (Si), bonds such as Si—Si bonds, Si—N bonds, and Si—C bonds can be suitably generated on the surface of the inorganic porous material. . For this reason, the fluorine atom contained in an organosilicon compound can be suitably added to the surface of an inorganic porous material through this silicon atom (Si). Further, since the bond has a relatively strong bonding force, fluorine atoms can be suitably left even after heat treatment.
該無機多孔質体表面に存在するフッ素原子の分布状態は、例えば、ＳＥＭ−ＥＤＸ（走査型電子顕微鏡（ＳＥＭ：Ｓｃａｎｎｉｎｇ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ）―エネルギー分散型Ｘ線分光法（ＥＤＸ：Ｅｎｅｒｇｙ Ｄｉｓｐｅｒｓｉｖｅ Ｘ−ｒａｙ Ｓｐｅｃｔｒｏｍｅｔｒｙ））を用いて解析（分析）することで把握し得る。また、該フッ素原子の定量は、上記ＥＤＸに基づく分析値を補正（典型的には、ＺＡＦ法；原子番号効果補正（Ｚ）、吸収補正（Ａ）、蛍光励起補正（Ｆ）の３要因に係る補正）し、算出することができる。
ここで開示される製造方法における好適な一態様では、上記無機多孔質体を構成する金属原子（例えば、α―アルミナの場合は、Ａｌ原子）１００原子数に対し、フッ素原子の数が０．１原子数以上、例えば０．１原子数以上１００原子数以下、好ましくは１原子数以上５０原子数以下であり、より好ましくは１原子数以上１０原子数以下である。上記組成比率で構成された無機多孔質材では、該多孔質材の表面にフッ素含有有機ケイ素化合物由来のフッ素原子が好適に残存している。このため該多孔質材の気孔を塞ぐことなく（即ち本来の性能を保ったまま）、該多孔質体の化学的安定性を従来に比べ向上させることができる。
The distribution state of fluorine atoms present on the surface of the inorganic porous material is, for example, SEM-EDX (Scanning Electron Microscope (SEM) -Energy Dispersive X-ray Spectrometry (EDX). )) Can be used for analysis (analysis). The fluorine atom is quantified by correcting the analysis value based on the EDX (typically, ZAF method; atomic number effect correction (Z), absorption correction (A), and fluorescence excitation correction (F). Correction) and can be calculated.
In a preferred embodiment of the production method disclosed herein, the number of fluorine atoms is 0.1 relative to the number of metal atoms (for example, Al atom in the case of α-alumina) constituting the inorganic porous body. 1 atom number or more, for example, 0.1 atom number or more and 100 atom number or less, preferably 1 atom number or more and 50 atom number or less, more preferably 1 atom number or more and 10 atom number or less. In the inorganic porous material having the above composition ratio, fluorine atoms derived from the fluorine-containing organosilicon compound are suitably left on the surface of the porous material. For this reason, the chemical stability of the porous body can be improved as compared with the prior art without blocking the pores of the porous material (that is, while maintaining the original performance).
なお、無機多孔質体の表面には、上記フッ素原子（Ｆ）の他に、炭素原子（Ｃ）や酸素原子（Ｏ）、ケイ素原子（Ｓｉ）等が存在していてもよい。例えば、上記無機多孔質体を構成する金属原子の数１００に対して、炭素原子の数は、３００〜６００（好ましくは４００〜５００、より好ましくは４５０±２５）であることが好ましい。また酸素原子の数は、上記金属原子の数１００に対して、５０〜３００（好ましくは１００〜２５０、より好ましくは１７５±２５）であることが好ましい。また、ケイ素原子の数は、上記金属原子の数１００に対して、少なくとも０．１（例えば０．１以上１００以下、好ましくは１以上５０以下）であることが好ましい。 In addition to the fluorine atom (F), a carbon atom (C), an oxygen atom (O), a silicon atom (Si), or the like may be present on the surface of the inorganic porous body. For example, it is preferable that the number of carbon atoms is 300 to 600 (preferably 400 to 500, more preferably 450 ± 25) with respect to the number 100 of metal atoms constituting the inorganic porous body. The number of oxygen atoms is preferably 50 to 300 (preferably 100 to 250, more preferably 175 ± 25) based on the number 100 of the metal atoms. The number of silicon atoms is preferably at least 0.1 (for example, 0.1 to 100, preferably 1 to 50) with respect to the number 100 of the metal atoms.
上記熱処理の温度は、少なくとも有機ケイ素化合物の沸点よりも高い温度であれば、付与した有機ケイ素化合物の種類や、熱処理の温度等に応じて適宜変更することができる。熱処理の温度が使用した有機ケイ素化合物の沸点よりも低い場合（典型的には１００℃以下、例えば５０℃）は、付与した有機ケイ素化合物が十分に除去されず、無機多孔質材の気孔が塞がれてしまうため、分離、精製など多孔質本来の機能性を発揮し得ない虞がある。一方、熱処理温度が高すぎる場合（典型的には６００℃以上、例えば１０００℃）は、有機ケイ素化合物が完全に気化してしまい、ここで開示される製造方法の効果が薄れる虞がある。よって、かかる熱処理の温度は、例えば１００℃以上であって、典型的には１００℃以上６００℃以下、例えば１５０℃以上４５０℃以下、好ましくは２００℃以上４００℃以下とすることができる。また、熱処理時間としては、例えば、凡そ０．５時間以上３時間以下（好ましくは０．５時間以上２時間以下）に設定することができる。熱処理温度を上記範囲とすることで、無機多孔質材の表面から有機ケイ素化合物を好適に取り除くことができる。このため、該多孔質材の気孔を塞ぐことなく、好適に本発明の効果（即ち、化学的安定性の向上）を発揮することができる。 If the temperature of the said heat processing is a temperature higher than the boiling point of an organosilicon compound at least, it can change suitably according to the kind of provided organosilicon compound, the temperature of heat processing, etc. When the temperature of the heat treatment is lower than the boiling point of the organosilicon compound used (typically 100 ° C. or less, for example, 50 ° C.), the applied organosilicon compound is not sufficiently removed, and the pores of the inorganic porous material are blocked. Therefore, there is a possibility that the original functionality of the porous material such as separation and purification cannot be exhibited. On the other hand, when the heat treatment temperature is too high (typically 600 ° C. or higher, for example, 1000 ° C.), the organosilicon compound is completely vaporized, and the effect of the production method disclosed herein may be diminished. Therefore, the temperature of the heat treatment is, for example, 100 ° C. or higher, and typically 100 ° C. or higher and 600 ° C. or lower, for example, 150 ° C. or higher and 450 ° C. or lower, preferably 200 ° C. or higher and 400 ° C. or lower. Moreover, as heat processing time, it can set to about 0.5 hour or more and 3 hours or less (preferably 0.5 hour or more and 2 hours or less), for example. By setting the heat treatment temperature within the above range, the organosilicon compound can be suitably removed from the surface of the inorganic porous material. For this reason, the effect (namely, improvement of chemical stability) of this invention can be exhibited suitably, without plugging the pore of this porous material.
多孔質体に形成されている気孔の孔径（気孔径）は、用途に応じて適したサイズとすることができる。例えば、サブミクロン以上（例えば０．１μｍ以上、好ましくは１μｍ以上）であって、１００μｍ以下（好ましくは５０μｍ以下、例えば３０μｍ以下）とすることができる。上記範囲を満たす無機多孔質材料は、比較的気孔径が大きいため、例えば後述するガス分離膜の支持体として好適に用いることができる。即ち、高いガス分離能や十分な機械的強度を保ちつつ、本発明の効果により化学的安定性を向上し得る。
また、多孔質体の気孔率は、例えば１０％〜７５％、好ましくは２０％〜６０％、より好ましくは３０％〜５０％であるとよい。また、例えば相対的に気孔径が大きい多孔質層の表面に、気孔径がより小さい多孔質層を積層したような、非対称構造の支持体であってもよい。さらに、三層以上の多孔質層が積層された（好ましくは、上層側すなわち多孔質基材が設けられる側に近い層ほど気孔径が小さくなるように積層された）構造の支持体であってもよい。
The pore diameter (pore diameter) of the pores formed in the porous body can be set to a suitable size according to the application. For example, it can be submicron or more (for example, 0.1 μm or more, preferably 1 μm or more) and 100 μm or less (preferably 50 μm or less, for example, 30 μm or less). Since the inorganic porous material satisfying the above range has a relatively large pore diameter, for example, it can be suitably used as a support for a gas separation membrane described later. That is, chemical stability can be improved by the effect of the present invention while maintaining high gas separation ability and sufficient mechanical strength.
The porosity of the porous body is, for example, 10% to 75%, preferably 20% to 60%, and more preferably 30% to 50%. Further, for example, a support having an asymmetric structure in which a porous layer having a smaller pore diameter is laminated on the surface of a porous layer having a relatively larger pore diameter may be used. Furthermore, a support having a structure in which three or more porous layers are laminated (preferably, the layers closer to the upper layer side, that is, the side on which the porous substrate is provided, is laminated so that the pore diameter becomes smaller). Also good.
＜無機多孔質体の使用＞
ここで開示されるいずれかの製造方法によって得られた無機多孔質体は、種々の用途に用いることができる。例えば、該無機多孔質体では化学的安定性（典型的には耐腐食性、例えば耐アルカリ性）や疎水性が従来に比べ向上しているため、使用時に腐食性物質（強酸性、強アルカリ性、有機溶剤）と接触し得る場合に好適に用いることができる。かかる一例として、上記無機多孔質体を支持体とし、該支持体の上に分離膜（例えば、酸素分離膜、水素分離膜、窒素分離膜等）を備えた分離膜エレメントが挙げられる。
<Use of inorganic porous material>
The inorganic porous material obtained by any of the production methods disclosed herein can be used for various applications. For example, since the inorganic porous body has improved chemical stability (typically corrosion resistance, for example, alkali resistance) and hydrophobicity as compared with conventional materials, corrosive substances (strongly acidic, strongly alkaline, It can be suitably used when it can come into contact with an organic solvent. As an example, a separation membrane element including the inorganic porous material as a support and a separation membrane (for example, an oxygen separation membrane, a hydrogen separation membrane, a nitrogen separation membrane) on the support can be mentioned.
図１に、無機多孔質体を用いた分離膜エレメント１を模式的に示す。図１では、チューブ状の無機多孔質体が支持体１０として用いられ、該支持体１０の外周面１０ａを覆うように分離膜（多孔質膜）２０が形成されている。そして、例えば水（水蒸気を含む）とガス（例えば、酸素（Ｏ２））とが混合している混合物から酸素ガスのみを分離する場合は、上記混合物を分離膜２０に接触させ、所定の圧力で加圧する。すると、酸素ガスのみが分離膜２０を透過し、支持体１０側（即ち、チューブ状の支持体の内側）に流入する。ここで開示される該多孔質体１０では化学的安定性および／または疎水性が従来に比べ向上している。このため、例えば還元雰囲気下等においても、水と酸素ガスとの混合物から酸素ガスのみを好適に分離することができる。 FIG. 1 schematically shows a separation membrane element 1 using an inorganic porous material. In FIG. 1, a tubular inorganic porous material is used as the support 10, and a separation membrane (porous membrane) 20 is formed so as to cover the outer peripheral surface 10 a of the support 10. For example, when only oxygen gas is separated from a mixture in which water (including water vapor) and gas (for example, oxygen (O 2 )) are mixed, the mixture is brought into contact with the separation membrane 20 and a predetermined pressure is obtained. Pressurize with. Then, only oxygen gas permeate | transmits the separation membrane 20, and flows in into the support body 10 side (namely, inner side of a tube-shaped support body). The porous body 10 disclosed herein has improved chemical stability and / or hydrophobicity as compared with the conventional one. For this reason, for example, even in a reducing atmosphere, only oxygen gas can be suitably separated from the mixture of water and oxygen gas.
該分離膜エレメントの典型的な製造方法では、強アルカリ環境下における水熱処理によって、該多孔質体の表面に分離膜を形成する。より具体的には、例えば、先ずアルカリ水熱処理用の溶液（典型的には、純水中に、アルカリ源と、所定の割合で混合した分離膜の元素源とを溶解させ、高粘度（ゾル状を含む）の水溶液）を調製する。次に、該多孔質体のうち分離膜を形成したくない（もしくは形成不要な）部分に、目止め等の保護処理（例えば、キャップ、カバー、テープ等による保護）を施す。そして、耐熱耐圧性の容器（典型的にはオートクレーブ）に、上記水熱合成用原料溶液と、かかる保護処理を施した多孔質体とを入れ（典型的には上記原料溶液中に該多孔質体を浸漬させ）、分離膜が好適に形成されるような条件（温度、時間）で水熱処理する。かかる水熱処理の終了後、例えば３５℃〜８０℃程度の温水で洗浄し、常温（典型的には２５℃）〜１００℃程度の温度下で乾燥させることにより該多孔質体の表面上に分離膜を形成する。 In a typical manufacturing method of the separation membrane element, a separation membrane is formed on the surface of the porous body by hydrothermal treatment in a strong alkaline environment. More specifically, for example, first, a solution for heat treatment with alkali water (typically, an alkali source and an element source of a separation membrane mixed in a predetermined ratio are dissolved in pure water to obtain a high viscosity (sol Prepared in the form of an aqueous solution). Next, a protective treatment such as sealing (for example, protection with a cap, a cover, a tape, or the like) is applied to a portion of the porous body where a separation membrane is not desired (or need not be formed). Then, the hydrothermal synthesis raw material solution and the porous body subjected to such protection treatment are placed in a heat and pressure resistant container (typically an autoclave) (typically, the porous material is contained in the raw material solution). The body is immersed) and hydrothermally treated under conditions (temperature, time) such that a separation membrane is suitably formed. After completion of the hydrothermal treatment, for example, it is washed with warm water of about 35 ° C. to 80 ° C. and dried on the surface of the porous body by drying at a temperature of room temperature (typically 25 ° C.) to about 100 ° C. A film is formed.
ここで開示されるいずれかの製造方法は、他の側面として、例えば上記保護処理の代替として機能し得る。即ち、多孔質体表面のうち、水熱処理を施したくない部分に、ここで開示される製造方法によってあらかじめ疎水性および／または化学的安定性を付与することにより、目的とする部分にのみ選択的に水熱処理を施す（膜を形成する）ことができる。このため、目止め等の保護処理を行う必要がなく、例えばハニカム構造のような複雑な形状の多孔質体に選択的な処理を施す場合に好適である。また、かかる製造方法によれば、該多孔質材の最表面上のみならず、気孔内（典型的には該気孔の内壁のうち開口部近傍の領域）にも好適に疎水性および／または化学的安定性が付与されているため、ナノ〜ミクロスケールで多孔質体内部の反応（膜形成）をも阻止し得る。 Any of the manufacturing methods disclosed herein can function as another aspect, for example, as an alternative to the protection treatment. That is, by selectively imparting hydrophobicity and / or chemical stability to the portion of the porous body surface that is not to be subjected to hydrothermal treatment by the manufacturing method disclosed herein, it is selective only to the target portion. Can be subjected to hydrothermal treatment (forming a film). For this reason, it is not necessary to carry out a protective treatment such as sealing, which is suitable for a case where a selective treatment is applied to a porous body having a complicated shape such as a honeycomb structure. Further, according to such a production method, not only on the outermost surface of the porous material, but also in the pores (typically, the region near the opening portion of the inner wall of the pores) is preferably hydrophobic and / or chemically Therefore, the reaction (film formation) inside the porous body can be prevented at the nano to micro scale.
次に、本発明に関する実施例を説明する。本実施例では、無機多孔質材としてのセラミックを用いて製造した多孔質体の特性評価を行った。なお、以下で説明する実施例は、本発明を限定することを意図したものではない。 Next, examples relating to the present invention will be described. In this example, characteristics of a porous body manufactured using ceramic as an inorganic porous material were evaluated. Note that the examples described below are not intended to limit the present invention.
＜実施例１＞
先ず、無機多孔質材としての酸化アルミニウム粉末（α―アルミナ、平均粒径３μｍ）と、バインダ（セルロース系ポリマー）とを、分散媒（水）に分散させることによって、押出成形用坏土を調製した。次に、押出成形を用いて押出成形用坏土をチューブ状に成形した。この成形体を空気雰囲気下で焼成（温度：１５００℃、時間：２時間）することによって、チューブ状の多孔質材を作製した。該多孔質材の気孔率は４０％、気孔径は９μｍであった。
<Example 1>
First, a clay for extrusion molding is prepared by dispersing an aluminum oxide powder (α-alumina, average particle size 3 μm) as an inorganic porous material and a binder (cellulosic polymer) in a dispersion medium (water). did. Next, the extrusion-molded clay was formed into a tube shape using extrusion molding. The molded body was fired in an air atmosphere (temperature: 1500 ° C., time: 2 hours) to produce a tubular porous material. The porosity of the porous material was 40%, and the pore diameter was 9 μm.
次に、得られた多孔質材を長さ１５ｍｍに切断し、圧縮空気を用いて表面の微小な異物を除去した。そして、該多孔質材の表面に、ディップコーティング法を用いてフッ素原子を含む有機ケイ素化合物を付与した。即ち、フッ素含有有機ケイ素化合物（ここでは、パーフルオロドデシルトリエトキシシラン（ＰＦＤＴＥＳ：ｐｅｒｆｌｕｏｒｏｄｏｄｅｃｙｌ―１Ｈ，１Ｈ，２Ｈ，２Ｈ−ｔｒｉｅｔｈｏｘｙｓｉｌａｎｅ）を用いた。）を含む溶液中に上記多孔質材を浸漬し、減圧処理（圧力：０．０１ＭＰａ、５分間）することで、該多孔質材の表面に凡そ５ｎｍの厚みで有機ケイ素化合物を付与した。 Next, the obtained porous material was cut into a length of 15 mm, and fine foreign substances on the surface were removed using compressed air. And the organosilicon compound containing a fluorine atom was provided to the surface of this porous material using the dip coating method. That is, the porous material is immersed in a solution containing a fluorine-containing organosilicon compound (here, perfluorododecyltriethoxysilane (PFDTES: perfluorododecyl-1H, 1H, 2H, 2H-triethoxysilane)) By carrying out pressure reduction treatment (pressure: 0.01 MPa, 5 minutes), the organosilicon compound was applied to the surface of the porous material with a thickness of about 5 nm.
そして、有機ケイ素化合物を付与した無機多孔質材を８０℃で乾燥し、３００℃で、２時間熱処理することで、上記付与した有機ケイ素化合物を適度に除去し、多孔質体（実施例１）を作製した。かかる多孔質体について、ＳＥＭ−ＥＤＸを用いてＡｌ（Ｋα）とＦ（Ｋα）とを定量したところ、Ａｌ原子を１００原子数とした場合に、Ｆ原子が４原子数存在していた。 Then, the inorganic porous material to which the organosilicon compound was imparted was dried at 80 ° C. and heat treated at 300 ° C. for 2 hours, so that the imparted organosilicon compound was appropriately removed, and the porous body (Example 1) Was made. About this porous body, when Al (K (alpha)) and F (K (alpha)) were quantified using SEM-EDX, when Al atom was made into 100 atomic number, F atom existed 4 atomic number.
＜実施例２＞
上記、熱処理温度を４００℃としたこと以外は、実施例１と同様の方法により多孔質体（実施例２）を作製した。
<Example 2>
A porous body (Example 2) was produced in the same manner as in Example 1 except that the heat treatment temperature was 400 ° C.
＜比較例１＞
比較例として、上記多孔質材そのもの（即ち、有機ケイ素化合物の付与および熱処理を施していないもの）を用意した。
<Comparative Example 1>
As a comparative example, the porous material itself (that is, a material that has not been provided with an organosilicon compound and not subjected to heat treatment) was prepared.
＜比較例２＞
比較例として、上記多孔質材そのものを用いた(即ち、有機ケイ素化合物を付与しなかった)こと以外は、実施例１と同様の方法により多孔質体（比較例２）を作製した。
<Comparative example 2>
As a comparative example, a porous body (Comparative Example 2) was produced in the same manner as in Example 1 except that the porous material itself was used (that is, no organosilicon compound was added).
＜比較例３＞
比較例として、上記多孔質材そのものを用いた(即ち、有機ケイ素化合物を付与しなかった)こと以外は、実施例２と同様の方法により多孔質体（比較例３）を作製した。
上述した各多孔質体の構成について下表１に纏める。
<Comparative Example 3>
As a comparative example, a porous body (Comparative Example 3) was produced in the same manner as in Example 2 except that the porous material itself was used (that is, the organosilicon compound was not added).
The structure of each porous body described above is summarized in Table 1 below.
〔疎水性試験〕
上記得られた多孔質体について、親水性／疎水性を評価した。ここでは、ＪＩＳ Ｒ ３２５７（１９９９）に準拠し、水接触角θを測定した。具体的には、１μＬの水をサンプルの表面に滴下し、サンプルの表面と滴下した水滴の接線との成す角度を、水接触角θ（°）とし、θ／２法を用いて水接触角θを測定した。結果を下表２に示す。
[Hydrophobic test]
The obtained porous body was evaluated for hydrophilicity / hydrophobicity. Here, the water contact angle θ was measured according to JIS R 3257 (1999). Specifically, 1 μL of water is dropped on the surface of the sample, and the angle between the surface of the sample and the tangent of the dropped water droplet is defined as the water contact angle θ (°), and the water contact angle using the θ / 2 method. θ was measured. The results are shown in Table 2 below.
表２に示すように、比較例では接触角が０°（即ち超親水性）だったのに対し、実施例の多孔質体は、アルカリ溶液浸漬前後共に接触角θが大きな値だった。このため、ここで開示される製造方法によって製造された多孔質体は、アルカリ溶液に浸漬しても疎水性を好適に維持し得る特性を有していることが示された。 As shown in Table 2, the contact angle in the comparative example was 0 ° (that is, superhydrophilicity), whereas the porous body of the example had a large contact angle θ before and after immersion in the alkaline solution. For this reason, it was shown that the porous body manufactured by the manufacturing method disclosed here has a characteristic that can maintain hydrophobicity suitably even when immersed in an alkaline solution.
〔耐アルカリ性試験〕
上記得られた多孔質体について、アルカリ溶液に対する耐久性を評価した。具体的には、９０℃に加熱した水酸化ナトリウム水溶液中（濃度：１２質量％）に、上記多孔質体を５時間浸漬した。そして、浸漬前後における質量変化を計測した。浸漬前の質量（Ｗｂ）と、浸漬後の質量（Ｗａ）との比（（Ｗａ／Ｗｂ）×１００）を質量変化率（％）として、表３の該当箇所に示す。
また、上記試験に用いた水酸化ナトリウム水溶液について、ＩＣＰ−発光分光法（ＩＣＰ−ＡＥＳ：Ｉｎｄｕｃｔｉｖｅｌｙ Ｃｏｕｐｌｅｄ Ｐｌａｓｍａ―Ａｔｏｍｉｃ Ｅｍｉｓｓｉｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｙ）を用いて分析し、該溶液中に含まれる成分（元素）を定量した。具体的には、ＩＣＰ−ＡＥＳ（型式「ＳＰＳ３５００」、エスアイアイ・ナノテクノロジー社製）を用いて、該多孔質体の主成分であるＡｌ元素とＳｉ元素について定量した。下表３の該当箇所に定量結果を示す。なお、下表３中の「Ｂｌａｎｋ」は、本試験に用いた水酸化ナトリウム水溶液のみの分析値（バックグラウンド値）を意味する。
[Alkali resistance test]
About the obtained porous body, durability with respect to an alkaline solution was evaluated. Specifically, the porous body was immersed in a sodium hydroxide aqueous solution heated to 90 ° C. (concentration: 12% by mass) for 5 hours. And the mass change before and behind immersion was measured. Table 3 shows the ratio of mass (W b ) before immersion to mass (W a ) after immersion ((W a / W b ) × 100) as a mass change rate (%).
Further, the aqueous solution of sodium hydroxide used in the above test was analyzed using ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectroscopy), and the components (elements) contained in the solution were quantified. . Specifically, using an ICP-AES (model “SPS3500”, manufactured by SII NanoTechnology Co., Ltd.), the Al element and the Si element as the main components of the porous body were quantified. The quantitative results are shown in the corresponding places in Table 3 below. In addition, “Blank” in the following Table 3 means an analytical value (background value) of only the sodium hydroxide aqueous solution used in this test.
さらに、アルカリ溶液に対する耐性を別の角度からも検討すべく、上記得られた多孔質体について、圧縮破壊試験を行った。具体的には、ＪＩＳ Ｒ １６０８（２００３）に準拠して、試験片たる円柱状の多孔質体を、加圧可能な試験機に設置し、０．５ｍｍ／ｍｉｎ．の速度で負荷を加えていき、試験片が圧縮破壊するまでの間における最大荷重を測定した。そして、下式（１）を用いて圧縮強度（Ｐａ）を算出した。そして浸漬前の圧縮強度（σｂ）と、浸漬後の圧縮強度（σａ）との比（（σａ／σｂ）×１００）を強度変化率（％）として、表３の該当箇所に示す。なお、表３中の「Ｎ．Ａ．」は、未計測であることを示す。
σ＝４Ｐ／πｄ２ （１）
ただし、σ；圧縮強さ（Ｐａ）
Ｐ；試験片が圧縮破壊した時の最大荷重（Ｎ）
ｄ；試験片の直径（ｍ）
Further, in order to examine the resistance to the alkaline solution from another angle, a compression fracture test was performed on the obtained porous body. Specifically, in accordance with JIS R 1608 (2003), a cylindrical porous body as a test piece is placed in a pressurizable tester and 0.5 mm / min. The load was applied at a speed of 1 mm, and the maximum load until the specimen was compressively fractured was measured. And compressive strength (Pa) was computed using the following formula (1). The ratio of compressive strength before immersion (σ b ) and compressive strength after immersion (σ a ) ((σ a / σ b ) × 100) is defined as the rate of change in strength (%). Show. In Table 3, “NA” indicates that no measurement has been performed.
σ = 4P / πd 2 (1)
Where σ: compressive strength (Pa)
P: Maximum load when the test piece is compressed and fractured (N)
d: Diameter of test piece (m)
表３に示すように、有機ケイ素化合物を付与しなかった比較例では、耐アルカリ性試験の前後における質量変化が大きく、また該試験に用いたアルカリ溶液中にＡｌやＳｉが大量に検出されたことから、該多孔質体がアルカリ溶液に侵され溶出したことが示された。
一方、多孔質体の表面に有機ケイ素化合物を付与した実施例では、耐アルカリ性試験の前後における質量変化が顕著に小さかった。また、該試験に用いたアルカリ溶液では、検出されたＡｌやＳｉが比較的少なく、アルカリ溶液に対し優れた耐性を有していることが示された。さらに、実施例の多孔質体はアルカリ溶液の浸漬前後で圧縮破壊強度の変化も小さかった。よって、ここで開示される製造方法は、化学的安定性（例えば耐アルカリ性）を向上させるだけでなく、該多孔質体の機械的強度を保つという観点からも有効であることがわかった。
As shown in Table 3, in the comparative example in which the organosilicon compound was not applied, mass change before and after the alkali resistance test was large, and a large amount of Al and Si was detected in the alkaline solution used in the test. From this, it was shown that the porous body was infiltrated with the alkaline solution.
On the other hand, in the Example which provided the organosilicon compound on the surface of the porous body, the mass change before and after the alkali resistance test was remarkably small. Moreover, it was shown that the alkaline solution used in the test has relatively little Al or Si detected and has excellent resistance to the alkaline solution. Furthermore, the porous bodies of the examples had little change in compressive fracture strength before and after immersion in the alkaline solution. Therefore, it has been found that the production method disclosed here is effective not only in improving the chemical stability (for example, alkali resistance) but also in maintaining the mechanical strength of the porous body.
＜アルカリ水熱処理＞
次に、応用的な用途の一検討として、アルカリ水熱合成法により分離膜を作製（成膜）する工程を検討した。具体的には、先ず、ゼオライト分離膜の原料となるアルカリ源（水酸化ナトリウム）と、アルミナ源（塩化アルミニウム）と、シリカ源（ケイ酸ナトリウム（水ガラス））とを、溶媒（純水）中に溶解させ、ゼオライト合成溶液を調製した。次に、上記多孔質体（実施例２、比較例１）を、調製したゼオライト合成溶液中に浸漬し、所定の条件（８０℃、５時間）で水熱処理した。そして、水熱処理前後の多孔質体について、走査型電子顕微鏡観察を行った。実施例２に係るＳＥＭ写真を図２（水熱処理前）および図３（水熱処理後）に、比較例１に係るＳＥＭ写真を図４（水熱処理前）および図５（水熱処理後）に示す。
<Alkaline hydrothermal treatment>
Next, as an application study, a process for producing (forming) a separation membrane by an alkaline hydrothermal synthesis method was examined. Specifically, first, an alkali source (sodium hydroxide), an alumina source (aluminum chloride), and a silica source (sodium silicate (water glass)), which are raw materials for the zeolite separation membrane, are used as a solvent (pure water). A zeolite synthesis solution was prepared by dissolving in the solution. Next, the porous body (Example 2, Comparative Example 1) was immersed in the prepared zeolite synthesis solution and hydrothermally treated under predetermined conditions (80 ° C., 5 hours). The porous body before and after hydrothermal treatment was observed with a scanning electron microscope. FIG. 2 (before hydrothermal treatment) and FIG. 3 (after hydrothermal treatment) show SEM photographs according to Example 2, and FIG. 4 (before hydrothermal treatment) and FIG. 5 (after hydrothermal treatment) show SEM photographs according to Comparative Example 1. .
図２、３に示すように、多孔質体の表面に有機ケイ素化合物を付与した多孔質体（実施例２）では、水熱処理前後で、該表面形状に大きな変化は見られなかった。これに対し、比較例１の多孔質体（多孔質体そのもの）では、水熱処理前（図４）に比べ、水熱処理後（図５）では、該多孔質体表面の不規則な層の発達が見られた。これは、長時間の水熱処理によって、不均一核生成（例えば、該多孔質材を形成する金属元素を中心とした核成長）が生じ、新たな層が形成されたものと考えられる。
よって、ここで開示される多孔質体の一つの応用的な用途として、例えば目止め等の保護処理の代替として機能し得ることが考えられる。即ち、該多孔質体表面のうち、水熱処理を施したくない部分に、ここで開示される製造方法によってあらかじめ疎水性および／または化学的安定性を付与することにより、目的とする部分にのみ選択的に水熱処理を施し、分離膜を形成させ得ることが示された。
As shown in FIGS. 2 and 3, in the porous body (Example 2) in which the organosilicon compound was added to the surface of the porous body, no significant change was observed in the surface shape before and after the hydrothermal treatment. On the other hand, in the porous body of Comparative Example 1 (porous body itself), the development of an irregular layer on the surface of the porous body after hydrothermal treatment (FIG. 5) compared to before hydrothermal treatment (FIG. 4). It was observed. This is probably because non-uniform nucleation (for example, nucleation centered on the metal element forming the porous material) occurred due to the hydrothermal treatment for a long time, and a new layer was formed.
Therefore, as one application of the porous body disclosed herein, it can be considered that it can function as an alternative to a protective treatment such as sealing. That is, by selecting hydrophobic portions and / or chemical stability in advance on the surface of the porous body that is not to be subjected to hydrothermal treatment by the manufacturing method disclosed herein, only the target portion is selected. It was shown that a hydrothermal treatment can be applied to form a separation membrane.
さらに、ここで開示される製造方法において好適な無機多孔質材を検討するため、異なる多孔質材を用いて検討を行った。
＜実施例１１＞
本例では、複合酸化物たる、ムライト（３Ａｌ２Ｏ３・２ＳｉＯ２）を用いたこと以外は、上述した実施例１と同様の手法により、多孔質材をチューブ状に成形した。なお、該多孔質材の気孔率は４１％、気孔径は３．３μｍだった。そして、熱処理温度を１５０℃としたこと以外は、実施例１と同様の方法により多孔質体（実施例１１）を作製した。
Furthermore, in order to investigate the suitable inorganic porous material in the manufacturing method disclosed here, it examined using a different porous material.
<Example 11>
In this example, serving complex oxide, except for using a mullite (3Al 2 O 3 · 2SiO 2 ) is the same manner as in Example 1 described above, was molded porous material into a tube. The porous material had a porosity of 41% and a pore diameter of 3.3 μm. And the porous body (Example 11) was produced by the method similar to Example 1 except heat processing temperature having been 150 degreeC.
＜実施例１２＞
上記熱処理温度を３００℃としたこと以外は、実施例１１と同様の方法により多孔質体（実施例１２）を作製した。
<Example 12>
A porous body (Example 12) was produced in the same manner as in Example 11 except that the heat treatment temperature was 300 ° C.
＜比較例１１＞
比較例として、上記多孔質材そのもの（即ち、何も処理を施していないもの）を用意した。
上述した各サンプルの構成について下表４に纏める。
<Comparative Example 11>
As a comparative example, the porous material itself (that is, a material that has not been subjected to any treatment) was prepared.
The configuration of each sample described above is summarized in Table 4 below.
〔耐アルカリ性試験〕
上記得られた多孔質体について、上述した実施例１と同様に、アルカリ溶液に対する耐久試験を行い、浸漬前後におけるサンプルの質量変化を計測した。結果を表５に示す。
[Alkali resistance test]
About the obtained porous body, the durability test with respect to the alkaline solution was done like Example 1 mentioned above, and the mass change of the sample before and behind immersion was measured. The results are shown in Table 5.
表５に示すように、無機多孔質材として酸化アルミニウム粉末を用いた場合と同様に、（有機ケイ素化合物を付与した）実施例１１および１２の多孔質体は、比較例１１の多孔質体に比べ質量変化が小さかった。また、熱処理温度が１５０℃だった実施例１１に比べ、より高温（３００℃）で熱処理を施した実施例１２では質量変化が小さかった。
以上の結果より、フッ素含有有機ケイ素化合物としてＰＦＤＴＥＳを用いた本例では、熱処理の温度を、２００℃以上４００℃以下に設定すること好ましいことが示された。
As shown in Table 5, similarly to the case of using aluminum oxide powder as the inorganic porous material, the porous bodies of Examples 11 and 12 (to which the organosilicon compound was added) were replaced with the porous body of Comparative Example 11. The change in mass was small. Moreover, compared with Example 11 in which the heat treatment temperature was 150 ° C., the mass change was small in Example 12 in which the heat treatment was performed at a higher temperature (300 ° C.).
From the above results, it was shown that in this example using PFDTE as the fluorine-containing organosilicon compound, it is preferable to set the temperature of the heat treatment to 200 ° C. or more and 400 ° C. or less.
１ 分離膜エレメント
１０ 支持体（無機多孔質体）
２０ 分離膜（無機多孔質膜）
DESCRIPTION OF SYMBOLS 1 Separation membrane element 10 Support body (inorganic porous body)
20 Separation membrane (inorganic porous membrane)
Claims (6)
Ａｌ，Ｚｒ，Ｍｇ，Ｔｉ，Ｃｅ，Ｙ，ＢａおよびＦｅからなる群から選択される１種または２種以上の金属原子を含む無機多孔質材の表面に、少なくともフッ素原子を含む有機ケイ素化合物を付与すること、ここで、前記無機多孔質材としては、水銀圧入法に基づく平均孔径が１μｍ以上１００μｍ以下のものを用いる；および
前記フッ素含有有機ケイ素化合物が付与された前記無機多孔質材を、前記フッ素含有有機ケイ素化合物の沸点以上の温度で、前記無機多孔質材の少なくとも一部の表面に前記フッ素含有有機ケイ素化合物由来のフッ素原子が残存するよう熱処理すること、ここで、前記熱処理は、前記フッ素含有有機ケイ素化合物を適度に除去することにより、走査型電子顕微鏡―エネルギー分散型Ｘ線分光法に基づく分析で、前記無機多孔質材を構成する前記金属原子１００原子数に対して前記フッ素原子が１原子数以上５０原子数以下の割合で残存するように行う；
を包含する、セラミック分離膜の支持体の製造方法。 A method for producing a support for a ceramic separation membrane, a method for producing an alkali-resistant support,
An organosilicon compound containing at least a fluorine atom is formed on the surface of an inorganic porous material containing one or more metal atoms selected from the group consisting of Al, Zr, Mg, Ti, Ce, Y, Ba and Fe. Here, as the inorganic porous material, those having an average pore diameter of 1 μm or more and 100 μm or less based on a mercury intrusion method are used; and the inorganic porous material to which the fluorine-containing organosilicon compound is applied, at a temperature higher than the boiling point of the fluorine-containing organic silicon compound, the inorganic porous material at least a part of the surface from the fluorine-containing organic silicon compound fluorine atoms to heat treatment so that the remaining, wherein said heat treatment, by appropriately removing the fluorine-containing organic silicon compound, a scanning electron microscope - in based on energy dispersive X-ray spectroscopy analysis, the The fluorine atom to the metal atom 100 the number of atoms constituting the machine porous material performed as to leave at a rate of less than 50 atoms or the number 1 atoms;
A method for producing a support for a ceramic separation membrane.
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