JP3500994B2 - Hydrocarbon gas adsorbent composed of mesoporous material - Google Patents
Hydrocarbon gas adsorbent composed of mesoporous materialInfo
- Publication number
- JP3500994B2 JP3500994B2 JP35975298A JP35975298A JP3500994B2 JP 3500994 B2 JP3500994 B2 JP 3500994B2 JP 35975298 A JP35975298 A JP 35975298A JP 35975298 A JP35975298 A JP 35975298A JP 3500994 B2 JP3500994 B2 JP 3500994B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- mesoporous material
- porous body
- hydrocarbon gas
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000013335 mesoporous material Substances 0.000 title claims description 99
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 75
- 229930195733 hydrocarbon Natural products 0.000 title claims description 74
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 70
- 239000003463 adsorbent Substances 0.000 title claims description 39
- 239000011148 porous material Substances 0.000 claims description 145
- 125000000962 organic group Chemical group 0.000 claims description 65
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 37
- 125000000524 functional group Chemical group 0.000 claims description 30
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 21
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 description 130
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 109
- 239000002243 precursor Substances 0.000 description 54
- 238000001179 sorption measurement Methods 0.000 description 47
- 239000004094 surface-active agent Substances 0.000 description 45
- 238000010335 hydrothermal treatment Methods 0.000 description 38
- 238000000034 method Methods 0.000 description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- 125000004429 atom Chemical group 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 238000006467 substitution reaction Methods 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 238000009826 distribution Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- 238000003860 storage Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 12
- 239000000693 micelle Substances 0.000 description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 11
- 239000011229 interlayer Substances 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000006068 polycondensation reaction Methods 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000012265 solid product Substances 0.000 description 9
- 238000006482 condensation reaction Methods 0.000 description 8
- -1 organosilane compound Chemical class 0.000 description 8
- 239000002250 absorbent Substances 0.000 description 7
- 230000002745 absorbent Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- 229910001510 metal chloride Inorganic materials 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 150000002894 organic compounds Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- ONLPKGMCOFNAJA-UHFFFAOYSA-N 3-methoxysilylpropane-1-thiol Chemical compound CO[SiH2]CCCS ONLPKGMCOFNAJA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- KXALBLJBEDOYEY-UHFFFAOYSA-N COS(OC)(OC)CCC[SiH3] Chemical compound COS(OC)(OC)CCC[SiH3] KXALBLJBEDOYEY-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 150000001450 anions Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- XKXHCNPAFAXVRZ-UHFFFAOYSA-N benzylazanium;chloride Chemical compound [Cl-].[NH3+]CC1=CC=CC=C1 XKXHCNPAFAXVRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
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- 239000002781 deodorant agent Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
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- 230000005661 hydrophobic surface Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、メタンその他の炭
化水素ガスを可逆的に吸着し、貯蔵し得る炭化水素ガス
吸着剤に関する。TECHNICAL FIELD The present invention relates to a hydrocarbon gas adsorbent capable of reversibly adsorbing and storing methane and other hydrocarbon gases.
【０００２】[0002]
【従来の技術】地球温暖化が環境問題としてクローズア
ップされるなか、自動車の代替燃料としてメタンガス等
の炭化水素ガスが期待されている。例えば、自動車用燃
料としてメタンガスを用いた場合、通常のガソリンを燃
料とした場合に比べて排気ガス中の窒素酸化物、反応性
炭化水素、一酸化炭素等が著しく低減されるとともに、
二酸化炭素排出量も削減することができる。また、メタ
ンガスは天然ガスの主成分であるため、その埋蔵量が豊
富でありさらにオクタン価も高い。2. Description of the Related Art With global warming being highlighted as an environmental problem, hydrocarbon gas such as methane gas is expected as an alternative fuel for automobiles. For example, when methane gas is used as a fuel for automobiles, nitrogen oxides, reactive hydrocarbons, carbon monoxide, etc. in the exhaust gas are significantly reduced as compared with the case of using normal gasoline as fuel,
Carbon dioxide emissions can also be reduced. Since methane gas is the main component of natural gas, its reserves are abundant and its octane number is high.
【０００３】ところで、産業用燃料として使用し得る炭
化水素ガスやそれを主成分とする天然ガスを貯蔵する手
段としては、従来、圧縮ボンベによる圧縮貯蔵、融点以
下の超低温にする液化貯蔵または繊維状活性炭、ゼオラ
イト等のガス吸収剤を利用した吸着貯蔵があり、用途に
応じてこれら貯蔵手段が使い分けられている。By the way, as a means for storing a hydrocarbon gas which can be used as an industrial fuel or a natural gas containing the hydrocarbon gas as a main component, conventionally, compression storage by a compression cylinder, liquefaction storage at ultra-low temperature below melting point, or fibrous state is carried out. There is an adsorption storage using a gas absorbent such as activated carbon or zeolite, and these storage means are properly used according to the application.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、自動車
のような貯蔵スペースに限りがある対象物に効率よく多
量に炭化水素ガスを貯蔵する手段がこれまで開発されて
いない。例えば、上記圧縮貯蔵による場合、重たいガス
ボンベを積載するわりに貯蔵量が少なく、ガスボンベ積
載許容量にも限度があるため、燃料補給無しに長距離走
行することが困難であった。また、上記液化貯蔵による
場合、超低温（メタンの場合で−１６２℃以下）を維持
する装置が必要となるため、実用的でない。また、繊維
状活性炭やゼオライト等のガス吸収剤による従来の吸着
貯蔵による場合、当該ガス吸収剤自体が著しく嵩高であ
ることと容積あたりのガス吸収量が少ないことから、自
動車の限られたスペースに長距離走行に十分な量の炭化
水素ガス（即ち十分量の炭化水素ガスを吸収したガス吸
収剤）を貯蔵することは困難であった。However, a means for efficiently storing a large amount of hydrocarbon gas in an object having a limited storage space such as an automobile has not been developed so far. For example, in the case of the compressed storage described above, it is difficult to travel a long distance without refueling because the storage amount is small even if a heavy gas cylinder is loaded and the allowable loading amount of the gas cylinder is limited. Further, in the case of the above-mentioned liquefied storage, a device for maintaining an ultralow temperature (-162 ° C or less in the case of methane) is required, which is not practical. Further, in the case of the conventional adsorption storage using a gas absorbent such as fibrous activated carbon or zeolite, the gas absorbent itself is extremely bulky and the amount of gas absorbed per volume is small, so that it is limited to a limited space of an automobile. It has been difficult to store a sufficient amount of hydrocarbon gas for long-distance travel (that is, a gas absorbent that has absorbed a sufficient amount of hydrocarbon gas).
【０００５】本発明は、かかる従来の炭化水素ガス貯蔵
に関する問題点を解決するものであり、その目的とする
ところは、自動車のような限られた貯蔵スペースにも多
量に炭化水素ガスを貯蔵し得る実用的な吸着手段を提供
することである。The present invention solves the above-mentioned problems associated with conventional hydrocarbon gas storage, and its object is to store a large amount of hydrocarbon gas in a limited storage space such as an automobile. The purpose is to provide a practical adsorption means to be obtained.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、ある種の
メソ多孔体がメタンガスのような常温で気体の低級炭化
水素ガスを常温常圧下においてもよく吸着することを見
出し、本発明を完成するに至った。すなわち、上記課題
を解決するため、本発明は、無機系または無機／有機ハ
イブリッド系のメソ多孔体であって細孔壁面に有機基お
よび／または官能基を含む多孔体から実質的に構成され
る、炭素数１〜４の炭化水素ガス（これらに該当するガ
スを本明細書において「低級炭化水素ガス」と総称す
る。）を吸着させるための炭化水素ガス吸着剤を提供す
る。本明細書において「メソ多孔体」とは、中心細孔直
径（細孔直径分布曲線における最大ピークを示す細孔直
径をいう。詳細は後述する。）が０．５ｎｍ〜５０ｎｍ
である開放細孔（以下「メソ細孔」という。）を有する
無機系または無機／有機ハイブリッド（混成）系の多孔
質固体材料をいう。ここで無機系とは、多孔体を構成す
る基本骨格（主鎖）中に炭素を含まないものをいい、無
機／有機ハイブリッド系とは、多孔体を構成する基本骨
格（主鎖）中に１又は２以上の炭素原子を含む有機基が
部分的に含まれているものをいう。The present inventors have found that a certain kind of mesoporous material adsorbs a lower hydrocarbon gas such as methane gas, which is a gas at room temperature, well at room temperature and atmospheric pressure, and the present invention provides It came to completion. That is, in order to solve the above-mentioned problems, the present invention is substantially composed of an inorganic or inorganic / organic hybrid mesoporous material having a pore wall surface containing an organic group and / or a functional group. A hydrocarbon gas adsorbent for adsorbing a hydrocarbon gas having 1 to 4 carbon atoms (gases corresponding to these are collectively referred to as "lower hydrocarbon gas" in the present specification). In the present specification, the "mesoporous material" has a central pore diameter (a pore diameter showing a maximum peak in a pore diameter distribution curve. Details will be described later) of 0.5 nm to 50 nm.
An inorganic or inorganic / organic hybrid (mixed) type porous solid material having open pores (hereinafter referred to as “mesopores”). Here, the inorganic system means that the basic skeleton (main chain) forming the porous body does not contain carbon, and the inorganic / organic hybrid system means 1 in the basic skeleton (main chain) forming the porous body. Alternatively, it means one partially containing an organic group containing two or more carbon atoms.
【０００７】本発明の炭化水素ガス吸着剤によれば、上
記細孔を形成する孔壁部に有機基および／または官能基
を有する結果、常温で常圧またはそれ以下の圧力条件
下、メタンガス等の低級炭化水素ガス即ち常温常圧で気
体状態を保つ炭化水素を効率よく可逆的に吸着すること
ができる。さらに、本発明の炭化水素ガス吸着剤は多孔
質固体材料から実質的に構成されるため、容積比(cc/g)
が比較的小さく、繊維状活性炭のように嵩張ることがな
い。このため、本発明の炭化水素ガス吸着剤によれば、
自動車のような限られた貯蔵スペースに多量のメタンガ
ス等の上記炭化水素ガスをメソ多孔体に吸着した形態で
貯蔵することができる。According to the hydrocarbon gas adsorbent of the present invention, as a result of having an organic group and / or a functional group on the wall of the pores forming the above-mentioned pores, methane gas etc. can be obtained under normal pressure or lower pressure at room temperature. The lower hydrocarbon gas, that is, the hydrocarbon that maintains a gas state at room temperature and normal pressure can be efficiently and reversibly adsorbed. Furthermore, since the hydrocarbon gas adsorbent of the present invention is substantially composed of a porous solid material, the volume ratio (cc / g)
Is relatively small and does not become bulky like fibrous activated carbon. Therefore, according to the hydrocarbon gas adsorbent of the present invention,
A large amount of the above hydrocarbon gas such as methane gas can be stored in a limited storage space such as an automobile in the form of being adsorbed on the mesoporous material.
【０００８】本発明の炭化水素ガス吸着剤として好まし
いものは、上記有機基および／または官能基がチオール
基を含んでいる。これにより、メタンガス等の低級炭化
水素ガスの細孔内への吸着率を向上させることができ
る。このため、より実用的なガス吸収剤を提供すること
ができる。また、上記多孔体自体が金属原子を有してい
るもの或いは該多孔体の細孔内に金属原子を保持してい
るものが本発明のガス吸着剤として好ましい。これによ
り、メタンガス等の上記炭化水素ガスの細孔内への吸着
率をより向上させることができる。このため、特に実用
的なガス吸収剤を提供することができる。かかる金属原
子として銅および／またはニッケルを有しているもの
が、特にメタンガスその他の低級炭化水素ガスの吸着率
を向上させ得る。The preferred hydrocarbon gas adsorbent of the present invention has a thiol group as the organic group and / or functional group. This can improve the adsorption rate of the lower hydrocarbon gas such as methane gas into the pores. Therefore, a more practical gas absorbent can be provided. Further, the above-mentioned porous body itself having metal atoms or those having metal atoms in the pores of the porous body are preferable as the gas adsorbent of the present invention. This makes it possible to further improve the adsorption rate of the hydrocarbon gas such as methane gas into the pores. Therefore, a particularly practical gas absorbent can be provided. Those having copper and / or nickel as such metal atoms can improve the adsorption rate of methane gas and other lower hydrocarbon gas.
【０００９】また、本発明の炭化水素ガス吸着剤として
好ましいものは、上記多孔体がシリケート骨格を有する
シリカ系メソ多孔体であって水中で５０℃〜２００℃の
加熱処理を施して調製された多孔体である。このような
水熱処理を行うことによって、該多孔体の構造規則性
（細孔分布の均一性）が安定化される。このため、重量
および容積あたりのガス吸着効率が向上し、より実用に
適したメタンガスその他の低級炭化水素ガス吸収剤が提
供される。Further, a preferable hydrocarbon gas adsorbent of the present invention is a silica-based mesoporous material having a silicate skeleton as the above-mentioned porous body, which is prepared by subjecting it to a heat treatment at 50 ° C. to 200 ° C. in water. It is a porous body. By carrying out such a hydrothermal treatment, the structural regularity (uniformity of pore distribution) of the porous body is stabilized. Therefore, the gas adsorption efficiency per unit weight and volume is improved, and methane gas or other lower hydrocarbon gas absorbent more suitable for practical use is provided.
【００１０】[0010]
【発明の実施の形態】本発明は典型的には以下のように
実施され得る。BEST MODE FOR CARRYING OUT THE INVENTION The present invention can be typically implemented as follows.
【００１１】先ず、本発明の炭化水素ガス吸着剤を実質
的に構成するメソ多孔体について説明する。本発明に適
用し得るメソ多孔体は、メタンまたはその他の低級炭化
水素ガスを吸着し得る中心細孔直径が０．５ｎｍ〜５０
ｎｍである細孔を有する無機系または無機／有機ハイブ
リッド系多孔体である。このような多孔体へのメタン等
の低級炭化水素ガスの吸着（貯蔵）は、典型的には細孔
内への濃縮により起こると考えられる。すなわち、中心
細孔直径が上記範囲内となるメソ多孔体によると、細孔
内に強い吸着ポテンシャルの場が生じ得、結果、メタン
等の低級炭化水素ガスを細孔内に高度に濃縮することが
可能となる。First, the mesoporous material which substantially constitutes the hydrocarbon gas adsorbent of the present invention will be described. The mesoporous material applicable to the present invention has a central pore diameter of 0.5 nm to 50 capable of adsorbing methane or other lower hydrocarbon gas.
It is an inorganic or inorganic / organic hybrid porous body having a pore size of nm. Adsorption (storage) of lower hydrocarbon gas such as methane to such a porous body is considered to be typically caused by concentration in the pores. That is, according to a mesoporous material having a central pore diameter within the above range, a strong adsorption potential field can be generated in the pores, and as a result, a lower hydrocarbon gas such as methane can be highly concentrated in the pores. Is possible.
【００１２】本発明に使用する無機系メソ多孔体は、シ
リカ(SiO2)等の無機酸化物からなる３次元の基本骨格
（高分子主鎖）を有するシリカ系その他のメソ多孔体で
あって構造的にメタン等の低級炭化水素ガス分子を十分
に取り込み得る細孔を有する多孔体である。シリケート
基本骨格中のケイ素原子に代え得る原子としてまたはシ
リケート骨格に付加し得る他の原子としては、アルミニ
ウム、チタン、マグネシウム、ジルコニウム、タンタ
ル、ニオブ、モリブデン、コバルト、ニッケル、ガリウ
ム、ベリリウム、イットリウム、ランタン、ハフニウ
ム、スズ、鉛、バナジウム、ホウ素等が挙げられる。シ
リカその他の無機酸化物からなる基本骨格またはその側
鎖にニッケル、銅等の金属原子を有する無機系メソ多孔
体は上記低級炭化水素ガスを吸着する機能が向上するた
め特に好ましい。The inorganic mesoporous material used in the present invention is a silica-based or other mesoporous material having a three-dimensional basic skeleton (polymer main chain) made of an inorganic oxide such as silica (SiO 2 ). It is a porous body having pores structurally capable of sufficiently incorporating lower hydrocarbon gas molecules such as methane. As an atom that can replace the silicon atom in the silicate basic skeleton or as another atom that can be added to the silicate skeleton, aluminum, titanium, magnesium, zirconium, tantalum, niobium, molybdenum, cobalt, nickel, gallium, beryllium, yttrium, and lanthanum can be used. , Hafnium, tin, lead, vanadium, boron and the like. An inorganic mesoporous material having a basic skeleton made of silica or another inorganic oxide or a metal atom such as nickel or copper in the side chain thereof is particularly preferable because the function of adsorbing the lower hydrocarbon gas is improved.
【００１３】而して、このようなメソ多孔体における無
機酸化物の基本骨格（典型的には-Si-O-からなるシリケ
ート骨格）に対して側鎖として種々の有機基および／ま
たは官能基が結合した構造のメソ多孔体が本発明の炭化
水素ガス吸着剤にかかる無機系メソ多孔体として好まし
い。例えば、シリカ系メソ多孔体の表面に生じたシラノ
ール基(Si-OH) 等に、式：R -Si-(OCH3)3 で表される有
機メトキシシラン等の有機アルコキシシランまたは他の
有機シラン化合物を反応させることにより、当該多孔体
の表面（細孔壁面を含む。以下同じ。）に所望する有機
基や官能基を有するメソ多孔体を製造し得る。このよう
に、側鎖として有機基および／または官能基を導入する
ことによって、当該導入有機基および／または官能基の
性状に応じて細孔内を含むメソ多孔体の表面性状を改変
することができる。例えば、アルキル基等の疎水性基を
側鎖として導入することによって疎水的表面特性を当該
メソ多孔体に付与することができる。かかる疎水性基の
導入によってメソ多孔体の表面における疎水性結合能を
向上させ得る。また、末端にチオール基(-SH) を含む有
機基（例えば-(CH2)n -SH ；ｎは１以上の整数）を導入
する場合、トリスメトキシメルカプトプロピルシラン(S
i(OCH3) 3C3H6SH)等の末端チオール基含有有機シラン化
合物を反応させることにより、多孔体表面に末端チオー
ル基を含む有機基が付与された無機系メソ多孔体を合成
することができる。同様にして、メチル基(-CH3)やエチ
ル基(-C2H5) 等の低級アルキル基、フェニル基(-C6H5)
、カルボキシル基(-COOH) 、アミノ基(-NH2)等を包含
する種々の有機基を側鎖としてメソ多孔体表面に付与す
ることができる。チオール基、カルボキシル基等の官能
基を細孔壁面に有するメソ多孔体は、ニッケル、銅等の
金属原子（金属イオン、金属塩化物等の化合物に含まれ
る形態を含む。以下同じ。）を細孔内に高効率に結合
（典型的には配位結合）させ得るため、本発明のガス吸
着剤として特に好ましい。かかる金属原子は、メタン等
の低級炭化水素ガスを可逆的に吸着させる能力に優れる
からである。Thus, various organic groups and / or functional groups are provided as side chains with respect to the basic skeleton (typically, a silicate skeleton made of —Si—O—) of the inorganic oxide in such a mesoporous material. A mesoporous material having a structure in which is bonded is preferable as the inorganic mesoporous material for the hydrocarbon gas adsorbent of the present invention. For example, a silanol group (Si-OH) formed on the surface of a silica-based mesoporous material has an organic alkoxysilane such as an organic methoxysilane represented by the formula: R -Si- (OCH 3 ) 3 or another organic silane. By reacting the compound, a mesoporous material having a desired organic group or functional group on the surface of the porous material (including the pore wall surface; the same applies hereinafter) can be produced. Thus, by introducing an organic group and / or a functional group as a side chain, it is possible to modify the surface properties of the mesoporous material containing the inside of the pores according to the properties of the introduced organic group and / or functional group. it can. For example, hydrophobic surface characteristics can be imparted to the mesoporous material by introducing a hydrophobic group such as an alkyl group as a side chain. By introducing such a hydrophobic group, the hydrophobic binding ability on the surface of the mesoporous material can be improved. The organic group containing a thiol group (-SH) at the terminal (e.g., - (CH 2) n -SH; n is an integer of 1 or more) When introducing, tris methoxy mercaptopropyl silane (S
i (OCH 3 ) 3 C 3 H 6 SH) or other terminal thiol group-containing organosilane compound is reacted to synthesize an inorganic mesoporous material having an organic group containing a terminal thiol group on the surface of the porous material. be able to. Similarly, lower alkyl groups such as methyl group (-CH 3 ) and ethyl group (-C 2 H 5 ), phenyl group (-C 6 H 5 )
, Various carboxyl groups (—COOH), amino groups (—NH 2 ) and the like can be attached to the surface of the mesoporous material as side chains. The mesoporous material having a functional group such as a thiol group and a carboxyl group on the wall surface of the pores has fine metal atoms such as nickel and copper (including forms contained in compounds such as metal ions and metal chlorides; the same applies hereinafter). It is particularly preferable as the gas adsorbent of the present invention because it can be bound (typically, coordinate bond) in the pores with high efficiency. This is because such metal atoms have an excellent ability to reversibly adsorb lower hydrocarbon gas such as methane.
【００１４】一方、本発明に好ましい無機／有機ハイブ
リッド系メソ多孔体は、シリカ等の無機酸化物を基本骨
格（高分子主鎖）とするとともに構造的にメタン等の炭
化水素ガス分子を十分に取り込み得る細孔を有するメソ
多孔体であって該基本骨格中に１または２以上の炭素原
子を含む有機基が含まれる多孔体である。例えば、−Ｓ
ｉ−Ｏ−からなる基本骨格中のケイ素原子に炭素が直接
結合するいわゆる炭素−ケイ素結合を基本骨格に有する
メソ多孔体が好ましい。このような基本骨格中に組み入
れられる有機基としては、特に限定しないが、アルキル
鎖、アルケニル鎖、ビニル鎖、アルキニル鎖、シクロア
ルキル鎖、ベンゼン環、ベンゼン環を含む炭化水素鎖等
を構成する炭化水素基、例えばメチレン基(-CH2CH2-)や
フェニレン基(-C6H4-)が好ましい。かかる有機基部分に
さらに側鎖として、チオール基(-SH) 、カルボキシル基
(-COOH) 、メチル基(-CH3)やエチル基(-C2H5) 等の低級
アルキル基、フェニル基(-C6H5) 、アミノ基(-NH2)を有
するものが好ましい。また、チオール基、カルボキシル
基等の官能基を細孔壁面に有する無機／有機ハイブリッ
ド系メソ多孔体はニッケル、銅等の金属原子を細孔内に
吸着（典型的には配位結合）させ得る能力が向上するた
め、特に好ましい。On the other hand, the inorganic / organic hybrid mesoporous material preferred in the present invention has an inorganic oxide such as silica as a basic skeleton (polymer main chain) and is structurally sufficient to contain hydrocarbon gas molecules such as methane. It is a mesoporous material having pores that can be incorporated, and has a basic skeleton containing an organic group containing one or more carbon atoms. For example, -S
A mesoporous material having a so-called carbon-silicon bond in which carbon is directly bonded to a silicon atom in a basic skeleton composed of i-O-as a basic skeleton is preferable. The organic group incorporated in such a basic skeleton is not particularly limited, but a carbon chain constituting an alkyl chain, an alkenyl chain, a vinyl chain, an alkynyl chain, a cycloalkyl chain, a benzene ring, a hydrocarbon chain containing a benzene ring, or the like. hydrogen group, a methylene group (-CH 2 CH 2 -) or a phenylene group (-C 6 H 4 -) is preferred. Further as a side chain to the organic group portion, a thiol group (-SH), a carboxyl group
(-COOH), a lower alkyl group such as a methyl group (-CH 3) or ethyl (-C 2 H 5), phenyl group (-C 6 H 5), those having an amino group (-NH 2) preferred . Further, an inorganic / organic hybrid mesoporous material having a functional group such as a thiol group or a carboxyl group on the pore wall surface can adsorb (typically coordinate bond) a metal atom such as nickel or copper into the pore. It is particularly preferable because the ability is improved.
【００１５】本発明の炭化水素ガス吸着剤を構成するメ
ソ多孔体の細孔は、炭素数１〜４の炭化水素ガスを効率
よく吸着するように中心細孔直径が０．５ｎｍ〜５０ｎ
ｍの範囲内にあることが好ましい。天然ガス等に含まれ
るメタンガスを対象とする場合には、中心細孔直径が
０．５ｎｍ〜２ｎｍのメソ多孔体が特に好ましい。さら
にこれらのうち、細孔直径分布曲線における最大ピーク
を示す細孔直径の±４０％の範囲に全細孔容積の６０％
以上が含まれる細孔を有するメソ多孔体がメタンガスそ
の他の低級炭化水素ガス等の吸着効率を高めることから
好ましい。The pores of the mesoporous material constituting the hydrocarbon gas adsorbent of the present invention have a central pore diameter of 0.5 nm to 50 n so as to efficiently adsorb the hydrocarbon gas having 1 to 4 carbon atoms.
It is preferably within the range of m. When targeting methane gas contained in natural gas or the like, a mesoporous material having a central pore diameter of 0.5 nm to 2 nm is particularly preferable. Further, of these, 60% of the total pore volume is within ± 40% of the pore diameter showing the maximum peak in the pore diameter distribution curve.
A mesoporous material having pores containing the above is preferable because it enhances the adsorption efficiency of methane gas and other lower hydrocarbon gases.
【００１６】上記の細孔直径分布曲線は、次のようにし
て求められる。細孔直径分布曲線とは、細孔容積（Ｖ）
を細孔直径（Ｄ）で微分した値（ｄｖ／ｄＤ）を細孔直
径（Ｄ）に対してプロットした曲線をいう。そして、そ
の細孔直径分布曲線のｄｖ／ｄＤ値が最も大きくなる
（最大ピークを示す）細孔直径がここでいう中心細孔直
径である。細孔直径分布曲線は、例えば窒素ガスの吸着
量測定により得られる吸着等温線から種々の計算式で導
かれる。吸着等温線の測定法を以下に例示する。この方
法において最もよく用いられるガスは窒素である。ま
ず、メソ多孔体を、液体窒素温度（−１９６℃）に冷却
して、窒素ガスを導入し、その吸着量を定容量法あるい
は重量法で求める。導入する窒素ガスの圧力を徐々に増
加させ、各平衡圧に対する窒素ガスの吸着量をプロット
することにより吸着等温線を作成する。この吸着等温線
から、Cranston-Inklay 法、Pollimore -Heal 法、ＢＪ
Ｈ法等の計算式により、細孔直径分布曲線を求めること
ができる。そして、例えば、細孔直径分布曲線における
最大のピークが３．００ｎｍにある場合、中心細孔直径
は３．００ｎｍとなる。このとき、「細孔直径分布曲線
における最大ピークを示す細孔直径の±４０％の範囲に
全細孔容積の６０％以上が含まれる」とは、細孔直径が
１．８０〜４．２０ｎｍの範囲にある細孔の容積の総計
が、全細孔容積の６０％以上を占めているということで
ある。より具体的にいえば細孔直径分布曲線における細
孔直径１．８０〜４．２０ｎｍにある細孔の細孔容積の
積分値が曲線の全積分値の６０％以上を占めているとい
うことである。このような「細孔直径分布曲線における
最大ピークを示す細孔直径の±４０％の範囲に全細孔容
積の６０％以上が含まれる」ことを特徴とするメソ多孔
体は、実質的には細孔径が十分に均一であることを意味
するものといえる。The above-mentioned pore diameter distribution curve is obtained as follows. Pore diameter distribution curve is the pore volume (V)
Is a curve obtained by plotting a value (dv / dD) obtained by differentiating with respect to the pore diameter (D) with respect to the pore diameter (D). Then, the pore diameter at which the dv / dD value of the pore diameter distribution curve becomes the largest (shows the maximum peak) is the central pore diameter here. The pore diameter distribution curve is derived from various adsorption formulas from the adsorption isotherm obtained by measuring the adsorption amount of nitrogen gas, for example. The method for measuring the adsorption isotherm is exemplified below. The most commonly used gas in this method is nitrogen. First, the mesoporous material is cooled to liquid nitrogen temperature (−196 ° C.), nitrogen gas is introduced, and the adsorption amount is determined by the constant volume method or the gravimetric method. The adsorption isotherm is created by gradually increasing the pressure of the introduced nitrogen gas and plotting the adsorption amount of nitrogen gas with respect to each equilibrium pressure. From this adsorption isotherm, Cranston-Inklay method, Pollimore-Heal method, BJ
The pore diameter distribution curve can be obtained by a calculation formula such as the H method. Then, for example, when the maximum peak in the pore diameter distribution curve is 3.00 nm, the central pore diameter is 3.00 nm. At this time, "60% or more of the total pore volume is included in the range of ± 40% of the pore diameter showing the maximum peak in the pore diameter distribution curve" means that the pore diameter is 1.80 to 4.20 nm. That is, the total volume of the pores in the range occupies 60% or more of the total pore volume. More specifically, it means that the integral value of the pore volume of the pores in the pore diameter distribution curve of 1.80 to 4.20 nm occupies 60% or more of the total integral value of the curve. is there. Such a mesoporous material characterized in that “60% or more of the total pore volume is included in the range of ± 40% of the pore diameter showing the maximum peak in the pore diameter distribution curve” is substantially It can be said that the pore diameter is sufficiently uniform.
【００１７】また、本発明で用いるメソ多孔体として、
そのＸ線回折パターンにおいて、１ｎｍ以上の範囲のｄ
値に相当する回折角度に１本以上のピークを持つことを
特徴とするメソ多孔体を用いることが好ましい。かかる
ピークを持つメソ多孔体は細孔直径がより均一である。Further, as the mesoporous material used in the present invention,
In the X-ray diffraction pattern, d in the range of 1 nm or more
It is preferable to use a mesoporous material having one or more peaks at a diffraction angle corresponding to the value. The mesoporous material having such a peak has a more uniform pore diameter.
【００１８】本発明に好適に使用し得るメソ多孔体は、
例えば、層状のシリケート（カネマイト等）を界面活性
剤の水溶液中で加熱し、縮合反応によって形成すること
ができる。すなわち、界面活性剤のミセルをテンプレー
トとしつつその周囲（隙間）に層状シリケートの層間架
橋による三次元シリケート骨格を形成させ、その後、当
該界面活性剤からなるミセルを除去することによりメソ
多孔体を製造することができる（以下この製造法を「層
間架橋製造法」という。）。使用し得る層状シリケート
としては、カネマイト(NaHSi2O5 ・3H2O) が好ましい。
カネマイトは非晶質状のケイ酸ソーダ（例えば一般に市
販されている乾燥水ガラス）を約７００℃で焼成し、水
に浸漬することで容易に得られる。また、本層間架橋製
造法に使用し得る他の層状シリケートとしては、ジケイ
酸ナトリウム結晶（α，β，γ，δ−Na2Si2O5）、マカ
タイト（Na2Sｉ4O9 ・5H2O）、アイアライト（Na2Sｉ8O
17・xH2O）、マガディアイト（Na2Sｉ14O29 ・xH2O）、
ケニヤイト（Na2Sｉ20O41 ・xH2O）等が挙げられる。ま
た、その他の層状シリケートとして、例えば、セピオラ
イト、モンモリロナイト、バーミキュライト、雲母、カ
オリナイト、スメクタイトのような粘土鉱物を酸性水溶
液で処理してシリカ以外の元素を除去したものも使用し
得る。The mesoporous material that can be preferably used in the present invention is
For example, a layered silicate (such as kanemite) can be heated in an aqueous solution of a surfactant to form a condensation reaction. That is, using a micelle of a surfactant as a template, a three-dimensional silicate skeleton is formed around it (interstices) by inter-layer cross-linking of a layered silicate, and then the micelle composed of the surfactant is removed to produce a mesoporous body. (Hereinafter, this manufacturing method is referred to as "interlayer cross-linking manufacturing method"). As the layered silicate that can be used, kanemite (NaHSi 2 O 5 .3H 2 O) is preferable.
Kanemite can be easily obtained by baking amorphous sodium silicate (for example, dry water glass generally commercially available) at about 700 ° C. and immersing it in water. Other layered silicates that can be used in the present inter-layer cross-linking production method include sodium disilicate crystals (α, β, γ, δ-Na 2 Si 2 O 5 ), macatite (Na 2 Si 4 O 9 · 5H 2 O), Iarite (Na 2 Si 8 O
17・ xH 2 O), Magadiite (Na 2 Si 14 O 29・ xH 2 O),
Kenyaite (Na 2 Si 20 O 41 · xH 2 O) and the like can be mentioned. Further, as other layered silicates, those obtained by treating clay minerals such as sepiolite, montmorillonite, vermiculite, mica, kaolinite, and smectite with an acidic aqueous solution to remove elements other than silica can also be used.
【００１９】一方、層間架橋製造法に使用される界面活
性剤は、種々の溶媒中でミセルを形成し得るものであれ
ば特に制限はなく、陽イオン性、陰イオン性あるいは非
イオン性である各種の界面活性剤を用いることができ
る。典型的にはアルキルトリメチルアンモニウム（C n
H2n+1N(CH3)3；ｎは２〜１８の整数）、アルキルアンモ
ニウム、ジアルキルジメチルアンモニウム、ベンジルア
ンモニウムの塩化物、臭化物、ヨウ化物あるいは水酸化
物等の他、脂肪酸塩、アルキルスルフォン酸塩、アルキ
ルリン酸塩、ポリエチレンオキサイド系非イオン性界面
活性剤等が用いられる。アルキルトリメチルアンモニウ
ムが特に好ましく、アルキル鎖の炭素数（上記式中の
ｎ）が８〜１８であるアルキルトリメチルアンモニウム
が特に好ましい。アルキル鎖の炭素数に応じて形成され
るミセルのサイズが変更され、結果、それをテンプレー
トとする細孔の径を調節し得る。なお、界面活性剤は、
これらのうち１種類でも、あるいは２種類以上を組み合
わせて用いることができる。以下に本層間架橋製造法の
典型的な一例を示す。On the other hand, the surfactant used in the inter-layer crosslinking production method is not particularly limited as long as it can form micelles in various solvents, and it is cationic, anionic or nonionic. Various surfactants can be used. Typically alkyl trimethyl ammonium (C n
H 2n + 1 N (CH 3 ) 3 ; n is an integer of 2 to 18), alkylammonium, dialkyldimethylammonium, benzylammonium chloride, bromide, iodide or hydroxide, as well as fatty acid salts and alkylsulfones Acid salts, alkyl phosphates, polyethylene oxide-based nonionic surfactants and the like are used. Alkyltrimethylammonium is particularly preferable, and alkyltrimethylammonium in which the carbon number of the alkyl chain (n in the above formula) is 8 to 18 is particularly preferable. The size of the micelles formed is changed according to the number of carbon atoms in the alkyl chain, and as a result, the diameter of the pores using the micelle as a template can be adjusted. The surfactant is
One of these may be used, or two or more may be used in combination. A typical example of the present inter-layer crosslinking production method is shown below.
【００２０】上記した層状シリケートと界面活性剤とを
溶媒中で混合し、これに酸またはアルカリ触媒を加える
ことにより、脱水縮合反応を行う。好ましくは、界面活
性剤を溶解した溶媒中に上記層状シリケートを分散させ
るとよい。ここで使用する溶媒は典型的には水である
が、使用する界面活性剤をミセル状態とし得る水・アル
コール混合溶媒やその他の溶媒も用いることができる。
ここで縮合反応は、上記層状シリケートを分散させた溶
液を３０〜１００℃（より好ましくは７０〜８０℃）の
加熱条件下で行うことが好ましく、また反応時間は２〜
２４時間とすることが好ましい。また、加熱反応中は分
散溶液を攪拌するほうが好ましい。分散溶液のｐＨは縮
合反応中の初期の段階（典型的には１〜５時間）は１０
以上に調整するのが好ましく、その後（典型的には１時
間以上）は１０以下とするのがよい。ｐＨ制御は水酸化
ナトリウム(NaOH)のようなアルカリおよび塩酸のような
酸によって行われ得る。このようなｐＨ制御により、結
晶性および耐熱性に優れるメソ多孔体を得ることができ
る。なお、上記カネマイトはアルカリ性であるので溶媒
が水の場合には、通常、特に処理を施さずとも分散溶液
のｐＨは１０以上となり得る。The above layered silicate and the surfactant are mixed in a solvent, and an acid or alkali catalyst is added thereto to carry out a dehydration condensation reaction. Preferably, the layered silicate is dispersed in a solvent in which a surfactant is dissolved. The solvent used here is typically water, but a water / alcohol mixed solvent or other solvent that can bring the surfactant used into a micelle state can also be used.
Here, the condensation reaction is preferably carried out under a heating condition of the solution in which the above layered silicate is dispersed at 30 to 100 ° C. (more preferably 70 to 80 ° C.), and the reaction time is 2 to
It is preferably 24 hours. Further, it is preferable to stir the dispersion solution during the heating reaction. The pH of the dispersion solution is 10 during the initial stage (typically 1 to 5 hours) during the condensation reaction.
It is preferable to adjust to the above, and it is preferable to set it to 10 or less after that (typically 1 hour or more). pH control can be accomplished with an alkali such as sodium hydroxide (NaOH) and an acid such as hydrochloric acid. By such pH control, a mesoporous material having excellent crystallinity and heat resistance can be obtained. Since the above-mentioned kanemite is alkaline, when the solvent is water, the pH of the dispersion solution can usually be 10 or more without any special treatment.
【００２１】このような脱水縮合反応を行うことによっ
て、使用した界面活性剤からなるミセルをテンプレート
としたメソ孔を有する構造体（メソ多孔体前駆体）が形
成される。而して、縮合反応終了後、分散液より固形生
成物（メソ多孔体前駆体）を濾過・回収する。ここで、
得られた固形生成物を脱イオン水で繰り返し洗浄するこ
とが耐熱性の高いメソ多孔体を得ることができる観点か
ら好ましい。洗浄後、固形生成物を乾燥するとよい。そ
の後、好ましくは５５０℃以上の温度で焼成処理するか
或いは塩酸／エタノール溶液等による浸漬処理(H+ 置換
処理）することにより、テンプレートとして前駆体細孔
内に取り込まれていた界面活性剤を除去することができ
る。例えば、陽イオン性の界面活性剤を使用した場合
は、少量の塩酸を添加したエタノール中に固形生成物を
分散させ、５０〜７０℃で加熱しながら攪拌を行う。こ
れにより、陽イオン性界面活性剤がプロトン(H+ ) とイ
オン交換され抽出され得る。陰イオン性の界面活性剤で
あれば、陰イオンを添加した溶媒中で界面活性剤が抽出
され得る。また、非イオン性の界面活性剤の場合は、溶
媒だけで抽出され得る。あるいは、塩酸を添加した水あ
るいは水を溶媒に用いることにより、界面活性剤の抽出
が可能な場合もある。例えば、酸／有機溶媒の組合せで
あれば、塩酸とメタノール以外の酸と有機溶媒との混合
溶液をH+置換処理用溶液として用いることもできる。な
お、上記焼成処理を行う場合には、着火防止のため不活
性ガス（窒素等）雰囲気で行うのが好ましい。しかし、
この場合でも焼成処理の終期には空気等の酸化雰囲気に
したほうがカーボン等の残存防止の観点から好ましい。By carrying out such a dehydration condensation reaction, a structure having mesopores (mesoporous precursor) using the micelle composed of the used surfactant as a template is formed. After completion of the condensation reaction, the solid product (mesoporous precursor) is filtered and recovered from the dispersion liquid. here,
It is preferable to repeatedly wash the obtained solid product with deionized water from the viewpoint that a mesoporous material having high heat resistance can be obtained. After washing, the solid product may be dried. After that, preferably, the surfactant incorporated in the precursor pores as a template is removed by baking treatment at a temperature of 550 ° C. or higher or dipping treatment (H + substitution treatment) with hydrochloric acid / ethanol solution or the like. can do. For example, when a cationic surfactant is used, the solid product is dispersed in ethanol to which a small amount of hydrochloric acid is added, and stirring is performed while heating at 50 to 70 ° C. This allows the cationic surfactant to be ion-exchanged with the proton (H + ) and extracted. If it is an anionic surfactant, the surfactant can be extracted in a solvent added with an anion. In the case of a nonionic surfactant, it can be extracted only with a solvent. Alternatively, in some cases, the surfactant can be extracted by using water containing hydrochloric acid or water as a solvent. For example, in the case of an acid / organic solvent combination, a mixed solution of an acid other than hydrochloric acid and methanol and an organic solvent can be used as the H + substitution treatment solution. When the above-mentioned firing treatment is performed, it is preferable to perform it in an atmosphere of an inert gas (such as nitrogen) to prevent ignition. But,
Even in this case, an oxidizing atmosphere such as air is preferably used at the end of the firing process from the viewpoint of preventing carbon and the like from remaining.
【００２２】以上の処理工程により、テンプレートが除
去された部分がすなわちメソ孔となり、所望するメソ多
孔体が合成され得る。かかる方法によって得られるメソ
多孔体の細孔構造は好ましくはヘキサゴナル構造であ
る。この構造を模式的に図１に示す。この図に示すよう
に、本製造法において得られ得る好ましいメソ多孔体
は、層状シリケートが層間架橋して形成され、且つ細孔
がヘキサゴナル（六辺形）の対称性で配列したいわゆる
ヘキサゴナル細孔構造多孔体である。図１に示すよう
に、この構造によると所望するサイズの細孔が多孔体表
面に均一に分布するため、本発明の炭化水素ガス吸着剤
として特に好ましい。本製造法によると、テンプレート
とする界面活性剤の分子長を変化させることにより、メ
ソ細孔の孔径を調整することができる。例えば、使用す
る界面活性剤をアルキル鎖の短いものに変更すれば、よ
り小さい径のミセルが形成され、それをテンプレートと
する結果、形成されたメソ多孔体の細孔径も小さくな
る。０．５ｎｍ〜１０ｎｍのメソ細孔を形成する場合、
特に炭素原子数２〜１８のものがよい。炭素原子数８〜
１８のものが特に好ましい。なお、以上の処理工程によ
り製造されるメソ多孔体としては例えばＦＳＭ−１６が
ある（T.Yanagisawaら, Bull.Chem.Soc.,Jpn.,63,988(1
990)、S.Inagaki ら, J.Chem.Soc., Chem.Commun., 68
0(1993) ）。このＦＳＭ−１６は、本発明の炭化水素ガ
ス吸着剤に適用し得るメソ多孔体の好典型例である。Through the above processing steps, the portion from which the template has been removed becomes mesopores, and a desired mesoporous material can be synthesized. The pore structure of the mesoporous material obtained by such a method is preferably a hexagonal structure. This structure is schematically shown in FIG. As shown in this figure, the preferred mesoporous material that can be obtained in this production method is a so-called hexagonal pore in which layered silicates are formed by inter-layer crosslinking and pores are arranged in hexagonal (hexagonal) symmetry. It is a porous structure. As shown in FIG. 1, according to this structure, pores having a desired size are uniformly distributed on the surface of the porous body, and therefore, it is particularly preferable as the hydrocarbon gas adsorbent of the present invention. According to this production method, the pore size of the mesopores can be adjusted by changing the molecular length of the surfactant used as the template. For example, when the surfactant used is changed to one having a short alkyl chain, micelles having a smaller diameter are formed, and as a result of using the micelle as a template, the pore size of the formed mesoporous material is also reduced. When forming mesopores of 0.5 nm to 10 nm,
Particularly, those having 2 to 18 carbon atoms are preferable. 8 carbon atoms
18 is especially preferable. As a mesoporous material produced by the above treatment process, there is, for example, FSM-16 (T. Yanagisawa et al., Bull. Chem. Soc., Jpn., 63,988 (1.
990), S. Inagaki et al., J. Chem. Soc., Chem. Commun., 68.
0 (1993)). This FSM-16 is a typical example of a mesoporous material applicable to the hydrocarbon gas adsorbent of the present invention.
【００２３】なお、上記層間架橋製造法によれば、ＦＳ
Ｍ−１６等に限られず、Ｓｉ以外の元素を含む基本骨格
から成るヘキサゴナル構造メソ多孔体を製造することも
できる。典型的には、上記多孔体にＳｉ以外の元素を添
加する方法として、(1).原料である層状シリケート中に
予めＳｉ以外の元素を組込む方法（即ち他の元素を含む
層状シリケートを使用する方法）、(2).メソ多孔体の合
成中に他元素を含む物質を添加する方法が挙げられる。
すなわち、上記(1).方法としては、水ガラス等のケイ酸
溶液にＳｉ以外の元素（例えばＡｌ、Ｔｉ、Ｍｇ、Ｂ）
の塩を溶解させ、乾燥後、焼成する方法がある。これに
より、溶解させた元素の多くは層状シリケートを構成す
る-Si-O-骨格の中に組込まれ、結果、最終的に合成され
るメソ多孔体の基本骨格中にも上記元素が組込まれるこ
ととなる。また、上記(2).方法としては、例えば、層状
シリケートと界面活性剤とからなるメソ多孔体前駆体に
Ｓｉ以外の元素の塩の水溶液を含浸させた後、これを焼
成する方法がある。これにより、メソ多孔体の表面に当
該元素が付着または結合するため、当該元素の特性を効
果的に発現させることができる。According to the above-mentioned inter-layer cross-linking manufacturing method, FS
Not limited to M-16 and the like, a hexagonal structure mesoporous material having a basic skeleton containing an element other than Si can be produced. Typically, as a method of adding an element other than Si to the porous body, (1). A method of previously incorporating an element other than Si into the layered silicate as a raw material (that is, a layered silicate containing other elements is used. Method), (2). A method of adding a substance containing another element during the synthesis of the mesoporous material.
That is, as the method (1) above, an element other than Si (for example, Al, Ti, Mg, B) is added to a silicic acid solution such as water glass.
There is a method in which the salt is dissolved, dried and then baked. As a result, most of the dissolved elements are incorporated into the -Si-O- skeleton constituting the layered silicate, and as a result, the above elements are also incorporated into the basic skeleton of the mesoporous material to be finally synthesized. Becomes As the method (2), there is, for example, a method in which a mesoporous precursor composed of a layered silicate and a surfactant is impregnated with an aqueous solution of a salt of an element other than Si and then baked. As a result, the element adheres or bonds to the surface of the mesoporous material, so that the characteristics of the element can be effectively exhibited.
【００２４】次に、上記層間架橋製造法において製造さ
れるメソ多孔体に有機基を側鎖として含ませる方法の好
ましい一態様を説明する。なお、図２はここで説明する
有機基付与方法を模式的に説明したものである。上記製
造法によって合成されたメソ多孔体（例えばＦＳＭ−１
６等の-Si-O-骨格からなる無機系多孔体）には、通常の
カップリング反応および種々の有機シランを用いること
によって所望する有機基を側鎖として導入することがで
きる。すなわち、図２に示すように、得られたメソ多孔
体を水存在下で環流処理を行い、当該メソ多孔体の細孔
壁面表面にシラノール基（Si-OH ）を生じさせる（図
２）。次いで、所望する有機基（Ｒ）を含む有機シラン
化合物（例えばRSi(OR')3 で表されるトリアルコキシシ
ラン）を含む溶媒中で環流処理を行うことによってシロ
キサン結合を介して当該有機基Ｒを細孔壁面に付与する
ことができる（図２）。例えば、末端にチオール基を有
するトリメトキシメルカプトプロピルシラン(Si(OCH3)3
C3H6SH) を図２に示すように表面シラノール基に反応さ
せることによって、細孔壁面に有機チオール基(-C3H6S
H) が含まれたメソ多孔体が得られ得る。Next, a preferred embodiment of a method of incorporating an organic group as a side chain into the mesoporous material produced by the above-mentioned inter-layer crosslinking production method will be described. Note that FIG. 2 schematically illustrates the organic group-adding method described here. A mesoporous material synthesized by the above production method (for example, FSM-1
A desired organic group can be introduced as a side chain into the inorganic porous material composed of —Si—O— skeleton such as 6) by a usual coupling reaction and various organic silanes. That is, as shown in FIG. 2, the obtained mesoporous material is subjected to reflux treatment in the presence of water to generate silanol groups (Si—OH) on the pore wall surface of the mesoporous material (FIG. 2). Then, a reflux treatment is carried out in a solvent containing an organic silane compound containing the desired organic group (R) (for example, trialkoxysilane represented by RSi (OR ') 3 ) to form the organic group R via the siloxane bond. Can be applied to the pore wall surface (FIG. 2). For example, trimethoxymercaptopropylsilane (Si (OCH 3 ) 3 having a thiol group at the terminal
As shown in Fig. 2, C 3 H 6 SH) is reacted with the surface silanol group to form an organic thiol group (-C 3 H 6 S) on the pore wall surface.
A mesoporous material containing H) can be obtained.
【００２５】本発明の炭化水素ガス吸着剤に適するメソ
多孔体は、上述の層間架橋製造法に限らず他の方法によ
っても製造し得る。例えば、カネマイト等の上記層状シ
リケートに代えて、ケイ酸ソーダ、シリカ、あるいはア
ルコキシシランを界面活性剤の水溶液中で加熱処理し、
これら原料物質を重合・成長させることによっても製造
することができる（以下この製造法を「重合・成長製造
法」という。）。かかる重合・成長製造法によって得ら
れるメソ多孔体として、Ｍ４１Ｓ（ＭＣＭ−４１、ＭＣ
Ｍ−４８等）がある(C.T.Kresge et al., Nature,359,7
10(1992), J.S.Beck et al., J.Am. Chem.Soc., 114,10
834(1992))がある。この製法の原料物質としては、例え
ば、テトラメトキシシラン、テトラエトキシシラン、テ
トラプロポキシシラン、メチルトリメトキシシラン等の
アルコキシシランが用いられる。これらの１種類あるい
は２種類以上を組み合わせて用いることもできる。本製
造法に使用する界面活性剤としては、上述の層状シリケ
ートを用いる層間架橋製造法で例示した界面活性剤が好
適に使用し得る。アルキル基及び親水基を有する化合物
を使用するのが好ましい。０．５ｎｍ〜４ｎｍのメソ細
孔を形成する場合には炭素原子数２〜１８のものがよ
く、上記ヘキサゴナル構造（図１参照）のメソ多孔体を
合成する場合には、アルキル基の炭素数が８〜１８のも
のが特に好ましい。一方、好ましい親水基としては、例
えば、-N+ (CH3)3、-NH2、-SO3 - 、-PO4 - 、-COO- 、-O
H が挙げられる。アルキルトリメチルアンモニウムの使
用が特に好ましい。以下に典型的な製造例を示す。Meso-suitable for the hydrocarbon gas adsorbent of the present invention
The porous body is not limited to the above-mentioned interlayer cross-linking production method, but can be produced by other methods.
Can be manufactured. For example, the above-mentioned layered sheet such as kanemite
Instead of silicate, sodium silicate, silica, or
Heat treatment of lucoxysilane in an aqueous solution of a surfactant,
Manufactured by polymerizing and growing these raw materials
(This production method is referred to as "polymerization / growth production" below.
Law ". ). Obtained by such polymerization / growth manufacturing method
As the mesoporous material, M41S (MCM-41, MC
M-48 etc.) (C.T.Kresge et al., Nature, 359, 7
10 (1992), J.S.Beck et al., J.Am. Chem.Soc., 114,10
834 (1992)). As a raw material for this manufacturing method, for example,
For example, tetramethoxysilane, tetraethoxysilane,
Such as trapropoxysilane and methyltrimethoxysilane
Alkoxysilane is used. There is one of these
Can also be used in combination of two or more kinds. Made in book
As the surfactant used in the manufacturing method, the above-mentioned layered liquor is used.
The surfactants exemplified in the interlayer cross-linking manufacturing method using
It can be used appropriately. Compound having alkyl group and hydrophilic group
Is preferably used. 0.5 to 4 nm mesofine
When forming pores, those with 2 to 18 carbon atoms should be used.
In addition, the mesoporous material having the above hexagonal structure (see FIG. 1) is
When synthesizing, if the alkyl group has 8 to 18 carbon atoms
Is particularly preferable. On the other hand, examples of preferable hydrophilic groups include
For example, -N+(CH3)3, -NH2, -SO3 -, -POFour -, -COO-, -O
H is mentioned. Use of alkyl trimethyl ammonium
Is especially preferred. A typical production example is shown below.
【００２６】上記したアルコキシシランと界面活性剤と
を溶媒中で混合し、酸またはアルカリ触媒を加えること
により、縮重合反応を行う。界面活性剤の濃度は、特に
限定しないが、２０〜３０wt％が好ましい。典型的には
約２５wt％である。また、反応原料中の界面活性剤とケ
イ素の比は、合成されるメソ多孔体の構造を決定するの
に重要である。例えば、ケイ素に対する界面活性剤のモ
ル比（以下Sur/Si比という）を１より小さくすると上記
ヘキサゴナル構造（図１参照）のメソ多孔体（例えばＭ
ＣＭ−４１）が合成され得る。また、Sur/Si比を１〜
１．５とするとキュービック構造のメソ多孔体（例えば
ＭＣＭ−４８）が合成され得る。また、Sur/Si比を１．
２〜２とするとラメラ構造のメソ多孔体が合成され得
る。また、Sur/Si比を２より大きくとるとケイ酸塩８量
体が形成される。本発明において、上記ヘキサゴナル構
造のメソ多孔体（図１参照）を合成するのが表面上の細
孔分布およびその均一性の観点から好ましい。この場合
のSur/Si比は０．１〜０．６が好適である。また、特に
密度の高いメソ多孔体を合成するには、原料の混合方法
および組成に関する次の２点の条件を満足することが好
ましい。すなわち、(1).最初にアルコキシシランに少量
の水（典型的には１モルのＳｉに対して０．５〜１０モ
ルの水）を添加し、室温で数分〜３時間程度攪拌した後
に界面活性剤を添加することが好ましい。また、(2).反
応液中のH2O/Si比(mol/mol) は１〜１０が好ましい。H2
O/Si比が１より小さすぎるとアルコキシシランの加水分
解が起こらず、結果として所望する無機／有機複合体
（界面活性剤とアルコキシシランとからなる前駆体）が
形成されないおそれがある。一方、H2O/Si比が１０より
大きすぎると得られる無機／有機複合体の密度が低下す
るおそれがある。A polycondensation reaction is carried out by mixing the above-mentioned alkoxysilane and a surfactant in a solvent and adding an acid or alkali catalyst. The concentration of the surfactant is not particularly limited, but 20 to 30 wt% is preferable. It is typically about 25 wt%. Further, the ratio of the surfactant to the silicon in the reaction raw material is important for determining the structure of the mesoporous material to be synthesized. For example, when the molar ratio of the surfactant to silicon (hereinafter referred to as Sur / Si ratio) is smaller than 1, the mesoporous material having the hexagonal structure (see FIG. 1) (for example, M
CM-41) can be synthesized. In addition, the Sur / Si ratio is 1 to
When it is set to 1.5, a mesoporous material having a cubic structure (for example, MCM-48) can be synthesized. The Sur / Si ratio is 1.
When it is 2 to 2, a mesoporous material having a lamella structure can be synthesized. Further, when the Sur / Si ratio is set to be larger than 2, a silicate octamer is formed. In the present invention, it is preferable to synthesize the hexagonal mesoporous material (see FIG. 1) from the viewpoint of pore distribution on the surface and its uniformity. In this case, the Sur / Si ratio is preferably 0.1 to 0.6. Further, in order to synthesize a mesoporous material having a particularly high density, it is preferable to satisfy the following two conditions regarding the mixing method and composition of raw materials. That is, (1). First, a small amount of water (typically 0.5 to 10 mol of water relative to 1 mol of Si) is added to the alkoxysilane, and after stirring at room temperature for several minutes to 3 hours, It is preferable to add a surfactant. Further, (2). The H 2 O / Si ratio (mol / mol) in the reaction solution is preferably 1 to 10. H 2
If the O / Si ratio is less than 1, the alkoxysilane will not be hydrolyzed, and as a result, the desired inorganic / organic composite (precursor composed of the surfactant and the alkoxysilane) may not be formed. On the other hand, if the H 2 O / Si ratio is more than 10, the density of the obtained inorganic / organic composite may decrease.
【００２７】縮重合反応時の温度は、０〜１００℃の範
囲が適するが、後述するようにメソ多孔体の骨格中に有
機基を含ませる場合は反応温度が低い方（好ましくは２
０〜４０℃）が得られた固体生成物の構造規則性が高く
なる傾向がある。縮重合反応時間はＳｉ原料の種類によ
って適宜異なり得るが、典型的には１２時間〜４８時間
またはそれ以上の時間行ってもよい。数時間の攪拌と数
時間の静置を繰り返すのが好ましい。縮重合反応後、生
成した沈殿あるいはゲル状態の無機／有機複合体を濾過
し、必要であれば洗浄を行った後に乾燥、粉砕、篩い分
け等することにより典型的には粒状若しくは紛状の固形
生成物が得られる。この固形生成物（前駆体）は、メソ
多孔体としての基本骨格を既に有しているが、細孔の位
置には界面活性剤（典型的にはミセル）が充填されたま
まになっている。而して、上述の焼成処理またはH+置換
処理と同様の処理を行うことによって、界面活性剤を除
去することによってメソ多孔体が得られる。すなわち、
焼成による方法では、固形生成物を３００〜１０００℃
（好ましくは４００〜７００℃）に加熱する。加熱時間
は３０分以上が好ましい。完全に有機物を除去するため
には１時間以上加熱することが特に好ましい。なお、上
記と同様、焼成処理は着火防止のために不活性ガス（窒
素等）雰囲気で行うのが好ましく、カーボン等の残存を
防止する観点から焼成処理の終期には空気等の酸化雰囲
気に切り替えてもよい。一方、アルコール等でH+置換処
理する方法では、界面活性剤の溶解度が大きい溶媒に少
量の陽イオン成分を添加した溶液に固形生成物を分散、
攪拌した後に固形成分を回収することにより行う。上記
溶媒としては例えばエタノール、メタノール、アセトン
等を用いることができる。添加する陽イオン成分を含む
物質としては塩酸、酢酸、塩化ナトリウム、塩化カリウ
ム等がある。陽イオンの添加濃度は０．１〜１０mol/l
が好ましい。特に限定するものではないが、上記溶媒と
してエタノール溶液を用いた場合、これに対する上記固
形生成物（前駆体）の分散量はエタノール溶液１００ｍ
ｌに対して当該複合体を０．５〜５０ｇ分散させること
が好ましい。また、上記分散液の攪拌は２５〜１００℃
の温度範囲内で行うことが好ましい。The temperature during the polycondensation reaction is preferably in the range of 0 to 100 ° C., but when the organic group is contained in the skeleton of the mesoporous material, the reaction temperature is lower (preferably 2) as described later.
The structural regularity of the obtained solid product tends to be high. The polycondensation reaction time may vary depending on the type of the Si raw material, but may typically be 12 hours to 48 hours or longer. It is preferable to repeat stirring for several hours and standing for several hours. After the polycondensation reaction, the formed precipitate or gel-state inorganic / organic complex is filtered, washed if necessary, and then dried, crushed, sieved, etc., typically to give a granular or powdery solid. The product is obtained. This solid product (precursor) already has a basic skeleton as a mesoporous material, but a surfactant (typically a micelle) remains filled in the positions of the pores. . Then, the mesoporous material is obtained by removing the surfactant by performing the same treatment as the above-mentioned firing treatment or H + substitution treatment. That is,
In the method by calcination, the solid product is heated at 300 to 1000 ° C.
(Preferably 400 to 700 ° C.). The heating time is preferably 30 minutes or more. It is particularly preferable to heat for 1 hour or more in order to completely remove the organic matter. As in the above case, it is preferable to perform the firing treatment in an inert gas (nitrogen etc.) atmosphere to prevent ignition, and from the viewpoint of preventing carbon and the like from remaining, switch to an oxidizing atmosphere such as air at the end of the firing treatment. May be. On the other hand, in the method of H + substitution treatment with alcohol or the like, the solid product is dispersed in a solution obtained by adding a small amount of a cation component to a solvent in which the surfactant has high solubility,
This is done by collecting the solid components after stirring. As the solvent, for example, ethanol, methanol, acetone or the like can be used. Examples of the substance containing a cation component to be added include hydrochloric acid, acetic acid, sodium chloride, potassium chloride and the like. Addition concentration of cation is 0.1-10mol / l
Is preferred. Although not particularly limited, when an ethanol solution is used as the solvent, the amount of the solid product (precursor) dispersed therein is 100 m of the ethanol solution.
It is preferable to disperse the composite in an amount of 0.5 to 50 g per liter. The stirring of the above dispersion liquid is 25 to 100 ° C.
It is preferable to carry out in the temperature range of.
【００２８】なお、本重合・成長製造法においても、上
記ＭＣＭ−４１、ＭＣＭ−４８等に限られず、Ｓｉ以外
の元素（例えば金属元素）を含む基本骨格から成るメソ
多孔体を製造することもできる。典型的には、基本骨格
を形成する原料物質として上記ケイ酸ソーダ、シリカ、
あるいはアルコキシシランとともに他の元素を含む化合
物を加えて上記縮重合反応を行うことによって実現され
る。例えば、Ａｌ源として擬ベーマイト、アルミン酸ソ
ーダ、硫酸アルミニウムあるいはジアルコキシアルミノ
トリアルコキシシランを添加することによって、SiO2-A
l2O3からなる基本骨格のメソ多孔体が合成され得る。ま
た、ＳｉをＴｉ、Ｚｒ、Ｔａ、Ｎｂ、Ｓｎ、Ｈｆ等の金
属に置き換えた酸化化合物も使用することができる。こ
れにより、種々の金属（Ｍn+；ｎは金属の電荷）をシリ
ケート骨格内に含むメタロシリケート系メソ多孔体(SiO
2-MO2/n)を得ることができる。例えば、Ti(OC2H5)4等の
チタネート化合物、硫酸バナジル(VOSO4) 、ホウ酸(H3B
O3) または塩化マンガン(MnCl2) をアルコキシシランに
加えて共縮合反応を行うことによって、それぞれＴｉ、
Ｖ、ＢまたはＭｎを導入したメタロシリケート系メソ多
孔体を得ることができる。Also in the present polymerization / growth production method, not only the above MCM-41, MCM-48, etc., but also a mesoporous body having a basic skeleton containing an element other than Si (for example, a metal element) may be produced. it can. Typically, the above-mentioned sodium silicate, silica, as a raw material forming the basic skeleton,
Alternatively, it is realized by adding a compound containing another element together with the alkoxysilane and conducting the above-mentioned polycondensation reaction. For example, by adding pseudo-boehmite, sodium aluminate, aluminum sulfate or dialkoxyaluminotrialkoxysilane as an Al source, SiO 2 -A
A mesoporous material having a basic skeleton composed of l 2 O 3 can be synthesized. Further, an oxide compound in which Si is replaced with a metal such as Ti, Zr, Ta, Nb, Sn, Hf can also be used. As a result, a metallosilicate-based mesoporous material (SiO 2) containing various metals (M n + ; n is the charge of the metal) in the silicate skeleton
2 -MO 2 / n) can be obtained. For example, titanate compounds such as Ti (OC 2 H 5 ) 4 , vanadyl sulfate (VOSO 4 ), boric acid (H 3 B
O 3 ) or manganese chloride (MnCl 2 ) is added to the alkoxysilane to carry out a cocondensation reaction to produce Ti,
A metallosilicate-based mesoporous material having V, B or Mn introduced therein can be obtained.
【００２９】同様に、基本骨格を形成する原料物質とし
て上記ケイ酸ソーダ、シリカ、あるいはアルコキシシラ
ンとともに有機基を含む化合物を加えて上記縮合反応を
行うことによって、メソ多孔体に有機基を含ませること
が実現される。このような方法に好ましく使用し得る有
機基含有化合物として例えば、(CH3O) 3Si-CH2-CH2-Si(O
CH3)3 がある。-CH2-CH2の部分を-C6H4-の様な他の有機
基で置き換えた(CH3O)3Si-C6H4-Si(OCH3)3も好適に使用
することができる。また、これら化合物中のＳｉをＡ
ｌ、Ｔｉ、Ｚｒ、Ｔａ、Ｎｂ、Ｓｎ、Ｈｆ等の他の金属
に置き換えた有機化合物も使用することができる。これ
らアルキル鎖部分(-C-C-)を含む有機化合物をアルコキ
シシラン(Si(OR)4) とともに共縮合反応を行うことによ
って、そのようなアルキル鎖部分を有機基として含む基
本骨格から成る無機／有機ハイブリッド系メソ多孔体を
得ることができる。Similarly, as a raw material forming the basic skeleton,
Sodium silicate, silica, or alkoxy sila
And a compound containing an organic group are added to the condensation reaction
By including an organic group in the mesoporous material
Is realized. It can be preferably used in such a method
Examples of the functional group-containing compound include (CH3O) 3Si-CH2-CH2-Si (O
CH3)3There is. -CH2-CH2Part of -C6HFour-Other organic like
Replaced with a group (CH3O)3Si-C6HFour-Si (OCH3)3Is also suitable for use
can do. In addition, Si in these compounds is
Other metals such as l, Ti, Zr, Ta, Nb, Sn, Hf
An organic compound substituted for can also be used. this
To an organic compound containing an alkyl chain moiety (-C-C-).
Sisilane (Si (OR)Four) Together with the co-condensation reaction
A group containing such an alkyl chain moiety as an organic group
Inorganic / organic hybrid mesoporous material consisting of this skeleton
Obtainable.
【００３０】なお、導入する有機基はこのようなアルキ
ル鎖に限られず、アルケニル鎖、ビニル鎖、アルキニル
鎖、シクロアルキル鎖、ベンゼン環、ベンゼン環を含む
炭化水素等の各種炭化水素の他、各種水酸基、カルボキ
シル基、チオール基等の官能基と１又は２以上の炭素原
子とを備えた化合物に由来する官能基含有有機基等が使
用し得る。チオール基、カルボキシル基等の官能基はメ
タンガス等の低級炭化水素ガスを高効率に吸着し得るた
め、これら官能基を導入するのが好ましい。また、チオ
ール基、カルボキシル基等の官能基は、メタンガス等の
低級炭化水素ガス高効率吸着に寄与し得る金属原子（イ
オン）またはその塩と結合（典型的には配位）する特性
を示すことから好ましい。導入する有機基および／また
は官能基は１種類に限定されることなく、低級炭化水素
ガス吸着能に悪影響を及ぼさない限り２種類以上を組み
合わせて用いることができる。The organic group to be introduced is not limited to such an alkyl chain, and various hydrocarbons such as alkenyl chain, vinyl chain, alkynyl chain, cycloalkyl chain, benzene ring, and hydrocarbons containing a benzene ring, as well as various hydrocarbons. A functional group-containing organic group derived from a compound having a functional group such as a hydroxyl group, a carboxyl group and a thiol group and one or more carbon atoms can be used. Since functional groups such as thiol group and carboxyl group can adsorb lower hydrocarbon gas such as methane gas with high efficiency, it is preferable to introduce these functional groups. In addition, functional groups such as thiol groups and carboxyl groups must exhibit the property of binding (typically coordinating) with metal atoms (ions) or their salts that can contribute to highly efficient adsorption of lower hydrocarbon gases such as methane gas. Is preferred. The organic group and / or functional group to be introduced are not limited to one type, and two or more types can be used in combination as long as they do not adversely affect the lower hydrocarbon gas adsorption capacity.
【００３１】あるいは、シリカ等からなる無機系基本骨
格の側鎖として有機基および／または官能基を導入する
ことができる。例えば、図３に模式的に示すように、原
料物質としてアルコキシシラン(Si(OR')4)と導入したい
有機基(R) を含むトリアルコキシシラン(R-Si(OR')4)と
を適当な界面活性剤とともに溶媒中で共縮合反応を行
う。これにより、上述のとおり、界面活性剤のミセルが
テンプレートとなってメソ多孔体前駆体が形成され、同
時に細孔壁内を含む多孔体表面に有機基(R) が付与され
る。而して、上記H+置換処理を行って、細孔内から界面
活性剤（ミセル）を抽出することによって所望する有機
基(R) を有するメソ多孔体が形成される（図３）。な
お、この方法に限らず、本重合・成長製造法によって得
られたメソ多孔体においても、上述の図２に示した方法
によっても側鎖として有機基を導入し得る。Alternatively, an organic group and / or a functional group can be introduced as a side chain of an inorganic basic skeleton made of silica or the like. For example, as schematically shown in FIG. 3, alkoxysilane (Si (OR ') 4 ) and trialkoxysilane (R-Si (OR') 4 ) containing an organic group (R) to be introduced are used as raw materials. The cocondensation reaction is carried out in a solvent with a suitable surfactant. Thereby, as described above, the micelle of the surfactant serves as a template to form the mesoporous material precursor, and at the same time, the organic group (R) is provided to the surface of the porous material including the inside of the pore walls. Then, the above H + substitution treatment is performed to extract the surfactant (micelle) from the inside of the pores, whereby a mesoporous material having a desired organic group (R) is formed (FIG. 3). Not only this method, but also in the mesoporous material obtained by the present polymerization / growth production method, the organic group can be introduced as a side chain by the method shown in FIG.
【００３２】次に、メソ多孔体の細孔内に金属原子を保
持させることについて説明する。上記のようにして細孔
内に有機チオール基等の官能基を導入したメソ多孔体に
は、図４に示すように（ヘキサゴナル構造について示
す）、細孔内表面にチオール基等の官能基が存在する。
従って、かかる官能基と金属塩を反応させて所望する金
属原子を細孔内に保持（典型的にはイオンまたは錯体形
態）することができる。例えば、図４に示すようなチオ
ール基を有するメソ多孔体を、CuCl2 、NiCl2、MnCl2
等の金属塩化物を溶解させたエタノール中に分散させ
て、好ましくは５０〜６０℃に加熱して数時間（典型的
には２〜３時間）反応させる。次いで、分散体を分別・
乾燥することによって、図５に示すように、細孔中に当
該金属を保持（典型的には配位結合）したメソ多孔体が
得られ得る。かかる金属原子が細孔内に保持されたメソ
多孔体は、メタンガス等の低級炭素ガス吸着能に特に優
れており、本発明の炭化水素ガス吸着剤を実質的に構成
するメソ多孔体として好適である。中でも銅および／ま
たはニッケルが細孔内に保持されたものが特に好まし
い。細孔壁面に存在するチオール基、カルボキシル基等
の官能基または該官能基を有する有機基と銅、ニッケル
等の金属とが有機金属錯体を形成して細孔内に保持され
ているものが特に好ましいメソ多孔体である。Next, the retention of metal atoms in the pores of the mesoporous material will be described. As shown in FIG. 4 (showing the hexagonal structure), the mesoporous material having a functional group such as an organic thiol group introduced into the pores as described above has a functional group such as a thiol group on the pore inner surface. Exists.
Thus, the functional group can be reacted with a metal salt to retain the desired metal atom in the pores (typically in ionic or complex form). For example, a mesoporous material having a thiol group as shown in FIG. 4 is added to CuCl 2 , NiCl 2 , MnCl 2
Etc. are dispersed in ethanol in which a metal chloride is dissolved, and the mixture is heated to preferably 50 to 60 ° C. and reacted for several hours (typically 2 to 3 hours). Then disperse the dispersion
By drying, as shown in FIG. 5, a mesoporous material in which the metal is retained in pores (typically, coordinate bond) can be obtained. The mesoporous material in which the metal atoms are held in the pores is particularly excellent in the ability to adsorb lower carbon gas such as methane gas, and is suitable as a mesoporous material that substantially constitutes the hydrocarbon gas adsorbent of the present invention. is there. Among them, those in which copper and / or nickel are held in the pores are particularly preferable. Those having a thiol group present on the pore wall surface, a functional group such as a carboxyl group or an organic group having the functional group and a metal such as copper or nickel and forming an organometallic complex and held in the pores are particularly preferable. It is a preferred mesoporous material.
【００３３】また、本発明の炭化水素ガス吸着剤として
用いるメソ多孔体として特に好ましいものはメソ多孔体
製造過程において後述するような水熱処理が施されたシ
リカ系メソ多孔体である。以下このことを説明する。上
記重合・成長製造法等によって製造された有機基含有メ
ソ多孔体前駆体（即ち界面活性剤が細孔内に充填された
ままのもの）を上記H+置換処理等の界面活性剤を取り除
く処理を行う前に、以下のように水熱処理する。すなわ
ち、上記縮重合反応によって、アルコキシシラン（Si(O
R')4）および有機シラン化合物（R-Si(OR')4等）等の原
料物質から合成して得た有機基含有メソ多孔体前駆体を
水存在下で加熱処理（水熱処理）する。好ましくは、当
該縮重合反応において使用したのと同様の界面活性剤を
含む水溶液（典型的には縮重合反応時と同等かそれ以下
の界面活性剤濃度とする）中に分散させ、当該前駆体を
５０℃〜２００℃の範囲内で水熱処理する。加熱温度は
好ましくは６０〜１００℃であり、より好ましくは７０
〜８０℃である。また、このときのｐＨはややアルカリ
性がよく、好ましくは８〜８．５である。適宜塩酸また
は水酸化ナトリウムで調整すればよい。この処理時間は
特に制限するものではないが、３時間以上が好ましく、
８時間〜１２時間がさらに好ましい。それ以上長時間継
続して行ってもよいが、あまり長時間行っても効果に顕
著な差はみられなくなる。なお、水熱処理は処理液を攪
拌しつつ行うのが好ましい。この水熱処理後、前駆体を
濾過、乾燥し、余剰の処理液を取り去る。而して、上述
のH+置換処理等の界面活性剤を取り除く処理を行うこと
によって、メソ多孔体を得る。なお、前駆体を上記水溶
液中に分散後、水熱処理を開始する前に予め室温で数時
間攪拌処理を行ってもよい。これにより、上記水熱処理
に基づく以下の効果をより高めることができる。Further, a particularly preferred mesoporous material used as the hydrocarbon gas adsorbent of the present invention is a silica-based mesoporous material that has been subjected to hydrothermal treatment as described later in the mesoporous material manufacturing process. This will be described below. Treatment for removing the surfactant such as H + substitution treatment for the organic group-containing mesoporous precursor produced by the above-mentioned polymerization / growth production method (that is, the one in which the surfactant remains filled in the pores) Before carrying out, hydrothermal treatment is carried out as follows. That is, the alkoxysilane (Si (O
R ') 4 ) and an organic group-containing mesoporous precursor obtained by synthesizing a starting material such as an organic silane compound (R-Si (OR') 4 etc.) in the presence of water (hydrothermal treatment) . Preferably, the precursor is dispersed in an aqueous solution containing the same surfactant as that used in the polycondensation reaction (typically, the surfactant concentration is equal to or lower than that in the polycondensation reaction). Is hydrothermally treated within the range of 50 ° C to 200 ° C. The heating temperature is preferably 60 to 100 ° C., more preferably 70.
~ 80 ° C. The pH at this time is slightly alkaline, and preferably 8 to 8.5. It may be adjusted appropriately with hydrochloric acid or sodium hydroxide. The treatment time is not particularly limited, but is preferably 3 hours or more,
More preferably 8 to 12 hours. It may be continued for a longer period of time, but if it is conducted for a too long period of time, no significant difference is observed in the effect. The hydrothermal treatment is preferably performed while stirring the treatment liquid. After this hydrothermal treatment, the precursor is filtered and dried to remove the excess treatment liquid. Thus, a mesoporous material is obtained by performing a treatment for removing the surfactant, such as the above H + substitution treatment. In addition, after the precursor is dispersed in the aqueous solution, stirring treatment may be performed at room temperature for several hours before starting the hydrothermal treatment. Thereby, the following effects based on the hydrothermal treatment can be further enhanced.
【００３４】以上のように水熱処理を施す結果、付与し
た有機基や官能基に特段の悪影響を及ぼすことなく、界
面活性剤テンプレート除去後のメソ多孔体の強度および
構造規則性を向上させることができる。このため、上記
水熱処理を施さないものと比較して、細孔安定性および
構造規則性即ち細孔分布の均一性に優れたメソ多孔体を
提供することができる。従って、例えば上記ヘキサゴナ
ル構造の多孔体前駆体を本水熱処理に供することによっ
て、メソ多孔体（最終生成物）における細孔のサイズ
を、細孔直径分布曲線における最大ピークを示す細孔直
径の±４０％の範囲に全細孔容積の６０％以上が含まれ
る程度に均一化させることができる。従って、上記水熱
処理を施したメソ多孔体によれば、全細孔におけるメタ
ンガス等の吸着に適する孔径（好ましくは中心細孔直
径：０．５ｎｍ〜２ｎｍ）を有する細孔の存在割合すな
わち表面積あたりの有効細孔容積率が向上する。このた
め、水熱処理を施したメソ多孔体から実質的に構成され
る本発明の炭化水素ガス吸着剤によればメタン等の低級
炭化水素ガスをさらに効率よく吸着することができ、重
量または容積あたりのガス吸着量を向上させることがで
きる。また、かかる多孔体に上述のようにして金属原子
（好ましくは銅および／またはニッケル）を保持させて
成る本発明の炭化水素ガス吸着剤は、メタンガス等の低
級炭化水素ガス吸着能に特に優れている。特に、細孔壁
面に存在するチオール基、カルボキシル基等の官能基を
有する有機基と銅、ニッケル、マンガン等の金属とが有
機金属錯体を形成して細孔内に保持されているものが特
に好ましい水熱処理済みメソ多孔体である。As a result of the hydrothermal treatment as described above, the strength and structural regularity of the mesoporous material after the removal of the surfactant template can be improved without particularly adversely affecting the imparted organic groups or functional groups. it can. Therefore, it is possible to provide a mesoporous material having excellent pore stability and structural regularity, that is, uniformity of pore distribution, as compared with those not subjected to the hydrothermal treatment. Therefore, for example, by subjecting the above-mentioned hexagonal structure porous body precursor to the present hydrothermal treatment, the size of the pores in the mesoporous body (final product) can be adjusted to be ± of the pore diameter showing the maximum peak in the pore diameter distribution curve. It can be made uniform to the extent that 60% or more of the total pore volume is included in the 40% range. Therefore, according to the mesoporous material subjected to the hydrothermal treatment, the existence ratio of pores having a pore diameter (preferably central pore diameter: 0.5 nm to 2 nm) suitable for adsorption of methane gas in all pores, that is, per surface area The effective pore volume ratio of is improved. Therefore, according to the hydrocarbon gas adsorbent of the present invention which is substantially composed of a mesoporous material subjected to hydrothermal treatment, it is possible to more efficiently adsorb lower hydrocarbon gas such as methane, and The amount of adsorbed gas can be improved. Further, the hydrocarbon gas adsorbent of the present invention in which such a porous body holds metal atoms (preferably copper and / or nickel) as described above is particularly excellent in the ability to adsorb lower hydrocarbon gas such as methane gas. There is. In particular, a thiol group present on the pore wall surface, an organic group having a functional group such as a carboxyl group and a metal such as copper, nickel or manganese, which forms an organometallic complex and is retained in the pores are particularly preferable. It is a preferred hydrothermally treated mesoporous material.
【００３５】本発明の炭化水素ガス吸着剤は、上記のよ
うにして得られた有機基および／または官能基を含むメ
ソ多孔体から実質的に構成されていればよく、その形態
は特に限定されない。粉末または顆粒状のもの、支持膜
等の膜状のもの、あるいは球状や繊維状の形態のもので
もよい。例えば、基板上のバーニングやμｍサイズの明
瞭な形態をもつ粒子状等が本発明の炭化水素ガス吸着剤
におけるメソ多孔体の形態の典型例として挙げられる。
例えば、上記重合・成長製造法において縮重合反応液
を、スピンコート法、キャスティング法、ディップコー
ト法等により種々の基材表面にコートさせることによっ
て、当該基材上に無機／有機複合体（即ち前駆体）が生
成される。而して、当該基材に対して上記焼成処理、H+
置換処理等の界面活性剤（テンプレート）除去処理およ
び好ましくは該処理前に水熱処理を施すことによって、
基材にコーティングされた膜形状のメソ多孔体からなる
本発明の炭化水素ガス吸着剤を製造することができる。
なお、かかる膜状ガス吸着剤においても、細孔内に銅、
ニッケル等の金属原子を保持させたものが特に好まし
い。The hydrocarbon gas adsorbent of the present invention is essentially composed of the mesoporous material containing the organic group and / or functional group obtained as described above, and its form is not particularly limited. . It may be in the form of powder or granules, in the form of a film such as a support film, or in the form of spheres or fibers. For example, burning on the substrate, particulates having a distinctive μm size morphology, and the like are typical examples of the morphology of the mesoporous material in the hydrocarbon gas adsorbent of the present invention.
For example, in the above-mentioned polymerization / growth production method, the polycondensation reaction solution is coated on the surface of various base materials by a spin coating method, a casting method, a dip coating method or the like to give an inorganic / organic composite (ie, A precursor) is produced. Then, the baking treatment, H +
By a treatment for removing the surfactant (template) such as a substitution treatment and preferably a hydrothermal treatment before the treatment,
It is possible to produce the hydrocarbon gas adsorbent of the present invention, which is composed of a film-shaped mesoporous material coated on a substrate.
Incidentally, even in such a film-shaped gas adsorbent, copper in the pores,
Those holding metal atoms such as nickel are particularly preferable.
【００３６】また、本発明の炭化水素ガス吸着剤は、上
述の無機系（典型的にはシリカ系）または無機／有機ハ
イブリッド系の多孔体であって、メタンガス吸着能を有
する有機基および／または官能基および／または金属原
子（好ましくは銅、ニッケル）を有する多孔体から実質
的に構成されておればよく、メタンガス吸着能に悪影響
を及ぼさない限りにおいて種々の副成分、例えば、乾燥
剤、芳香剤、着色剤、難燃剤、抗菌防臭剤等を配合して
もよい。The hydrocarbon gas adsorbent of the present invention is a porous body of the above-mentioned inorganic type (typically silica type) or inorganic / organic hybrid type, which has an organic group and / or an organic group having a methane gas adsorbing ability. It suffices that it is substantially composed of a porous material having a functional group and / or a metal atom (preferably copper, nickel), and various subcomponents such as a desiccant and an aroma as long as they do not adversely affect the methane gas adsorption ability. Agents, colorants, flame retardants, antibacterial deodorants, etc. may be added.
【００３７】また、本発明のガス吸着剤に吸着・貯蔵さ
れたメタンガス等の低級炭化水素ガス（即ちメタン、エ
タン、プロパン、ブタン、エチレン、アセチレン、ブテ
ン、イソブテン等）は種々の方法によってふたたび放出
することができる。例えば、これらの低級炭化水素ガス
の吸着剤への吸着・貯蔵を１気圧（大気圧）以上の圧力
をかけることにより行った場合は、圧力を当該吸着させ
たときの圧力より下げることにより、吸着・貯蔵された
ガスが放出される。急速にあるいは大量にガスを放出す
る場合は、吸着剤の温度が脱着熱により下がるため、熱
を加えて吸着剤の温度が一定あるいは上がるようにする
ことが好ましい。Further, lower hydrocarbon gas such as methane gas (ie, methane, ethane, propane, butane, ethylene, acetylene, butene, isobutene, etc.) adsorbed and stored in the gas adsorbent of the present invention is released again by various methods. can do. For example, when these lower hydrocarbon gases are adsorbed and stored in the adsorbent by applying a pressure of 1 atm (atmospheric pressure) or more, the adsorbing is performed by lowering the pressure from the pressure at which the adsorbing is performed. -The stored gas is released. When the gas is released rapidly or in a large amount, the temperature of the adsorbent is lowered by the heat of desorption, so it is preferable to add heat so that the temperature of the adsorbent is constant or rises.
【００３８】[0038]
【実施例】以下、本発明を具体的に実施した実施例につ
いて説明する。なお、本発明は、以下の実施例に限定さ
れるものではない。EXAMPLES Examples in which the present invention has been concretely carried out will be described below. The present invention is not limited to the examples below.
【００３９】＜実施例１＞
−水熱処理したメソ多孔体の作製および構造解析−
１０００ｍｌ容ビーカーに１５．１ｇの６Ｎ−ＮａＯＨ
水溶液と２９８ｇのイオン交換水を入れ、さらに界面活
性剤として５．７ｇ（１８ｍｍｏｌ）のセチルトリメチ
ルアンモニウムクロリド（C16H33N(CH3)3Cl:以下「ＣＴ
ＡＣ」という）を加えた。次いで、室温で激しく振盪し
ながら、１２０ｍｍｏｌに相当する量のテトラメトキシ
シラン(Si(OCH3)4) と３０ｍｍｏｌに相当する量の式：
R-Si-(OCH 3)3 で表される有機メトキシシランとの混合
物を加えた。なお、本実施例においては、上記ＲがC
H3 、C2H5、C6H5、C3H6SHおよびC3H6NH2 である計５種
類の有機メトキシシランを別個に使用して得た５種類の
混合物を使用した。上記混合物を添加後、室温で１２時
間攪拌した後、１４時間放置し、さらに１２時間攪拌し
た。攪拌処理終了後、内容物を濾過し、沈殿物をほぼ５
００ｍｌのイオン交換水で３回洗浄した。風乾後、上記
各有機メトキシシラン（各混合物）に対応した計５種類
のメソ多孔体前駆体を得た。<Example 1> -Preparation and structural analysis of mesoporous material subjected to hydrothermal treatment- 15.1 g of 6N-NaOH in a 1000 ml beaker
An aqueous solution and 298 g of ion-exchanged water were added, and 5.7 g (18 mmol) of cetyltrimethylammonium chloride (C 16 H 33 N (CH 3 ) 3 Cl: as a surfactant was used below as “CT.
"AC") was added. Then, with vigorous shaking at room temperature, an amount of tetramethoxysilane (Si (OCH 3 ) 4 ) equivalent to 120 mmol and an amount of formula equivalent to 30 mmol:
R-Si- (OCH 3) mixture of an organic silane represented by 3 was added. In the present embodiment, R is C
A mixture of 5 kinds obtained by separately using a total of 5 kinds of organic methoxysilanes which are H 3 , C 2 H 5 , C 6 H 5 , C 3 H 6 SH and C 3 H 6 NH 2 was used. After the above mixture was added, the mixture was stirred at room temperature for 12 hours, allowed to stand for 14 hours, and further stirred for 12 hours. After the stirring process was completed, the contents were filtered and the precipitate was removed to approximately 5
It was washed 3 times with 00 ml of deionized water. After air-drying, a total of five types of mesoporous material precursors corresponding to the above-mentioned organic methoxysilanes (each mixture) were obtained.
【００４０】次に、上記５種類のメソ多孔体前駆体につ
いて以下のように水熱処理を施した。すなわち、４．０
ｇの前駆体をＣＴＡＣ溶液（２．３０４ｇのＣＴＡＣを
１２０ｍｌのイオン交換水に溶解したもの）に入れ、１
Ｎ−ＨＣｌによってｐＨを８〜８．５に調整した。次い
で、室温で５時間攪拌処理を行い、１５時間放置した。
その後、当該ＣＴＡＣ溶液を７０〜７５℃に至るまで加
熱するとともに同温度域で８時間攪拌処理を行った。こ
の攪拌処理終了後、内容物を濾過して沈殿物を回収し、
風乾した。Next, the above-mentioned five kinds of mesoporous material precursors were subjected to hydrothermal treatment as follows. That is, 4.0
1 g of the precursor was added to a CTAC solution (2.304 g of CTAC dissolved in 120 ml of ion-exchanged water), and 1
The pH was adjusted to 8-8.5 with N-HCl. Then, the mixture was stirred at room temperature for 5 hours and left for 15 hours.
Then, the CTAC solution was heated to 70 to 75 ° C. and stirred for 8 hours in the same temperature range. After completion of this stirring process, the content is filtered to collect the precipitate,
Air dried.
【００４１】このようにして水熱処理された前駆体に対
し、次にH+置換処理を施した。すなわち、３．８ｇの濃
塩酸と１５０ｍｌのエタノールとからなる溶液に１．０
ｇの水熱処理済み前駆体を加えて５０℃で６時間の攪拌
処理を行った。この攪拌処理終了後、内容物を濾過して
沈殿物を回収し、当該沈殿物を風乾した。さらにもう一
度同条件でH+置換処理を施した後、内容物を濾過して沈
殿物を回収し、当該沈殿物を風乾することによって、本
実施例にかかるメソ多孔体（以下「水熱処理済み多孔
体」という。）を得た。なお、得られた多孔体は、それ
ぞれ多孔体表面に、上記Ｒに応じてCH3 、C2H5、C6H5、
C3H6SHまたはC3H6NH2 がそれぞれ付与されている有機基
含有多孔体である。以下、これらをそれぞれCH3 基含有
多孔体、C2H5基含有多孔体、C6H5基含有多孔体、C3H6SH
基含有多孔体およびC3H6NH2 基含有多孔体とよぶ。な
お、比較対照のために、上記５種類の前駆体について水
熱処理を行わずに同様のH+置換処理を施して多孔体（以
下「非水熱処理多孔体」という。）を作製した。The hydrothermally treated precursor was then subjected to H + substitution treatment. That is, 1.0 in a solution consisting of 3.8 g of concentrated hydrochloric acid and 150 ml of ethanol.
g of the hydrothermally treated precursor was added, and the mixture was stirred at 50 ° C. for 6 hours. After completion of this stirring treatment, the content was filtered to collect the precipitate, and the precipitate was air-dried. After the H + substitution treatment was again performed under the same conditions, the content was filtered to collect the precipitate, and the precipitate was air-dried to obtain a mesoporous material according to the present example (hereinafter referred to as “hydrothermally treated porous material”). Body.). The obtained porous bodies had CH 3 , C 2 H 5 , C 6 H 5 , and
It is an organic group-containing porous body to which C 3 H 6 SH or C 3 H 6 NH 2 is added. Hereinafter, these are respectively CH 3 group-containing porous body, C 2 H 5 group-containing porous body, C 6 H 5 group-containing porous body, C 3 H 6 SH
It is called a group-containing porous body and a C 3 H 6 NH 2 group-containing porous body. For comparison and comparison, the above five kinds of precursors were subjected to the same H + substitution treatment without hydrothermal treatment to prepare a porous body (hereinafter referred to as “non-hydrothermally treated porous body”).
【００４２】得られた上記５種の有機基含有多孔体（水
熱処理済みのもの）について、固体 13ＣＮＭＲスペクト
ルおよび固体29ＳｉＮＭＲスペクトル解析を行った。そ
れぞれの結果を図６および図７に示す。これらの解析図
から明らかなように、いずれの有機基含有多孔体（図中
において各有機基で表示している）のスペクトル解析に
おいても29ＳｉＮＭＲにおけるＴ2 およびＴ3 種のシリ
コン共鳴ピーク（図７）および13ＣＮＭＲにおける各有
機基に対応する炭素共鳴ピーク（図６）が観察された。
これらのことから、各有機基含有多孔体はいずれも当該
含有する有機基またはチオール基等の官能基を含有する
有機基が細孔壁面に付与されていることが確認された。The above-mentioned five kinds of organic group-containing porous bodies (water
Heat treated), solid 13CNMR spectrum
And solid29SiNMR spectrum analysis was performed. So
The respective results are shown in FIGS. 6 and 7. These analysis charts
As is clear from any of the above, any organic group-containing porous material (in the figure
In each organic group in)
Aside29T in SiNMR2And T3Seed Siri
Con resonance peak (Fig. 7) and13Each in CNMR
A carbon resonance peak (FIG. 6) corresponding to the mechanism was observed.
From these things, each organic group-containing porous body is
Contains organic groups or functional groups such as thiol groups
It was confirmed that the organic groups were attached to the wall surfaces of the pores.
【００４３】次に、Ｘ線回折等の手段によって、得られ
た各メソ多孔体および前駆体についての構造解析を行っ
た。先ず、C3H6SH基含有多孔体およびその前駆体につい
てのＸ線回折パターンを調べた。図８〜図１１はそれぞ
れ、C3H6SH基含有多孔体に関する水熱処理前前駆体、非
水熱処理メソ多孔体、水熱処理済み前駆体および水熱処
理済みメソ多孔体についてのＸ線回折パターンを示すグ
ラフである。これらのグラフから明らかなように、水熱
処理前前駆体では構造規則性の高いヘキサゴナル構造に
対応するＸ線回折パターンを示した（図８）が、非水熱
処理メソ多孔体（即ち水熱処理をせずに界面活性剤テン
プレートを抽出除去したもの）では、当該規則性の高い
メソ構造がやや崩壊してしまうことを示した（図９）。
これに対して、水熱処理済み前駆体のＸ線回折パターン
において、熱水処理によってもその回折Ｘ線強度ピーク
はシャープであり構造規則性が保持されていることが示
された（図１０）。また、水熱処理済みメソ多孔体につ
いても同様に、その回折Ｘ線強度ピークはシャープであ
り構造規則性が保持されていることが示された（図１
１）。以上のように、熱水処理を施すことによって、界
面活性剤（テンプレート）を抽出・除去した後も細孔構
造を安定化させ得ること即ちヘキサゴナル構造の規則性
を極めて高く保持し得ることが示された。Next, the structure of each of the obtained mesoporous materials and precursors was analyzed by means such as X-ray diffraction. First, the X-ray diffraction patterns of the C 3 H 6 SH group-containing porous body and its precursor were examined. 8 to 11 show X-ray diffraction patterns of the precursor before hydrothermal treatment, the non-hydrothermally treated mesoporous body, the hydrothermally treated precursor and the hydrothermally treated mesoporous body, respectively, for the C 3 H 6 SH group-containing porous body. It is a graph shown. As is clear from these graphs, the precursor before hydrothermal treatment showed an X-ray diffraction pattern corresponding to a hexagonal structure having a high structural regularity (Fig. 8), but the precursor before hydrothermal treatment showed mesoporous non-hydrothermal treatment (that is, hydrothermal treatment was not performed). It was shown that the mesostructure with high regularity was slightly disintegrated (Fig. 9).
On the other hand, in the X-ray diffraction pattern of the hydrothermally treated precursor, it was shown that the diffracted X-ray intensity peak was sharp and the structural regularity was maintained even after the hot water treatment (FIG. 10). Similarly, for the hydrothermally treated mesoporous material, the diffraction X-ray intensity peak was sharp and the structural regularity was maintained (FIG. 1).
1). As described above, it is shown that the hot water treatment can stabilize the pore structure even after the surfactant (template) is extracted and removed, that is, the regularity of the hexagonal structure can be kept extremely high. Was done.
【００４４】同様に、上記５種類の有機基含有多孔体お
よびその前駆体についてのＸ線回折パターンを調べた。
図１２〜図１４は、それぞれ、上記５種の有機基含有メ
ソ多孔体に関する水熱処理前前駆体、水熱処理済み前駆
体および水熱処理済み多孔体（H+置換処理後多孔体）に
ついてのＸ線回折パターンを示すグラフである。図１２
〜図１４に表されたチャートはいずれも最上段がC3H6SH
基含有多孔体または前駆体についてのものであり、以
下、C6H5基含有多孔体または前駆体、C2H5基含有多孔体
または前駆体、C3H6NH2 基含有多孔体または前駆体、お
よびCH3 基含有多孔体または前駆体（最下段）の順に示
している。図１２〜図１４に示すＸ線回折パターンから
明らかなように、これら有機基含有多孔体のうち、C3H6
SH基含有多孔体、C2H5基含有多孔体およびCH3 基含有多
孔体については、水熱処理前前駆体においてすでにヘキ
サゴナル構造を有していることが認められた（図１
２）。一方、C6H5基含有多孔体およびC3H6NH2 基含有多
孔体については、水熱処理前前駆体の段階では層状構造
を有していることが認められた（図１２）が、C6H5基含
有多孔体については水熱処理済み前駆体の段階ではC3H6
SH基含有多孔体、C2H5基含有多孔体およびCH3 基含有多
孔体における水熱処理済み前駆体と同様、ヘキサゴナル
構造を有していることが認められた（図１３）。而し
て、これら４種の有機基含有多孔体については、H+置換
処理後においても、ヘキサゴナル構造が安定して保持さ
れていることが確認された（図１４）。なかでも官能基
としてチオール基を含んでいるC3H6SH基含有多孔体につ
いては、３本のヘキサゴナル構造に帰属される回折Ｘ線
強度ピークが顕著に認められ、特に構造規則性の高い３
次元構造を有していることが示唆された。なお、本実施
例においてはC3H6NH2 基含有多孔体については、水熱処
理後も層状構造であり、H+置換処理後には３次元構造の
崩壊も認められた。従って、C3H6NH2 基含有多孔体につ
いてはH+置換処理に代えて焼成処理によって界面活性剤
テンプレートの除去を行うことが好ましいと思われる。Similarly, the X-ray diffraction patterns of the above five kinds of organic group-containing porous materials and their precursors were examined.
FIGS. 12 to 14 are X-rays of the precursor before hydrothermal treatment, the precursor after hydrothermal treatment and the porous body after hydrothermal treatment (porous body after H + substitution treatment) for the above-mentioned five kinds of organic group-containing mesoporous materials, respectively. It is a graph which shows a diffraction pattern. 12
~ In the charts shown in Fig. 14, the top row is C 3 H 6 SH
The group-containing porous body or precursor, hereinafter, C 6 H 5 group-containing porous body or precursor, C 2 H 5 group-containing porous body or precursor, C 3 H 6 NH 2 group-containing porous body or The order of the precursor and the CH 3 group-containing porous body or precursor (bottom row) is shown. As is clear from the X-ray diffraction patterns shown in FIGS. 12 to 14, among these organic group-containing porous bodies, C 3 H 6
Regarding the SH group-containing porous body, C 2 H 5 group-containing porous body and CH 3 group-containing porous body, it was confirmed that the precursor before hydrothermal treatment already had a hexagonal structure (Fig. 1).
2). On the other hand, it was confirmed that the C 6 H 5 group-containing porous body and the C 3 H 6 NH 2 group-containing porous body had a layered structure at the stage of the precursor before hydrothermal treatment (FIG. 12). For porous materials containing C 6 H 5 groups, C 3 H 6
It was confirmed that the SH group-containing porous body, the C 2 H 5 group-containing porous body and the CH 3 group-containing porous body had a hexagonal structure similarly to the hydrothermally treated precursors (FIG. 13). Thus, it was confirmed that the hexagonal structure of these four types of organic group-containing porous bodies was stably retained even after the H + substitution treatment (FIG. 14). Among them, regarding the C 3 H 6 SH group-containing porous body containing a thiol group as a functional group, the diffraction X-ray intensity peaks attributed to the three hexagonal structures are remarkably observed, and the structure regularity is particularly high.
It was suggested to have a dimensional structure. In addition, in this example, the C 3 H 6 NH 2 group-containing porous body had a layered structure even after hydrothermal treatment, and collapse of the three-dimensional structure was also observed after H + substitution treatment. Therefore, for the C 3 H 6 NH 2 group-containing porous body, it is preferable to remove the surfactant template by firing treatment instead of H + substitution treatment.
【００４５】次に、ヘキサゴナル構造が認められた上記
４種の有機基含有多孔体について、ヘキサゴナル格子の
ｄ100 値を算出した。結果を表１に示す。なお、表中の
前駆体１は水熱処理前前駆体を示し、前駆体２は水熱処
理後前駆体を示す。また、表中の界面活性剤抽出後は上
記塩酸／エタノ−ル溶液への浸漬によるH+置換処理を施
した水熱処理済み多孔体のことである。Next, the d 100 value of the hexagonal lattice was calculated for the above-mentioned four kinds of organic group-containing porous bodies in which the hexagonal structure was recognized. The results are shown in Table 1. In addition, the precursor 1 in a table | surface shows the precursor before hydrothermal treatment, and the precursor 2 shows the precursor after hydrothermal treatment. Further, in the table, it means a hydrothermally treated porous body which has been subjected to H + substitution treatment by immersion in the hydrochloric acid / ethanol solution after the extraction of the surfactant.
【００４６】[0046]
【表１】 [Table 1]
【００４７】表１から明らかなように、ｄ値は有機基
（Ｒ）の種類によって異なるがいずれも水熱処理済み前
駆体（前駆体２）および界面活性剤抽出後の水熱処理済
み多孔体において、水熱処理前前駆体（前駆体１）より
もｄ値が小さくなっている。このことは、上記水熱処理
および塩酸／エタノ−ル溶液への浸漬処理によって骨格
内のシリケート縮合が促進され、結果、骨格自体が収縮
したことが示唆される。また、このことは、図１５に示
したC6H5基含有多孔体について行った固体29ＳｉＮＭＲ
スペクトル解析の結果からも明らかである。図１５に示
すように、水熱処理後の前駆体およびテンプレート（界
面活性剤）抽出後の多孔体において、Ｔ3とＱ4 シリコ
ン種が増えたことは、上記シリケート縮合を裏付けるも
のである。As is clear from Table 1, the d value varies depending on the type of the organic group (R), but in both the hydrothermally treated precursor (precursor 2) and the hydrothermally treated porous body after extraction of the surfactant, The d value is smaller than that of the precursor before hydrothermal treatment (precursor 1). This suggests that the hydrothermal treatment and the immersion treatment in the hydrochloric acid / ethanol solution promoted the silicate condensation in the skeleton, and as a result, the skeleton itself contracted. In addition, this means that solid-state 29 SiNMR performed on the C 6 H 5 group-containing porous body shown in FIG.
It is also clear from the result of spectrum analysis. As shown in FIG. 15, the increase in T 3 and Q 4 silicon species in the precursor after hydrothermal treatment and the porous body after extraction of the template (surfactant) supports the above silicate condensation.
【００４８】次に、上記４種の有機基含有多孔体につい
ての窒素ガス吸着等温線を測定した。結果を図１６に示
す。図中の横軸は相対蒸気圧(P/Po)を示しており、縦軸
は各有機基含有多孔体の窒素吸着量(cc/g)を示してい
る。図１６に示すように、各有機基含有多孔体とも細孔
の存在が確認された。また、C2H5基含有多孔体およびCH
3 基含有多孔体については相対蒸気圧０．１〜０．３で
吸着量の立ち上がりが見られることから比較的大きな細
孔（１ｎｍ以上）の存在が示された。一方、C3H 6SH 基
含有多孔体およびC6H5基含有多孔体については、相対蒸
気圧が０．１より小さい領域で吸着等温線が立ち上がる
いわゆるＩ型を示しており、より小さな細孔（１ｎｍ未
満）の存在が示された。Next, the above-mentioned four kinds of organic group-containing porous materials will be described.
The nitrogen gas adsorption isotherm was measured. The results are shown in Figure 16.
You The horizontal axis in the figure shows the relative vapor pressure (P / Po), and the vertical axis.
Indicates the nitrogen adsorption amount (cc / g) of each organic group-containing porous material.
It As shown in FIG. 16, each organic group-containing porous body has pores.
Was confirmed. Also, C2HFiveGroup-containing porous material and CH
3For group-containing porous materials, the relative vapor pressure is 0.1 to 0.3.
Since the rise of the adsorption amount can be seen,
The presence of pores (1 nm and above) was shown. On the other hand, C3H 6SH group
Containing porous material and C6HFiveFor group-containing porous materials,
The adsorption isotherm rises in the region where the atmospheric pressure is less than 0.1
It shows so-called type I, which has smaller pores (1 nm
The existence of Mitsuru was shown.
【００４９】次に、上記得られた窒素吸着等温線から上
記４種の有機基含有多孔体についてＢＥＴ比表面積(m2/
g)を算出し、ＢＪＨ法によって細孔直径（Å）を算出し
た。結果を表２に示す。Next, from the nitrogen adsorption isotherm obtained above, the BET specific surface area (m 2 / m 2
g) was calculated, and the pore diameter (Å) was calculated by the BJH method. The results are shown in Table 2.
【００５０】[0050]
【表２】 [Table 2]
【００５１】表２から明らかなように、本実施例にかか
る有機基含有多孔体はいずれもメタン等の低級炭化水素
ガスを吸着し得るのに十分な細孔直径および比表面積を
有している。また、中心細孔直径の±４０％の細孔径範
囲に全細孔容積の８０％以上が含まれていた（図示せ
ず）。As is clear from Table 2, each of the organic group-containing porous bodies of this example has a pore diameter and a specific surface area sufficient to adsorb lower hydrocarbon gas such as methane. . Further, 80% or more of the total pore volume was included in the pore diameter range of ± 40% of the central pore diameter (not shown).
【００５２】＜実施例２＞
−メソ多孔体の細孔内への金属原子の導入−
振盪攪拌可能な容器中にイオン交換水と所望量のＣＴＡ
Ｃを加え、６０ｍＭのＣＴＡＣ溶液を調製した。この溶
液中にテトラエトキシシラン(Si(OC2H5)4)とトリスメト
キシメルカプトプロピルシラン（HSCH2CH2CH2Si(OC
H3)3）とをモル比が４：１となるようにして加えた。而
して、少量のＮａＯＨを加えてｐＨを１１〜１３に調製
後、７０℃で７時間の攪拌処理により縮重合反応を行っ
た。得られた沈殿物を吸引濾過し、１Ｎ−塩酸／エタノ
ール溶液でテンプレートであるセチルトリメチルアンモ
ニウム塩を除去した。その後、室温で乾燥することによ
って本実施例にかかるチオール基含有多孔体を得た。こ
の多孔体は、上記実施例におけるC3H6SH基含有多孔体と
同様、細孔壁面に有機チオール基が付与されていること
が確認された。<Example 2> -Introduction of metal atom into pores of mesoporous material-Ion-exchanged water and desired amount of CTA in a container capable of shaking and stirring
C was added to prepare a 60 mM CTAC solution. Tetraethoxysilane (Si (OC 2 H 5 ) 4 ) and trismethoxymercaptopropylsilane (HSCH 2 CH 2 CH 2 Si (OC
H 3) 3) and a molar ratio of 4: was added to 1 so as. Then, after adjusting the pH to 11 to 13 by adding a small amount of NaOH, the polycondensation reaction was performed by stirring at 70 ° C. for 7 hours. The obtained precipitate was suction filtered, and the template cetyltrimethylammonium salt was removed with a 1N hydrochloric acid / ethanol solution. Then, it was dried at room temperature to obtain a thiol group-containing porous body according to this example. It was confirmed that the porous body has an organic thiol group attached to the pore wall surface, like the C 3 H 6 SH group-containing porous body in the above-mentioned Examples.
【００５３】次に、本実施例に係るチオール基含有多孔
体の細孔内に、金属塩化物として塩化第二銅(CuCl2) 、
塩化ニッケル(NiCl2) および二塩化マンガン(MnCl2) を
それぞれ導入した３種類の金属原子導入多孔体を作製し
た。すなわち、上記金属塩化物０．５モルをエタノール
に溶解して得た溶液を含む密閉可能な容器中に、０．１
ｇの本実施例にかかるチオール基含有多孔体を入れ、当
該溶液中にかかる多孔体を分散させた。次いで、上記容
器を６０℃の湯浴中で３時間反応させた。その後、吸引
濾過して得た沈殿物（多孔体）をエタノールで洗浄後、
室温にて乾燥させた。この結果、有機チオール基が分布
している細孔内に銅、ニッケルまたはマンガンがそれぞ
れ導入（典型的には配位）された３種の金属原子導入多
孔体（以下、それぞれCu−導入多孔体、Ni−導入多孔体
およびMn−導入多孔体という。）を得ることができた
（上述の図５参照）。Next, in the pores of the thiol group-containing porous material according to this example, cupric chloride (CuCl 2 ) as a metal chloride,
Three kinds of metal atom-introduced porous bodies, into which nickel chloride (NiCl 2 ) and manganese dichloride (MnCl 2 ) were introduced, were prepared. That is, in a sealable container containing a solution obtained by dissolving 0.5 mol of the above metal chloride in ethanol,
g of the thiol group-containing porous body according to this example was put therein, and the porous body was dispersed in the solution. Then, the container was reacted in a water bath at 60 ° C. for 3 hours. Then, after washing the precipitate (porous material) obtained by suction filtration with ethanol,
It was dried at room temperature. As a result, three types of metal atom-introduced porous bodies (hereinafter, typically Cu-introduced porous bodies) into which copper, nickel, or manganese are introduced (typically coordinated) in the pores in which the organic thiol groups are distributed , Ni-introduced porous body and Mn-introduced porous body) were obtained (see FIG. 5 described above).
【００５４】＜実施例３＞
−金属原子導入多孔体に関するメタンガス吸着能の評価
−
次に、上記Cu−導入多孔体、Ni−導入多孔体およびMn−
導入多孔体に関するメタンガス吸着能を以下のようにし
て評価した。本実施例におけるメタンガス吸着試験は、
いわゆるマイクロ天秤を用いた重量法に基づくものであ
る。具体的には、図１７に示すようなマイクロ天秤利用
に基づくガス吸着量測定装置１を用いて行った。以下、
詳述する。<Example 3> -Evaluation of methane gas adsorption capacity of metal atom-introduced porous body-Next, the above Cu-introduced porous body, Ni-introduced porous body and Mn-
The methane gas adsorption capacity of the introduced porous material was evaluated as follows. The methane gas adsorption test in this example is
It is based on a weight method using a so-called microbalance. Specifically, the measurement was performed using a gas adsorption amount measuring device 1 based on the use of a microbalance as shown in FIG. Less than,
Detailed description.
【００５５】図１７において、この装置１には、試料Ｓ
（上記金属原子導入多孔体）を配置するための密閉可能
な試料室２が備えられている。この試料室２内には、差
動トランス４を介して石英スプリング５に連結している
秤量管３が備えられている。一方、この試料室２には第
一コック９を介した送気管１３が接続されている。ま
た、試料室２および石英スプリング５の周囲には、循環
恒温槽６に連通するウォータージャケット１６が備えら
れている。送気管１３には真空ポンプ１１が接続されて
いる他、コック８，１４，１５を介してメタンガスボン
ベ７、バッファタンク１０および圧力計（10Torrスケールお
よび1000Torrスケールの二連）１２ａ，１２ｂがそれぞれ接
続されている。以下、この装置１を用いたガス吸着量測
定の方法を説明する。In FIG. 17, this apparatus 1 is equipped with a sample S
A sealable sample chamber 2 for disposing the (metal atom-introduced porous body) is provided. In the sample chamber 2, a weighing tube 3 connected to a quartz spring 5 via a differential transformer 4 is provided. On the other hand, an air supply pipe 13 is connected to the sample chamber 2 via a first cock 9. Around the sample chamber 2 and the quartz spring 5, a water jacket 16 communicating with the circulating constant temperature bath 6 is provided. In addition to the vacuum pump 11 being connected to the air supply pipe 13, a methane gas cylinder 7, a buffer tank 10 and a pressure gauge (two units of 10 Torr scale and 1000 Torr scale) 12a, 12b are connected via cocks 8, 14, 15 respectively. Has been done. Hereinafter, a method of measuring a gas adsorption amount using the device 1 will be described.
【００５６】１０ｍｇの試料Ｓを試料室２内の秤量管３
先端部に配置する。その後、真空ポンプ１１を作動させ
つつ第一コック９を開放し、試料室２内を真空排気し
た。同時に、循環恒温槽６を作動させて２５℃に水温が
安定した水をウォータージャケット１６内に循環させ
た。これにより、試料室および石英スプリング５（測定
部）を常温（ここでは２５℃）に保つことができる。而
して、試料Ｓの重量が一定になったのを確認後、コック
８を開いて所定圧のメタンガスをメタンガスボンベ７よ
り供給する。そして、試料Ｓにおけるメタンガスの吸着
量を石英スプリング５の負荷量から算出した。なお、石
英スプリング５および試料室２等の浮力の補正値は予め
試料なしの状態で測定したメタン圧−変位の関係から求
めた。なお、本メタンガス吸着試験では、上記３種の金
属原子導入多孔体の他、上記実施例２に係る有機チオー
ル基含有多孔体（即ち金属原子導入前のもの）および上
述の層間架橋製造法に従ってカネマイトと界面活性剤と
から得られた上記ＦＳＭ−１６（即ち有機基を含まない
ヘキサゴナル構造メソ多孔体）についても、同条件でメ
タン吸着能を調べた。併せて、ガス吸着特性の比較対照
として、活性炭繊維（Ａ２０；細孔径1.13mm、比表面積
1770m2/g、細孔容積0.97ml/g、嵩密度0.03g/cc）および
キャタラー社製の粒状活性炭（ＡＣ）を用いて、同条件
でメタン吸着能を調べた。A weighing tube 3 in the sample chamber 2 for 10 mg of the sample S
Place it at the tip. Then, the first cock 9 was opened while operating the vacuum pump 11, and the sample chamber 2 was evacuated. At the same time, the circulating constant temperature bath 6 was operated to circulate water having a stable water temperature of 25 ° C. in the water jacket 16. Thereby, the sample chamber and the quartz spring 5 (measurement part) can be kept at room temperature (here, 25 ° C.). Then, after confirming that the weight of the sample S has become constant, the cock 8 is opened and methane gas having a predetermined pressure is supplied from the methane gas cylinder 7. Then, the adsorption amount of the methane gas in the sample S was calculated from the load amount of the quartz spring 5. The correction value of the buoyancy of the quartz spring 5 and the sample chamber 2 was obtained from the methane pressure-displacement relationship measured in advance without the sample. In addition, in the present methane gas adsorption test, in addition to the above-mentioned three kinds of metal atom-introduced porous bodies, the organic thiol group-containing porous body according to Example 2 (that is, before introduction of metal atoms) and the above-described interlayer cross-linking manufacturing method were used to produce kanemite. With respect to the above FSM-16 (that is, a mesoporous hexagonal structure containing no organic group) obtained from the above and a surfactant, the methane adsorption ability was examined under the same conditions. In addition, activated carbon fiber (A20; pore size 1.13 mm, specific surface area)
1770 m 2 / g, pore volume 0.97 ml / g, bulk density 0.03 g / cc) and granular activated carbon (AC) manufactured by Catala Co., Ltd. were used to examine the methane adsorption capacity under the same conditions.
【００５７】各平衡圧力（５０〜７００Torr）におけ
る、各試料の容積あたりのメタンガス吸着量（mmol/cc
）を吸着等温線として図１８に示す。併せて、７００T
orr(0.92 atm)時の各試料の容積あたりおよび重量あた
りのメタンガス吸着量（mmol/ccおよびmmol/g）を表３
に示す。Adsorption amount (mmol / cc) of methane gas per volume of each sample at each equilibrium pressure (50 to 700 Torr)
18 is shown as an adsorption isotherm in FIG. In addition, 700T
Table 3 shows the methane gas adsorption amount (mmol / cc and mmol / g) per volume and weight of each sample at orr (0.92 atm).
Shown in.
【００５８】[0058]
【表３】 [Table 3]
【００５９】図１８および表３から明らかなように、３
種の金属原子含有多孔体および有機チオール基含有多孔
体（表、図中のCuCl2/HS- 、NiCl2/HS- 、MnCl2/HS- お
よびHS- ）のいずれもが、常温で常圧またはそれ以下の
圧力条件下において粒状活性炭（表、図中のAC）と同等
またはそれ以上のメタンガス吸着能を有することが示さ
れた。これに対して、繊維状活性炭(A20) および有機基
非含有多孔体(FSM-16)のメタンガス吸着能は上記粒状活
性炭等よりも劣っており、繊維状活性炭(A20)について
の容積あたりのガス吸着能が最低であった。このこと
は、繊維状活性炭が極めて比表面積の大きい嵩高な物質
であるため、容積あたりのガス吸着能が他の供試多孔材
料よりもはるかに劣ることを示している。また、特に金
属原子として銅またはニッケルを導入したものは、容積
(cc)あたりのガス吸着量が粒状活性炭のおよそ１．６〜
１．８倍であることが明らかとなった。また、これら金
属原子導入多孔体は重量あたりのメタンガス吸着量でも
粒状活性炭のそれを上回っていた。このことは、本発明
の炭化水素ガス吸着剤の中でも特に、これら金属原子を
細孔内に導入した多孔体が容積あたりのガス吸着能に優
れており、例えば、自動車のようにガス吸着剤搭載スペ
ースが限られている場合に好適に使用し得るガス吸着剤
であることを示すものである。As is clear from FIG. 18 and Table 3, 3
All kinds of metal atom-containing porous materials and organic thiol group-containing porous materials (CuCl 2 / HS-, NiCl 2 / HS-, MnCl 2 / HS- and HS- in the table and figures) are at normal pressure at room temperature. It was shown that it has a methane gas adsorption capacity equal to or higher than that of granular activated carbon (AC in the table and figure) under pressure conditions of or lower. On the other hand, the methane gas adsorption capacity of the fibrous activated carbon (A20) and the organic group-free porous body (FSM-16) is inferior to that of the granular activated carbon or the like, and the gas per volume of the fibrous activated carbon (A20). The adsorption capacity was the lowest. This indicates that the fibrous activated carbon is a bulky substance having an extremely large specific surface area, and therefore the gas adsorption capacity per volume is far inferior to that of the other tested porous materials. In addition, especially when copper or nickel is introduced as a metal atom,
The amount of gas adsorbed per (cc) is about 1.6 for granular activated carbon.
It was revealed to be 1.8 times. In addition, the amount of adsorbed methane gas per weight of these metal atom-introduced porous bodies exceeded that of granular activated carbon. This means that, among the hydrocarbon gas adsorbents of the present invention, a porous body in which these metal atoms are introduced into the pores has an excellent gas adsorbing capacity per volume. This shows that the gas adsorbent can be preferably used when the space is limited.
【００６０】[0060]
【発明の効果】本発明によれば、自動車のような限られ
た貯蔵スペースにも多量にメタンおよびその他の低級炭
化水素ガスを貯蔵し得る実用的な炭化水素ガス吸着剤を
提供することができる。すなわち、本発明の炭化水素ガ
ス吸着剤によれば、容積あたりのガス吸着能が優れてお
り、常温で常圧またはそれ以下の圧力条件下において、
メタンガスその他の常温常圧で気体状態を保ち得る低級
炭化水素ガスを効率よく可逆的に吸着することができ
る。According to the present invention, it is possible to provide a practical hydrocarbon gas adsorbent capable of storing a large amount of methane and other lower hydrocarbon gas even in a limited storage space such as an automobile. . That is, according to the hydrocarbon gas adsorbent of the present invention, the gas adsorption capacity per volume is excellent, under normal pressure or normal pressure conditions at room temperature,
It is possible to reversibly and efficiently adsorb lower hydrocarbon gas such as methane gas which can maintain a gas state at room temperature and atmospheric pressure.
【図１】ヘキサゴナル構造多孔体の細孔壁構造を模式的
に示す説明図である。FIG. 1 is an explanatory view schematically showing a pore wall structure of a hexagonal structure porous body.
【図２】シリカ系多孔体の細孔壁に有機基を付与する手
段の一例を示す説明図である。FIG. 2 is an explanatory diagram showing an example of means for providing an organic group to the pore walls of a silica-based porous body.
【図３】シリカ系多孔体の細孔壁に有機基を付与する手
段の一例を示す説明図である。FIG. 3 is an explanatory diagram showing an example of means for providing an organic group to the pore walls of a silica-based porous body.
【図４】ヘキサゴナル構造多孔体の細孔壁に付与された
有機チオール基の状態を模式的に示す説明図である。FIG. 4 is an explanatory view schematically showing a state of an organic thiol group provided on a pore wall of a hexagonal structure porous body.
【図５】有機チオール基が付与されたヘキサゴナル構造
多孔体の細孔内に金属原子が導入された状態を模式的に
示す説明図である。FIG. 5 is an explanatory view schematically showing a state in which a metal atom is introduced into the pores of a hexagonal structure porous body to which an organic thiol group has been added.
【図６】実施例１で得た有機基含有多孔体についての13
ＣＮＭＲスペクトルを示す図である。[6] 13 of the organic group-containing porous body obtained in Example 1
It is a figure which shows a CNMR spectrum.
【図７】実施例１で得た有機基含有多孔体についての29
ＳｉＮＭＲスペクトルを示す図である。[7] 29 for organic-group-containing porous body obtained in Example 1
It is a figure which shows SiNMR spectrum.
【図８】実施例１で得たC3H6SH基含有多孔体に係る水熱
処理前前駆体のＸ線回折パターンを示す図である。FIG. 8 is a view showing an X-ray diffraction pattern of a precursor before hydrothermal treatment related to the C 3 H 6 SH group-containing porous body obtained in Example 1.
【図９】実施例１で得た非水熱処理C3H6SH基含有多孔体
のＸ線回折パターンを示す図である。FIG. 9 is a view showing an X-ray diffraction pattern of the non-hydrothermally treated C 3 H 6 SH group-containing porous body obtained in Example 1.
【図１０】実施例１で得たC3H6SH基含有多孔体に係る水
熱処理後前駆体のＸ線回折パターンを示す図である。10 is a view showing an X-ray diffraction pattern of a precursor after hydrothermal treatment of the C 3 H 6 SH group-containing porous body obtained in Example 1. FIG.
【図１１】実施例１で得た水熱処理済みC3H6SH基含有多
孔体のＸ線回折パターンを示す図である。FIG. 11 is a view showing an X-ray diffraction pattern of the hydrothermally treated C 3 H 6 SH group-containing porous body obtained in Example 1.
【図１２】実施例１で得た各有機基含有多孔体に係る水
熱処理前前駆体のＸ線回折パターンを示す図である。FIG. 12 is a view showing an X-ray diffraction pattern of a precursor before hydrothermal treatment relating to each organic group-containing porous body obtained in Example 1.
【図１３】実施例１で得た各有機基含有多孔体に係る水
熱処理後前駆体のＸ線回折パターンを示す図である。13 is a view showing an X-ray diffraction pattern of a precursor after hydrothermal treatment of each organic group-containing porous body obtained in Example 1. FIG.
【図１４】実施例１で得た各水熱処理済み有機基含有多
孔体のＸ線回折パターンを示す図である。FIG. 14 is a view showing an X-ray diffraction pattern of each hydrothermally treated organic group-containing porous body obtained in Example 1.
【図１５】実施例１で得たC6H5基含有多孔体ならびに該
多孔体の水熱処理前前駆体および水熱処理後前駆体につ
いての29ＳｉＮＭＲスペクトルを示す図である。FIG. 15 is a diagram showing 29 Si NMR spectra of a C 6 H 5 group-containing porous body obtained in Example 1, and a precursor before hydrothermal treatment and a precursor after hydrothermal treatment of the porous body.
【図１６】実施例１で得た各有機基含有多孔体の窒素吸
着等温線を示す図である。16 is a diagram showing a nitrogen adsorption isotherm of each organic group-containing porous body obtained in Example 1. FIG.
【図１７】マイクロ天秤利用に基づくガス吸着量測定装
置の一例を示した図である。FIG. 17 is a diagram showing an example of a gas adsorption amount measuring device based on the use of a microbalance.
【図１８】実施例３における各多孔材料のメタンガス吸
着等温線を示す図である。18 is a diagram showing a methane gas adsorption isotherm of each porous material in Example 3. FIG.
１ 装置 ２ 試料室 ５ 石英スプリング ７ メタンガスボンベ Ｓ 試料 1 device 2 Sample chamber 5 Quartz spring 7 Methane gas cylinder S sample
フロントページの続き (56)参考文献 特開 平６−15165（ＪＰ，Ａ) 特開 平７−80296（ＪＰ，Ａ) 特開 平８−67578（ＪＰ，Ａ) 特開 平９−313929（ＪＰ，Ａ) 特開2000−128521（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 20/00 - 20/34 C01B 33/00 Continuation of the front page (56) Reference JP-A-6-15165 (JP, A) JP-A-7-80296 (JP, A) JP-A-8-67578 (JP, A) JP-A-9-313929 (JP , A) JP 2000-128521 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) B01J 20/00-20/34 C01B 33/00
Claims (6)
のメソ多孔体であって細孔壁面に有機基および／または
官能基を含む多孔体から実質的に構成される、炭素数１
〜４の炭化水素ガスを吸着させるための炭化水素ガス吸
着剤。1. A carbon number 1 having an inorganic or inorganic / organic hybrid mesoporous material, which is substantially composed of a porous material having an organic group and / or a functional group on the pore wall surface.
A hydrocarbon gas adsorbent for adsorbing the hydrocarbon gas of ~ 4.
求項１に記載の炭化水素ガス吸着剤。2. The hydrocarbon gas adsorbent according to claim 1, wherein the porous body has metal atoms.
ール基を含んでいる、請求項１に記載の炭化水素ガス吸
着剤。3. The hydrocarbon gas adsorbent according to claim 1, wherein the organic group and / or the functional group contains a thiol group.
ている、請求項１または３に記載の炭化水素ガス吸着
剤。4. The hydrocarbon gas adsorbent according to claim 1, which holds metal atoms in the pores of the porous body.
ルである、請求項２または４に記載の炭化水素ガス吸着
剤。5. The hydrocarbon gas adsorbent according to claim 2 or 4, wherein the metal atom is copper and / or nickel.
シリカ系メソ多孔体であって水中で５０℃〜２００℃の
加熱処理を施して調製された多孔体である、請求項１〜
５のいずれかに記載の炭化水素ガス吸着剤。6. The porous body is a silica-based mesoporous body having a silicate skeleton, and is a porous body prepared by heat treatment in water at 50 ° C. to 200 ° C.
5. The hydrocarbon gas adsorbent according to any one of 5.
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| JP3500994B2 true JP3500994B2 (en) | 2004-02-23 |
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| JP3530926B2 (en) | 2000-07-04 | 2004-05-24 | 独立行政法人産業技術総合研究所 | Method for producing crystalline layered metallosilicate |
| JP4830078B2 (en) * | 2000-11-28 | 2011-12-07 | 独立行政法人産業技術総合研究所 | Method for retaining methane molecules and pressure vessel filled with imogolite |
| FR2822470B1 (en) * | 2001-03-21 | 2003-08-15 | Air Liquide | PROCESS FOR THE PREPARATION OF ORGANIC-INORGANIC, MESOPOROUS HYBRID MATERIALS. NEW MATERIALS AND THEIR USE FOR SEPARATING GASES |
| JP5258318B2 (en) * | 2008-02-12 | 2013-08-07 | 豊田通商株式会社 | Method for surface treatment of mesoporous silica, slurry composition for resin addition, filler for resin, and method for producing resin composition |
| JP5291980B2 (en) * | 2008-04-25 | 2013-09-18 | 花王株式会社 | Core-shell mesoporous silica particles |
| JP5332821B2 (en) * | 2009-03-31 | 2013-11-06 | 株式会社豊田中央研究所 | Mesopore orientation material |
| JP5373497B2 (en) * | 2009-07-21 | 2013-12-18 | 日本分光株式会社 | Measuring device with temperature chamber control function |
| KR101344698B1 (en) | 2011-06-01 | 2013-12-26 | 한국화학연구원 | Method for producing porous organic-inorganic hybrid |
| JP6355077B2 (en) * | 2013-12-20 | 2018-07-11 | 学校法人慶應義塾 | Method for producing coating liquid for porous mesoporous silica membrane and method for producing porous mesoporous silica membrane |
| JP7086342B2 (en) * | 2017-03-21 | 2022-06-20 | 株式会社豊田中央研究所 | CO2 separator and its manufacturing method |
| JP7414636B2 (en) * | 2020-05-08 | 2024-01-16 | セトラスホールディングス株式会社 | Gas adsorbent, method for producing the gas adsorbent, and gas adsorption method |
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