JPH09313950A - Metal halide-supporting mesopore material, metal hydroxide-supporting mesopore material, metal oxide-supporting mesopore material, metal-supporting mesopore material and production of them - Google Patents
Metal halide-supporting mesopore material, metal hydroxide-supporting mesopore material, metal oxide-supporting mesopore material, metal-supporting mesopore material and production of themInfo
- Publication number
- JPH09313950A JPH09313950A JP8127465A JP12746596A JPH09313950A JP H09313950 A JPH09313950 A JP H09313950A JP 8127465 A JP8127465 A JP 8127465A JP 12746596 A JP12746596 A JP 12746596A JP H09313950 A JPH09313950 A JP H09313950A
- Authority
- JP
- Japan
- Prior art keywords
- mesopore
- supporting
- metal halide
- metal
- mesopore material
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 185
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 125
- 239000002184 metal Substances 0.000 title claims abstract description 125
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 239000011148 porous material Substances 0.000 claims abstract description 105
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 93
- 150000005309 metal halides Chemical class 0.000 claims abstract description 93
- 125000000524 functional group Chemical group 0.000 claims abstract description 24
- 238000009826 distribution Methods 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 9
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 59
- 239000003960 organic solvent Substances 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 28
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 150000004820 halides Chemical class 0.000 claims description 6
- 239000003849 aromatic solvent Substances 0.000 claims description 4
- 238000009739 binding Methods 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 229910001502 inorganic halide Inorganic materials 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 2
- 230000005540 biological transmission Effects 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 331
- 239000000377 silicon dioxide Substances 0.000 description 164
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 87
- 229910052757 nitrogen Inorganic materials 0.000 description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- 239000003054 catalyst Substances 0.000 description 33
- 238000001816 cooling Methods 0.000 description 30
- 229910052782 aluminium Inorganic materials 0.000 description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 25
- 239000003921 oil Substances 0.000 description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 21
- 239000000047 product Substances 0.000 description 21
- 239000007787 solid Substances 0.000 description 20
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 18
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 16
- 239000010410 layer Substances 0.000 description 16
- 150000002892 organic cations Chemical class 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- 229910001413 alkali metal ion Inorganic materials 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 235000002597 Solanum melongena Nutrition 0.000 description 11
- 238000010586 diagram Methods 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- -1 (V) Chemical class 0.000 description 10
- 238000000634 powder X-ray diffraction Methods 0.000 description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 125000005372 silanol group Chemical group 0.000 description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000012937 correction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- 239000011973 solid acid Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000000859 sublimation Methods 0.000 description 3
- 230000008022 sublimation Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000002781 deodorant agent Substances 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229910003091 WCl6 Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、金属ハロゲン化物
担持メソポア材料、金属水酸化物担持メソポア材料、金
属酸化物担持メソポア材料、金属担持メソポア材料およ
びそれらの製造方法に関する。これらの材料は、触媒、
吸着材、脱臭剤その他の利用が可能である。TECHNICAL FIELD The present invention relates to a metal halide-supporting mesopore material, a metal hydroxide-supporting mesopore material, a metal oxide-supporting mesopore material, a metal-supporting mesopore material, and a method for producing them. These materials are catalysts,
It is possible to use adsorbents, deodorants, etc.
【０００２】[0002]
【従来の技術】従来、シリカやアルミナなどの無機酸化
物を担体として用いて、非水条件下で金属ハロゲン化物
との反応をおこない金属ハロゲン化物担持触媒が合成さ
れている。その合成方法としては、有機溶媒を用いる方
法と金属ハロゲン化物の蒸気を接触させる方法がある
が、無機酸化物と金属ハロゲン化物をより均一に反応さ
せるには、有機溶媒法が優れている。2. Description of the Related Art Conventionally, a metal halide-supported catalyst has been synthesized by using an inorganic oxide such as silica or alumina as a carrier to react with a metal halide under non-aqueous conditions. As the synthesis method, there are a method using an organic solvent and a method in which vapor of a metal halide is brought into contact, but the organic solvent method is excellent for more uniformly reacting the inorganic oxide and the metal halide.
【０００３】特開昭４８−６１４０３号公報には、γ−
アルミナと塩化亜鉛、塩化第二錫、または四塩化チタン
のトルエン中での反応による合成が開示されている。ま
た、特開昭５０−９２８７９号公報には、シリカと塩化
マグネシウムとの高温（３００℃）での固相反応、およ
びシリカと四塩化チタンのヘキサン中での反応による合
成が開示されている。In Japanese Patent Laid-Open No. 48-61403, γ-
Synthesis is disclosed by reaction of alumina with zinc chloride, stannic chloride, or titanium tetrachloride in toluene. Further, Japanese Patent Application Laid-Open No. 50-92879 discloses a solid phase reaction between silica and magnesium chloride at high temperature (300 ° C.) and a reaction between silica and titanium tetrachloride in hexane.
【０００４】これらの無機酸化物担体は、不均一な孔径
の細孔しかもっていないため、均一な細孔を有する無機
酸化物から金属ハロゲン化物担持触媒はまだ得られてい
ない。均一な細孔を有する無機酸化物から金属ハロゲン
化物担持触媒を合成するには、金属ハロゲン化物分子が
侵入できる大きさの均一な細孔（メソポア）が無機酸化
物に存在することが必要である。しかも、有機溶媒を用
いる方法によって、無機酸化物粒子の外表面および細孔
内表面と、金属ハロゲン化物とを均一に反応させるため
には、金属ハロゲン化物分子が有機溶媒に溶解するかま
たは室温で液状であること、および無機酸化物の有機溶
媒中での分散性が良いことがさらに必要である。したが
って、従来の有機溶媒中での金属ハロゲン化物担持触媒
の合成反応では、使用される金属ハロゲン化物は主に室
温で液状のものや有機溶媒に対する溶解性が優れたもの
に限られていた。Since these inorganic oxide carriers have only pores having a non-uniform pore size, a metal halide-supported catalyst has not yet been obtained from an inorganic oxide having uniform pores. In order to synthesize a metal halide-supported catalyst from an inorganic oxide having uniform pores, it is necessary for the inorganic oxide to have uniform pores (mesopores) of a size that allows metal halide molecules to penetrate. . Moreover, in order to uniformly react the outer surface and the inner surface of the pores of the inorganic oxide particles with the metal halide by the method using the organic solvent, the metal halide molecule is dissolved in the organic solvent or at room temperature. It is further necessary that it be liquid and that the dispersibility of the inorganic oxide in the organic solvent is good. Therefore, in the conventional synthesis reaction of a metal halide-supported catalyst in an organic solvent, the metal halide used is mainly limited to those which are liquid at room temperature and those which have excellent solubility in an organic solvent.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記の事情
に鑑みてなされたもので、一定の大きさの細孔（メソポ
ア）を均一に有する無機酸化物に、金属ハロゲン化物、
金属酸化物、金属水酸化物、金属が一層または二層以上
結合した担持材料およびその製造方法を提供することを
目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an inorganic oxide uniformly having pores (mesopores) of a certain size is added to a metal halide,
An object of the present invention is to provide a metal oxide, a metal hydroxide, a carrier material in which one or more layers of metal are bonded, and a method for producing the same.
【０００６】[0006]
【課題を解決するための手段】本発明の金属ハロゲン化
物担持メソポア材料は、２〜１０ｎｍの範囲内でかつ均
一な径の細孔を多数有する無機酸化物の多孔体であっ
て、少なくとも前記細孔内表面に備えた官能基に金属ハ
ロゲン化物が結合してなることを特徴とする。メソポア
材料の細孔の径は、２〜６ｎｍの範囲内で均一であるこ
とが好ましい。また、このメソポア材料の細孔は、細孔
分布曲線における最大ピークを示す細孔直径が２〜１０
ｎｍの範囲にあり、かつ細孔の６０％以上が細孔径分布
曲線における最大ピークを示す細孔直径の±４０％の範
囲の細孔径を有することが好ましい。The metal halide-supporting mesopore material of the present invention is a porous body of an inorganic oxide having a large number of pores having a uniform diameter within the range of 2 to 10 nm, and at least the above-mentioned fine particles. It is characterized in that a metal halide is bonded to a functional group provided on the inner surface of the hole. The pore diameter of the mesopore material is preferably uniform within the range of 2 to 6 nm. The pores of this mesopore material have a pore diameter of 2 to 10 at which the maximum peak in the pore distribution curve is shown.
It is preferable that 60 nm or more of the pores have a pore diameter in the range of ± 40% of the pore diameter showing the maximum peak in the pore diameter distribution curve.
【０００７】金属ハロゲン化物は、メソポア担体の細孔
内表面に均一に一分子層または二分子層以上に結合して
いることが好ましい。このメソポア担体の細孔内表面の
官能基に対する金属ハロゲン化物の反応率は、単量体換
算で３０〜３００％であることが好ましい。金属ハロゲ
ン化物としては、周期律表のIVa 〜VIII族あるいはＩｂ
族のハロゲン化物、またはIa,IIa,IIb〜VIb の金属のハ
ロゲン化物であることが好ましい。具体的により好まし
い金属ハロゲン化物は、ルイス酸として作用するもので
たとえば、無水塩化アルミニウム（AlCl3)または無水塩
化第二鉄(FeCl3) が挙げられる。It is preferable that the metal halide is uniformly bonded to the inner surface of the pores of the mesopore carrier in a monolayer or bilayer or more. The reaction rate of the metal halide with respect to the functional group on the inner surface of the pores of the mesopore carrier is preferably 30 to 300% in terms of monomer. Examples of the metal halide include IVa to VIII or Ib of the periodic table.
It is preferably a group halide or a metal halide of Ia, IIa, IIb to VIb. More specifically preferable metal halides are those which act as a Lewis acid, and examples thereof include anhydrous aluminum chloride (AlCl 3 ) or anhydrous ferric chloride (FeCl 3 ).
【０００８】本発明の金属ハロゲン化物担持メソポア材
料の製造方法は、２〜１０ｎｍの範囲内で均一な径の多
数の細孔を有し、該細孔内表面には少なくとも金属ハロ
ゲン化物が結合できる官能基を有する無機酸化物の多孔
体と、金属ハロゲン化物とを有機溶媒中で反応させて該
金属ハロゲン化物と該無機酸化物の官能基との結合を形
成することを特徴とする。The method for producing a metal halide-supporting mesopore material of the present invention has a large number of pores having a uniform diameter within a range of 2 to 10 nm, and at least a metal halide can be bound to the inner surfaces of the pores. It is characterized in that a porous body of an inorganic oxide having a functional group is reacted with a metal halide in an organic solvent to form a bond between the metal halide and the functional group of the inorganic oxide.
【０００９】該有機溶媒は、予め脱水処理され、該無機
ハロゲン化物も予め乾燥され、反応が非水雰囲気下でお
こなわれることが好ましい。この有機溶媒は、具体的に
は、ハロゲン系溶媒（クロロホルム、四塩化炭素な
ど）、ニトロ化物溶媒（ニトロベンゼン、ニトロメタン
など）、芳香族溶媒（ベンゼン、トルエン、キシレンな
ど）の少なくとも１種から選ばれることが望ましい。The organic solvent is preferably dehydrated in advance, the inorganic halide is also dried in advance, and the reaction is preferably carried out in a non-aqueous atmosphere. This organic solvent is specifically selected from at least one selected from halogen solvents (chloroform, carbon tetrachloride, etc.), nitrate compounds (nitrobenzene, nitromethane, etc.), and aromatic solvents (benzene, toluene, xylene, etc.). Is desirable.
【００１０】該無機酸化物は粒径分布が、透過型電子顕
微鏡写真下での粒子直径が０．０２〜５μｍの範囲にあ
り、かつ６０％以上の粒子が粒子直径の比１：１０の範
囲内にあることが好ましい。該金属ハロゲン化物は、有
機溶媒易溶性のもの、たとえば、３価あるいは５価のＳ
ｂの塩化物、３価のＵの塩化物、３価のＧａの塩化物、
２価あるいは４価のＧｅの塩化物、４価のＳｎの塩化
物、１価のＳｅの塩化物、６価のＷの塩化物、４価のＴ
ｅの塩化物、４価のＰｂの塩化物、２価のＰｔの塩化
物、４価のＶの塩化物、３価あるいは５価のＰの塩化物
から選ばれる少なくとも１種を用いることが好ましい。The particle size distribution of the inorganic oxide is such that the particle diameter under a transmission electron micrograph is in the range of 0.02 to 5 μm, and 60% or more of the particles have a particle diameter ratio of 1:10. It is preferable to be within. The metal halide is easily soluble in an organic solvent, for example, trivalent or pentavalent S.
b chloride, trivalent U chloride, trivalent Ga chloride,
Divalent or tetravalent Ge chloride, tetravalent Sn chloride, monovalent Se chloride, hexavalent W chloride, tetravalent T
It is preferable to use at least one selected from the chloride of e, the chloride of tetravalent Pb, the chloride of divalent Pt, the chloride of tetravalent V, the chloride of trivalent and pentavalent P. .
【００１１】金属塩化物を例にすると、Zn,In(III),U(I
V),U(V),Ca,Au(III),Si,Co(II),Hg(II),Zr(II),Sn(II),
Tl(III),W(V),Ta(V),Fe(II),Fe(III),Te(II),Cu(II),V
(II),Pd(II),Pt(IV),Bi,As(III),Be,B(III),Mo(II),Mo
(V),Li,Re(IV) などの塩化物を挙げることができる。ま
た、この金属ハロゲン化物は、融点が２５℃であり、の
室温で液体のもの、たとえば、４価のＳｉの塩化物、４
価のＧｅの塩化物、４価のＳｎの塩化物、１価のＳｅの
塩化物、４価のＴｉの塩化物、４価のＰｂの塩化物、４
価のＶの塩化物、３価のＡｓの塩化物、２価のＢの塩化
物、３価のＰの塩化物から選ばれる少なくとも１種を用
いることが好ましい。Taking metal chlorides as an example, Zn, In (III), U (I
V), U (V), Ca, Au (III), Si, Co (II), Hg (II), Zr (II), Sn (II),
Tl (III), W (V), Ta (V), Fe (II), Fe (III), Te (II), Cu (II), V
(II), Pd (II), Pt (IV), Bi, As (III), Be, B (III), Mo (II), Mo
Chlorides such as (V), Li and Re (IV) can be mentioned. This metal halide has a melting point of 25 ° C. and is liquid at room temperature, such as tetravalent Si chloride, 4
Tetravalent Ge chloride, tetravalent Sn chloride, monovalent Se chloride, tetravalent Ti chloride, tetravalent Pb chloride, 4
It is preferable to use at least one selected from a valent V chloride, a trivalent As chloride, a divalent B chloride, and a trivalent P chloride.
【００１２】金属ハロゲン化物担持メソポア材料は、金
属ハロゲン化物の蒸気をメソポア担体に接触させて該金
属ハロゲン化物と該メソポア担体の官能基との結合を形
成する製造方法も可能である。本発明の金属水酸化物担
持メソポア材料は、メソポア担体の細孔内表面に備えた
官能基に金属水酸化物が結合していることを特徴とす
る。The metal halide-supporting mesopore material can also be produced by a method in which the vapor of the metal halide is brought into contact with the mesopore carrier to form a bond between the metal halide and the functional group of the mesopore carrier. The metal hydroxide-supporting mesopore material of the present invention is characterized in that the metal hydroxide is bonded to the functional group provided on the inner surface of the pores of the mesopore carrier.
【００１３】金属水酸化物担持メソポア材料の製造方法
は、金属ハロゲン化物担持メソポア材料を加水分解して
得られることを特徴とする。本発明の金属酸化物担持メ
ソポア材料は、２〜１０ｎｍのメソポアを有し、各メソ
ポアの細孔径が均一で、少なくとも細孔内表面に金属ハ
ロゲン化物が結合された官能基を有する無機酸化物から
なることを特徴とする。The method for producing a metal hydroxide-supporting mesopore material is characterized by being obtained by hydrolyzing a metal halide-supporting mesopore material. The metal oxide-supporting mesopore material of the present invention comprises an inorganic oxide having a mesopore of 2 to 10 nm, a uniform pore size of each mesopore, and at least a functional group having a metal halide bonded to the inner surface of the pore. It is characterized by
【００１４】金属酸化物担持メソポア材料の製造方法
は、金属ハロゲン化物担持メソポア材料、金属水酸化物
担持メソポア担体を焼成して得られることを特徴とす
る。本発明の金属担持メソポア材料は、２〜１０ｎｍの
メソポアを有し、各メソポアの細孔径が均一で、少なく
とも細孔内表面に金属ハロゲン化物が固定された官能基
を有する無機酸化物からなることを特徴とする。The method for producing a metal oxide-supporting mesopore material is characterized by being obtained by firing a metal halide-supporting mesopore material and a metal hydroxide-supporting mesopore carrier. The metal-supporting mesopore material of the present invention has an inorganic oxide having a mesopore of 2 to 10 nm, a uniform pore size of each mesopore, and at least a functional group having a metal halide fixed on the inner surface of the pore. Is characterized by.
【００１５】金属担持メソポア材料の製造方法は、金属
ハロゲン化物担持メソポア材料を還元または熱分解する
ことを特徴とする。The method for producing a metal-supporting mesopore material is characterized by reducing or thermally decomposing a metal halide-supporting mesopore material.
【００１６】[0016]
【発明の実施の形態】本発明の金属類担持メソポア材料
は、メソポア担体に金属ハロゲン化物、金属酸化物、金
属水酸化物、金属が結合して構成されている。このメソ
ポア担体は、たとえば、耐熱性層状シリカ多孔体が利用
できる。耐熱性層状シリカ多孔体は、結晶性層状珪酸塩
の板状のシート層が複数積層し、隣接する上記シート層
の層間がシロキサン結合による結合点において縮幅し、
該結合点の間においては拡幅して微孔を形成しているハ
ニカム状多孔構造をもつ。BEST MODE FOR CARRYING OUT THE INVENTION The metal-supporting mesopore material of the present invention is composed of a metal halide, a metal oxide, a metal hydroxide and a metal bonded to a mesopore carrier. As this mesopore carrier, for example, a heat resistant layered silica porous material can be used. The heat-resistant layered silica porous material has a plurality of plate-shaped sheet layers of crystalline layered silicate laminated, and the interlayers of the adjacent sheet layers are narrowed at a bonding point by a siloxane bond,
It has a honeycomb-like porous structure that widens between the connecting points to form fine pores.
【００１７】この結晶性層状珪酸塩中に含まれるアルカ
リ金属イオンの含有率は０．２重量％以下でかつ比表面
積は１０００ｍ2 ／ｇ以上であることが好ましい。アル
カリ金属イオンの含有率が０．２重量％を超えた場合に
は、比較的低温で原子の移動が促進され、クリストバラ
イトなどへの結晶化が起こる。そのため、層状シリカ多
孔体の比表面積が減少し、さらには耐熱性が低下してし
まう。また、層状シリカ多孔体の比表面積が１０００ｍ
2 ／ｇ未満の場合には、層状シリカ多孔体に触媒を担持
させるとき、触媒の活性を十分に発揮することができ
ず、また吸着剤として使用するときに有機物などに対す
る吸着能力が低い。It is preferable that the content of the alkali metal ion contained in the crystalline layered silicate is 0.2% by weight or less and the specific surface area is 1000 m 2 / g or more. When the content of the alkali metal ion exceeds 0.2% by weight, the movement of atoms is promoted at a relatively low temperature, and crystallization to cristobalite or the like occurs. Therefore, the specific surface area of the layered silica porous material is reduced, and further the heat resistance is reduced. In addition, the specific surface area of the layered silica porous material is 1000 m.
When the amount is less than 2 / g, the activity of the catalyst cannot be sufficiently exhibited when the catalyst is supported on the layered silica porous material, and the ability to adsorb organic substances is low when used as an adsorbent.
【００１８】代表的な層状シリカ多孔体を図１２の生成
機構の模式図に示すように、骨格の組成がＳｉＯ2 で、
板状のシートが上下方向に湾曲又は屈曲している。そし
て上下の各シート間が部分的に結合し、ハニカム状の骨
格を形成している。ハニカムの微孔の直径は、１〜６０
Åである。シート層は、ＳｉＯ2 四面体が２次元的に結
合することで形成されるシリケート層であり、ＳｉＯ2
四面体の結合点が屈曲可能であるため、シート層全体と
しても湾曲または屈曲が可能である。シート層は、マグ
ネシウムイオン（Ｍｇ2+）、アルミニウムイオン（Ａｌ
3+）などのシート層の屈曲性を妨げる八面体を含まな
い。また、上記シート層は、Ｎａ+ などのアルカリ金属
イオンおよびＨ+ を挟んで、複数枚積層している。ま
た、具体的には、結晶性層状珪酸塩としては、たとえ
ば、カネマイト（ＮａＨＳｉ2 Ｏ5 ・３Ｈ2 Ｏ）が好ま
しい。A typical layered silica porous material has a skeleton composition of SiO 2 as shown in the schematic diagram of the production mechanism of FIG.
The plate-shaped sheet is curved or bent in the vertical direction. The upper and lower sheets are partially connected to each other to form a honeycomb skeleton. The diameter of the fine holes of the honeycomb is 1 to 60.
Å. Sheet layer is a silicate layer SiO 2 tetrahedra are formed by combining two-dimensionally, SiO 2
Since the connecting point of the tetrahedron can be bent, the sheet layer as a whole can be curved or bent. The sheet layer is made of magnesium ions (Mg 2+ ), aluminum ions (Al
3+ ) and other octahedrons that hinder the flexibility of the sheet layer are not included. Further, the above-mentioned sheet layers are laminated by sandwiching an alkali metal ion such as Na + and H + . Further, specifically, as the crystalline layered silicate, for example, kanemite (NaHSi 2 O 5 .3H 2 O) is preferable.
【００１９】また、他の結晶性層状珪酸塩としては、ジ
珪酸ナトリウム（Ｎａ2 Ｓｉ2 Ｏ3）マカタイト（Ｎａ
2 Ｓｉ4 Ｏ9 ・５Ｈ2 Ｏ）、アイアライト（Ｎａ2 Ｓｉ
8 Ｏ 17・ＸＨ2 Ｏ）、マガディアイト（Ｎａ2 Ｓｉ14Ｏ
29・ＸＨ2 Ｏ）、ケニヤイト（Ｎａ2 Ｓｉ20Ｏ41・ＸＨ
2 Ｏ）などが代表的であるが、これらに限定されるもの
ではない。Further, as another crystalline layered silicate,
Sodium silicate (NaTwoSiTwoOThree) Macatite (Na
TwoSiFourO9・ 5HTwoO), Iarite (NaTwoSi
8O 17・ XHTwoO), Magadiite (NaTwoSi14O
29・ XHTwoO), Kenyaite (NaTwoSi20O41・ XH
TwoO) and the like are typical, but are not limited to these
is not.
【００２０】上記層状シリカ多孔体の製造方法について
は、含水率１０重量％以上の結晶性層状珪酸塩中の層間
に存在するアルカリ金属イオンを有機物陽イオンとイオ
ン交換させ、該有機陽イオンを層間に導入する層間拡幅
工程と、上記イオン交換により遊離した上記アルカリ金
属イオンを除去する洗浄工程と、洗浄した上記結晶性層
状珪酸塩を焼成することにより、上記有機物陽イオンを
燃焼せしめて多孔性の層状シリカ多孔体を得る多孔化工
程とを含む耐熱性層状シリカ多孔体の製造方法がある。Regarding the method for producing the above layered silica porous material, the alkali metal ion existing between the layers in the crystalline layered silicate having a water content of 10% by weight or more is ion-exchanged with an organic cation, and the organic cation is intercalated. Introduced into the interlayer widening step, a washing step to remove the alkali metal ions liberated by the ion exchange, by firing the washed crystalline layered silicate, by burning the organic cations of the porous There is a method for producing a heat-resistant layered silica porous body including a porosification step of obtaining a layered silica porous body.
【００２１】結晶性層状珪酸塩は非晶質珪酸塩から合成
することができる。非晶質珪酸塩としては、市販の粉末
珪酸ナトリウム、水ガラスを乾燥して粉末としたものな
どである。たとえば、結晶性層状珪酸塩の１種であるカ
ネマイトを合成する場合、Ｎａ2 Ｏ／ＳｉＯ2 ＝２にで
きるだけ近い組成の非晶質の珪酸ナトリウムを用いるこ
とが好ましい。The crystalline layered silicate can be synthesized from an amorphous silicate. Examples of the amorphous silicate include commercially available powdered sodium silicate and powder obtained by drying water glass. For example, when synthesizing kanemite, which is one type of crystalline layered silicate, it is preferable to use amorphous sodium silicate having a composition as close as possible to Na 2 O / SiO 2 = 2.
【００２２】この非晶質珪酸ナトリウムを空気中、６５
０〜７５０℃で焼成すると、δ型Ｎａ2 Ｓｉ2 Ｏ5 に結
晶化する。６５０℃より低い温度ではβまたはγ型Ｎａ
2 Ｓｉ2 Ｏ5 に、７５０℃を超える温度ではα型Ｎａ2
Ｓｉ2 Ｏ5 に結晶化する。α、β、γ型では水との反応
で結晶性層状珪酸塩が生成しない。次に、このδ型Ｎａ
2 Ｓｉ2 Ｏ5 を２倍から５０倍の水に分散させ、１５時
間攪拌した後、濾過する。これにより、δ型Ｎａ2 Ｓｉ
2 Ｏ5 のＮａ+ の一部が水中のＨ+ と置換し、ＮａＨＳ
ｉ2 Ｏ5 ・３Ｈ2 Ｏとなり、結晶性層状珪酸塩であるカ
ネマイトが得られる。This amorphous sodium silicate was mixed with 65% in air.
When baked at 0 to 750 ° C., it crystallizes into δ-type Na 2 Si 2 O 5 . Β or γ-type Na at temperatures below 650 ° C
2 Si 2 O 5, the at temperatures above 750 ° C. alpha-type Na 2
Crystallize to Si 2 O 5 . The α, β, γ type does not form a crystalline layered silicate due to the reaction with water. Next, this δ-type Na
2 Si 2 O 5 is dispersed in 2 to 50 times water, stirred for 15 hours, and then filtered. As a result, δ-type Na 2 Si
Part of Na + of 2 O 5 is replaced with H + in water, and NaHS
i 2 O 5 · 3H 2 O is obtained, and kanemite which is a crystalline layered silicate is obtained.
【００２３】上記結晶性層状珪酸塩における含水率は１
０重量％以上である。１０重量％未満では、結晶性層状
珪酸塩が凝集し、次の層間拡幅工程において、水中での
分散性が低下し、有機物陽イオンとアルカリ金属イオン
との交換が起こりにくくなる。１０重量％以上であれ
ば、結晶性珪酸塩が、次の層間拡幅工程の際に水によく
分散し、層間のアルカリ金属イオンと有機物陽イオンと
のイオン交換がスムースに短時間で行われる。その結
果、層状シリカ多孔体の比表面積が１０００ｍ2 ／ｇ以
上となり、また、アルカリ金属イオンの残存量が０．２
重量％以下の優れた耐熱性層状シリカ多孔体を得ること
ができる。The water content of the crystalline layered silicate is 1
0% by weight or more. If it is less than 10% by weight, the crystalline layered silicate aggregates, the dispersibility in water decreases in the next interlayer widening step, and the exchange of organic cations and alkali metal ions becomes difficult to occur. When the content is 10% by weight or more, the crystalline silicate is well dispersed in water in the next interlayer widening step, and the ion exchange between the interlayer alkali metal ion and the organic cation is smoothly performed in a short time. As a result, the specific surface area of the layered silica porous material was 1000 m 2 / g or more, and the residual amount of alkali metal ions was 0.2.
It is possible to obtain an excellent heat-resistant layered silica porous body having a weight percentage of not more than.
【００２４】上記層間拡幅工程においては、結晶性層状
珪酸塩中にあるアルカリ金属イオンが有機物陽イオンと
イオン交換される。有機物陽イオンはアルカリ金属イオ
ンよりも嵩高のため、結晶性層状珪酸塩の層間は拡幅さ
れる。これにより、シート層は有機物陽イオンを取り囲
む形で湾曲する。それと同時に、有機物陽イオンが導入
された部分を除く、隣合うシート層中のシラノール（Ｓ
ｉ−ＯＨ）が形成される。これにより、隣合うシート層
どうしが、部分的にシロキサン結合により結合され、三
次元的ハニカム状の層構造を形成する。図１３のａ（活
性化前）およびｂ（活性化後）に三次元的ハニカム状の
層構造の説明模式図を示した。In the interlayer widening step, alkali metal ions in the crystalline layered silicate are ion-exchanged with organic cations. Since organic cations are bulkier than alkali metal ions, the layers of the crystalline layered silicate are widened. As a result, the sheet layer curves around the organic cations. At the same time, except for the portion where the organic cations are introduced, the silanol (S
i-OH) is formed. Thereby, adjacent sheet layers are partially bonded by siloxane bonds to form a three-dimensional honeycomb-like layer structure. FIG. 13 a (before activation) and b (after activation) show schematic explanatory views of the three-dimensional honeycomb-shaped layer structure.
【００２５】上記有機物陽イオンとしては、アルキルト
リメチルアンモニウム、ジメチルジアルキルアンモニウ
ム、アルキルアンモニウム、ベンジルトリメチルアンモ
ニウムなどがある。上記イオン交換の際、ｐＨを８〜９
に調整することが好ましい。さらに、その後、３０〜９
０℃にて加熱することが好ましい。上記洗浄工程におい
ては、上記イオン交換により遊離したアルカリ金属イオ
ン、有機物陽イオンの対イオン、または未反応の有機物
陽イオンが除かれる。特に、遊離したアルカリ金属イオ
ンの含有率が０．２重量％以下となる。Examples of the organic cations include alkyltrimethylammonium, dimethyldialkylammonium, alkylammonium and benzyltrimethylammonium. During the above ion exchange, the pH should be 8-9.
It is preferable to adjust to. After that, 30 to 9
It is preferable to heat at 0 ° C. In the washing step, alkali metal ions, counter ions of organic cations, or unreacted organic cations released by the ion exchange are removed. In particular, the content of the released alkali metal ions is 0.2% by weight or less.
【００２６】上記多孔体化工程においては、層間に取り
込まれた有機物陽イオンを燃焼させ、微細な微孔を形成
させる。また、シロキサン結合の三次元骨格を安定化さ
せる。焼成は、酸化雰囲気中で温度６００〜１２００℃
で行うことが望ましい。６００℃未満の場合、あるいは
酸化雰囲気以外の場合には、有機物陽イオンを十分に除
去することはできない。一方、１２００℃を超える場
合、焼結が進み過ぎ、微孔が破れ、比表面積が低下する
ので好ましくない。In the step of forming a porous body, the organic cations taken in between the layers are burned to form fine micropores. Further, the three-dimensional skeleton of the siloxane bond is stabilized. The firing is performed in an oxidizing atmosphere at a temperature of 600 to 1200 ° C.
It is desirable to perform in. If the temperature is lower than 600 ° C. or if the atmosphere is not in an oxidizing atmosphere, organic cations cannot be sufficiently removed. On the other hand, when the temperature exceeds 1200 ° C., sintering proceeds excessively, micropores are broken, and the specific surface area is undesirably reduced.
【００２７】層状シリカ多孔体は、アルカリ金属イオン
の含有量が０．２重量％以下であるので、８００℃以上
の高温状態でも結晶化しにくく、微孔も安定である。そ
のため、耐熱性に優れている。また、１０００ｍ2 ／ｇ
以上の比表面積を有するため、触媒担体、燃料等の有機
物の吸収材などの優れた吸着性能を発揮する。また、上
記の製造方法によれば、上記の如き優れた耐熱性層状シ
リカ多孔体を製造することができる。Since the layered silica porous material has an alkali metal ion content of 0.2% by weight or less, it is difficult to crystallize even at a high temperature of 800 ° C. or higher, and the micropores are stable. Therefore, it has excellent heat resistance. Also, 1000 m 2 / g
Since it has the above-mentioned specific surface area, it exhibits excellent adsorption performance for catalyst carriers, absorbents for organic substances such as fuel, and the like. Moreover, according to the above-mentioned manufacturing method, the excellent heat-resistant layered silica porous material as described above can be manufactured.
【００２８】上記のメソポア担体は、２〜６ｎｍのメソ
ポアの細孔径が均一で、少なくとも細孔内表面に金属ハ
ロゲン化物などと結合できる官能基を有する無機酸化物
多孔体である。その表面積が非常に大きくかつ耐熱性が
優れるので、触媒担体や吸着剤としての応用が期待され
ている。なお、本発明の金属ハロゲン化物担持メソポア
材料を構成するメソポア担体の具体例として主として層
状鉱物より合成するものを説明したが、これに限られる
ものではなく、たとえば、表面活性剤のミセルを囲む用
にセラミックスの殻を形成してメソポア担体とするもの
等、他の方法で作られたメソポア担体を用いることがで
きる。The above-mentioned mesopore carrier is an inorganic oxide porous body in which the mesopores of 2 to 6 nm have a uniform pore size and at least the inner surface of the pores has a functional group capable of binding a metal halide or the like. Since its surface area is very large and its heat resistance is excellent, its application as a catalyst carrier or an adsorbent is expected. As a specific example of the mesopore carrier constituting the metal halide-supporting mesopore material of the present invention, the one mainly synthesized from a layered mineral has been described, but the present invention is not limited to this, for example, for surrounding a micelle of a surfactant. It is possible to use a mesopore carrier prepared by another method, such as one in which a ceramic shell is formed into a mesopore carrier.
【００２９】メソポア担体の細孔表面の官能基数は、特
定の活性化処理によりその存在数を増加させることがで
きる。たとえば、（シリカ）メソポア担体の場合には、
１Ｎ濃度の塩酸中で加熱することにより、シラノール基
を増加させることができる。金属ハロゲン化物とシラノ
ール基とを反応させる前に、メソポア担体の吸着水を除
去する操作が必要である。メソポア担体の吸着水は８０
〜１５０℃の加熱で脱離するが、２００℃以上の高温で
は官能基の脱離が生じる恐れがある。したがって、減圧
下で吸着水の除去をおこなえば、８０℃以下の低温で脱
水・乾燥が可能である。たとえば、（シリカ）メソポア
担体の場合には、真空ポンプ減圧下に１１０℃で４時間
乾燥させることが可能である。The number of functional groups on the pore surface of the mesopore carrier can be increased by the specific activation treatment. For example, in the case of (silica) mesopore support,
The silanol groups can be increased by heating in 1N hydrochloric acid. Before reacting the metal halide with the silanol group, it is necessary to remove adsorbed water on the mesopore carrier. Adsorbed water of mesopore carrier is 80
Although it is desorbed by heating up to 150 ° C, desorption of the functional group may occur at a high temperature of 200 ° C or higher. Therefore, if the adsorbed water is removed under reduced pressure, dehydration / drying can be performed at a low temperature of 80 ° C. or lower. For example, in the case of (silica) mesopore carrier, it is possible to dry at 110 ° C. for 4 hours under reduced pressure of a vacuum pump.
【００３０】メソポア担体を分散させる有機溶媒として
は、たとえば、以下のような有機溶媒がメソポア担体と
馴染みがよく、それらの溶媒中でメソポア担体の見掛け
の体積が増加することが判明した。 １）メソポア担体が室温で膨張・透明になる溶媒：スル
ホラン、トリクレン、ピリジンなど。 ２）メソポア担体が加熱で膨張・透明になる溶媒：ニト
ロベンゼン、ベンゾニトリル、テトラクロロエタン、テ
トラクロロエチレン、クロロベンゼン、アニソールな
ど。 ３）メソポア担体が室温で膨張・半透明になる溶媒：Ｎ
−メチル−２−ピロリドン、ジメチルスルホキシドな
ど。As the organic solvent in which the mesopore carrier is dispersed, for example, the following organic solvents are well compatible with the mesopore carrier, and it has been found that the apparent volume of the mesopore carrier increases in these solvents. 1) Solvents in which the mesopore carrier expands and becomes transparent at room temperature: sulfolane, trichlene, pyridine, etc. 2) Solvents in which the mesopore carrier expands and becomes transparent when heated: nitrobenzene, benzonitrile, tetrachloroethane, tetrachloroethylene, chlorobenzene, anisole, etc. 3) Solvent in which the mesopore carrier expands and becomes translucent at room temperature: N
-Methyl-2-pyrrolidone, dimethyl sulfoxide and the like.
【００３１】これらの有機溶媒が上記メソポア担体を高
分散できる理由は、上記メソポア担体の粒径が小さいこ
とにあると考えられる。すなわち、大きさがあまり異な
らない一次粒子どうしが疎にかつ弱く会合して二次粒子
が形成されているので、有機溶媒中で二次粒子の一次粒
子への解離が容易に起こると考えられる。したがって、
無機酸化物を有機溶媒中で高分散させるためには、無機
酸化物の粒径分布が小さいことが必要であり、また用い
る有機溶媒の種類は無機酸化物中の官能基の種類によっ
て変わるものである。It is considered that the reason why these organic solvents can highly disperse the mesopore carrier is that the particle size of the mesopore carrier is small. That is, since the primary particles that do not differ in size are associated with each other sparsely and weakly to form the secondary particles, it is considered that the secondary particles are easily dissociated into the primary particles in the organic solvent. Therefore,
In order to highly disperse an inorganic oxide in an organic solvent, it is necessary that the particle size distribution of the inorganic oxide is small, and the type of organic solvent used depends on the type of functional groups in the inorganic oxide. is there.
【００３２】無水金属ハロゲン化物は、共有結合性が高
く、有機溶媒に溶解するものが多い。有機溶媒に対する
溶解性によって、金属ハロゲン化物を４つに分類でき
る。塩化物について、以下にその分類を示す。なお、金
属ハロゲン化物は、ハロゲンが大きくなる順番（フッ化
物＜塩化物＜臭化物＜沃化物）に、共有結合性が増加し
て有機溶媒への溶解性が良くなる。 １）有機溶媒に不溶：IrCl3,BaCl2,KCl,CrCl3,Hg2Cl2,P
Cl5,RbCl,RhCl3,AuCl など。 ２）アルコールに溶ける：IrCl4,CdCl2,CeCL3,CsCl,TiC
l3,TiCl4,NbCl5,NiCl3,VCl3,MgCl2,MnCl2,LaCl3,CuCl2,
NaCl,PbCl2 など。 ３）アセトンや酢酸エチルやエーテルなどの非プロトン
性極性溶媒に溶ける（多くはアルコールにも溶ける）：
ZnCl2,InCl3,UCl4,UCl5,CaCl2,AuCl3,SiCl4,CoCl 2,HgCl
2,ZrCl2,SnCl2,TiCl3,WCl2,WCl5,TaCl5,FeCl2,FeCl3,Te
Cl2,CuCl2,VCl2,PdCl2,PtCl4,BiCl3, AsCl3,BeCl2, BCl
3,MoCl2,MoCl5, LiCl,ReCl4など。 ４）クロロホルム、四塩化炭素などのハロゲン系溶媒、
ニトロベンゼン、ニトロメタンなどのニトロ化物系溶
媒、あるいはベンゼンなどの芳香族系溶媒に溶ける（多
くはアルコールまたは前記非プロトン性極性溶媒にも溶
ける）：AlCl3,SbCl3,SbCl5,UCl3,GaCl3,GeCl3,GeCl2,S
nCl4,SeCl,WCl6,TeCl4,PbCl4,PtCl2,VCl4,PCl3,PCl5な
ど。Anhydrous metal halides have high covalent bondability.
Many are soluble in organic solvents. For organic solvents
According to solubility, metal halides can be classified into 4
You. The classification of chlorides is shown below. In addition, gold
In the group halide, the order of increasing halogen (fluorination
Covalent bond increases with the product <chloride> <bromide <iodide>
The solubility in organic solvents is improved. 1) Insoluble in organic solvent: IrCl3,BaCl2,KCl, CrClThree, HgTwoClTwo, P
ClFive, RbCl, RhClThree, AuCl etc. 2) Soluble in alcohol: IrClFour, CdCl2,CeCLThree, CsCl, TiC
lThree, TiClFour, NbClFive, NiClThree, VClThree, MgClTwo, MnClTwo, LaClThree, CuClTwo,
NaCl, PbClTwoSuch. 3) Non-proton such as acetone, ethyl acetate and ether
Soluble in polar solvents (mostly alcohol):
ZnClTwo, InClThree, UClFour, UClFive, CaClTwo, AuClThree, SiClFour, CoCl Two, HgCl
Two, ZrClTwo, SnClTwo, TiClThree, WClTwo, WClFive, TaClFive, FeCl2,FeClThree, Te
ClTwo, CuClTwo, VClTwo, PdClTwo, PtClFour, BiClThree, AsClThree, BeClTwo, BCl
Three, MoClTwo, MoClFive, LiCl, ReClFourSuch. 4) Halogen-based solvents such as chloroform and carbon tetrachloride,
Nitrides such as nitrobenzene and nitromethane
Soluble in medium or aromatic solvent such as benzene
Soluble in alcohol or the aprotic polar solvent
): AlClThree, SbClThree, SbClFive, UClThree, GaClThree, GeClThree, GeClTwo, S
nClFour, SeCl, WCl6, TeClFour, PbClFour, PtClTwo, VClFour, PClThree, PClFiveWhat
What.
【００３３】有機溶媒中でメソポア担体との反応に用い
られる無水金属ハロゲン化物は、上記分類の４）に相当
する有機溶媒易溶性のもの、上記分類の３）に相当する
有機溶媒可溶性のもの、またはTiCl4 などの室温で液状
のものである。なお、室温で液状の無水金属ハロゲン化
物としては、塩化物を例にすると、SiCl4,GeCl4,SnCl 4,
SeCl,TiCl4,PbCl4,VCl4,AsCl3,B2Cl4,PCl3などを挙げる
ことができる。Used for reaction with mesopore carrier in organic solvent
The corresponding anhydrous metal halides correspond to 4) of the above classification
Organic solvent easily soluble, corresponding to 3) of the above classification
Organic solvent soluble, or TiClFourLiquid at room temperature such as
belongs to. In addition, anhydrous metal halides that are liquid at room temperature
For example, if chloride is an example, SiClFour, GeClFour, SnCl Four,
SeCl, TiClFour, PbClFour, VClFour, AsClThree, BTwoClFour, PClThreeEtc.
be able to.
【００３４】これら無水金属ハロゲン化物を溶解する有
機溶媒としては、上記の該当する有機溶媒を用いるが、
無水金属ハロゲン化物が室温で液体の場合には無溶媒で
もよい。無水金属ハロゲン化物と無機酸化物との反応溶
媒に求められる特性は、無機酸化物を分散させること
と、無水金属ハロゲン化物を溶解状態または液状に保つ
ことである。したがって、反応溶媒は、純溶媒でも混合
溶媒でもよい。As the organic solvent for dissolving these anhydrous metal halides, the above-mentioned corresponding organic solvents are used.
When the anhydrous metal halide is liquid at room temperature, it may be solventless. The properties required for the reaction solvent of the anhydrous metal halide and the inorganic oxide are to disperse the inorganic oxide and to keep the anhydrous metal halide in a dissolved state or a liquid state. Therefore, the reaction solvent may be a pure solvent or a mixed solvent.
【００３５】無水金属ハロゲン化物と有機溶媒可溶性か
つ無機酸化物に対して有機溶媒中で非反応性である場合
には、有機溶媒に脱酸剤を添加する。脱酸剤としてはト
リアルキルアミン、ピリジン、ピコリン、ピラジンなど
の水素原子をもたない有機塩基が望ましい。有機溶媒
は、脱水処理して不活性雰囲気下に保存したものを用い
ることが好ましい。もしも反応系に水が存在すると、無
水金属ハロゲン化物が加水分解されて一部が水酸化物と
なるために、無機酸化物の官能基との均一な反応が期待
できなくなる。In the case where the anhydrous metal halide is soluble in the organic solvent and is nonreactive with the inorganic oxide in the organic solvent, a deoxidizing agent is added to the organic solvent. As the deoxidizing agent, organic bases having no hydrogen atom such as trialkylamine, pyridine, picoline, and pyrazine are preferable. As the organic solvent, it is preferable to use one that has been dehydrated and stored under an inert atmosphere. If water is present in the reaction system, the anhydrous metal halide is hydrolyzed and a part thereof is converted into hydroxide, so that uniform reaction with the functional group of the inorganic oxide cannot be expected.
【００３６】有機溶媒中での無水金属ハロゲン化物と無
機酸化物との反応は不活性雰囲気下におこなう。反応操
作の詳細は実施例で説明する。反応生成物の精製は次の
ようにおこなった。反応終了後に濾別した粗生成物を、
少なくとも無水金属ハロゲン化物を溶解する有機溶媒に
分散して加熱攪拌した後に濾別する操作により、未反応
の金属ハロゲン化物を洗いだした。この洗浄した粗生成
物を、さらに、真空ポンプ減圧下に加熱して残存する未
反応金属ハロゲン化物を蒸留又は昇華により除去した。The reaction between the anhydrous metal halide and the inorganic oxide in the organic solvent is carried out under an inert atmosphere. Details of the reaction operation will be described in Examples. The reaction product was purified as follows. The crude product filtered off after the reaction was
Unreacted metal halide was washed out by an operation of dispersing in an organic solvent in which at least anhydrous metal halide is dissolved, stirring with heating, and then filtering. The washed crude product was further heated under reduced pressure of a vacuum pump to remove the residual unreacted metal halide by distillation or sublimation.
【００３７】金属ハロゲン化物の蒸気を無機酸化物に接
触させて金属ハロゲン化物担持メソポア材料を製造する
場合には、用いる金属ハロゲン化物は、無機酸化物の官
能基が分離する温度未満の温度で、昇華または蒸発によ
り蒸気となるものであればよい。たとえば、シラノール
基を有する（シリカ）メソポア担体の場合には、約２０
０℃以下で蒸気となる金属ハロゲン化物が望ましい。無
機酸化物の前処理は、有機溶媒法と同様に行えばよい。
金属ハロゲン化物の蒸気を無機酸化物に接触させる反応
操作は、従来知られている方法にしたがうものとする。
金属ハロゲン化物担持メソポア材料の説明！ゼオライト
と異なる機構で酸点を発現する無水金属ハロゲン化物担
持メソポア材料の特徴を列挙する。 １ 無水金属ハロゲン化物には、ルイス酸性を発現する
ものが多く、特に無水塩化アルミニウムは超強酸として
作用するルイス酸である。したがって、無水金属ハロゲ
ン化物担持（シリカ）メソポア材料は、金属ハロゲン化
物の種類により酸強度を制御できる。 ２ （シリカ）メソポア担体が大きな表面積を有するの
で、大きな酸量を付加できる。 ３ 無水金属ハロゲン化物が細孔（メソポア）の大きさ
と分布が均一である（シリカ）メソポア材料に共有結合
性の高い結合で均一に固定・担持されているので、得ら
れた無水金属ハロゲン化物担持（シリカ）メソポア材料
も細孔（メソポア）の大きさと分布が均一である。 ４ 細孔の均一な大きさに基づく、触媒反応の形状選択
性の発現が期待できる。 ５ 酸点が均一に分布した大きい表面を有しているため
に、触媒反応効率が高いことが期待できる。 ６ 無水金属ハロゲン化物が（シリカ）メソポア材料に
高い共有結合性の高い結合で固定・担持されているの
で、ある程度の耐熱性が期待できる。 ７ 無水金属ハロゲン化物が（シリカ）メソポア材料に
高い共有結合性の高い結合で固定・担持されているの
で、無水金属ハロゲン化物の揮発性に基づく反応装置腐
食の問題などが改善できる。 ８ ルイス酸性を発現する無水金属ハロゲン化物以外
に、多様な無水金属ハロゲン化物を担持できる。When the vapor of the metal halide is brought into contact with the inorganic oxide to produce the metal halide-supporting mesopore material, the metal halide used is at a temperature below the temperature at which the functional groups of the inorganic oxide separate. Any material can be used as long as it becomes vapor by sublimation or evaporation. For example, in the case of a (silica) mesopore carrier having a silanol group, about 20
A metal halide that becomes vapor at 0 ° C. or lower is desirable. The pretreatment of the inorganic oxide may be performed in the same manner as the organic solvent method.
The reaction operation of bringing the vapor of the metal halide into contact with the inorganic oxide shall be in accordance with a conventionally known method.
Explanation of metal halide-supporting mesopore materials! The characteristics of anhydrous metal halide-supported mesopore materials that develop acid sites by a mechanism different from that of zeolite are listed. 1. Many anhydrous metal halides exhibit Lewis acidity, and anhydrous aluminum chloride is a Lewis acid that acts as a superacid. Therefore, the anhydrous metal halide-supported (silica) mesopore material can control the acid strength depending on the type of metal halide. Since the 2 (silica) mesopore carrier has a large surface area, a large amount of acid can be added. 3 Since the anhydrous metal halide is uniformly fixed and supported on the (silica) mesopore material in which the size and distribution of pores (mesopores) are uniform, the resulting anhydrous metal halide support is obtained. The (silica) mesopore material also has a uniform size and distribution of pores (mesopores). 4 It can be expected that the shape selectivity of the catalytic reaction is exhibited based on the uniform size of the pores. 5 Since it has a large surface in which acid points are uniformly distributed, it can be expected that the catalytic reaction efficiency is high. 6. Since the anhydrous metal halide is fixed and supported on the (silica) mesopore material with a bond having a high covalent bond, a certain degree of heat resistance can be expected. 7. Since the anhydrous metal halide is fixed and supported on the (silica) mesopore material with a bond having a high covalent bond, the problem of reactor corrosion due to the volatility of the anhydrous metal halide can be improved. 8. Various anhydrous metal halides can be supported in addition to the anhydrous metal halide that exhibits Lewis acidity.
【００３８】種々の反応に利用される固体触媒は、反応
効率などを向上させるために、一般に担体に期待されて
表面積を増やした形で使用されることが多いが、担体を
構成する無機酸化物の種類が異なると触媒活性も変化す
ることが知られている。担体が触媒金属を電子的に活性
化する効果は、シリカよりもアルミナ、チタニア、ジル
コニアなどが優れている場合が多いが、シリカ以外の無
機酸化物担体は高温条件下（たとえば５００℃以上）で
の表面積が小さい（２００ｍ2 ／ｇ以下）という欠点が
あった。Solid catalysts used in various reactions are generally used in a form expected to have a large surface area in order to improve reaction efficiency and the like. Inorganic oxides constituting the carrier are generally used. It is known that the catalytic activity changes depending on the type. Alumina, titania, zirconia, etc. are often superior to silica in the effect of electronically activating the catalytic metal by the carrier, but inorganic oxide carriers other than silica are not suitable under high temperature conditions (for example, 500 ° C. or higher). Has a drawback that the surface area is small (200 m 2 / g or less).
【００３９】そこで（シリカ）メソポア担体の全表面を
別の酸化物薄膜で被覆すると、表面積が大きくかつ耐熱
性が優れる別種メソポア担体として、（シリカ）メソポ
ア担体を改質できる。図１３ｃおよびｄにメソポア担体
に塩化アルミニウムが結合した状態の説明模式図を示し
た。ｃは塩化アルミニウムが一分子層結合した場合であ
り、ｄは塩化アルミニウムが二分子層結合した場合であ
る。そのため細孔（メソポア）に基づく形状選択性の発
現も当然期待できる。このような改質目的の報告はまだ
なされていない。Therefore, if the entire surface of the (silica) mesopore carrier is covered with another oxide thin film, the (silica) mesopore carrier can be modified as another kind of mesopore carrier having a large surface area and excellent heat resistance. 13C and 13D are schematic explanatory views showing a state in which aluminum chloride is bound to the mesopore carrier. c is the case where aluminum chloride is monolayer-bonded, and d is the case where aluminum chloride is bilayer-bonded. Therefore, it can be expected that the shape selectivity based on the pores (mesopores) is manifested. No report has been made on the purpose of such modification.
【００４０】金属水酸化物担持（シリカ）メソポア材
料、金属酸化物担持（シリカ）メソポア材料、金属担持
（シリカ）メソポア材料の特徴を次にまとめる。 １．金属ハロゲン化物は、簡単な処理で水酸化物や酸化
物や金属に変換できる。したがって、無水金属ハロゲン
化物担持（シリカ）メソポア材料から、上記担持物を簡
単な処理で容易に合成できる。The characteristics of the metal hydroxide-supported (silica) mesopore material, the metal oxide-supported (silica) mesopore material, and the metal-supported (silica) mesopore material are summarized below. 1. Metal halides can be converted into hydroxides, oxides and metals with simple processing. Therefore, the supported material can be easily synthesized from the anhydrous metal halide-supported (silica) mesopore material by a simple process.
【００４１】２．金属水酸化物（シリカ）メソポア材料
と金属酸化物担持（シリカ）メソポア材料は、（シリ
カ）メソポア材料の全表面を別の酸化物薄膜で被覆した
ものであり、シリカと別種の無機酸化物メソポア材料に
相当する。（なお、無機水酸化物を表面酸化状態が異な
る無機酸化物と見做すことができる。） ３．金属水酸化物担持（シリカ）メソポア材料と金属酸
化物担持（シリカ）メソポア材料は、これまでにない大
きさの表面積を有する、シリカとは別種の無機酸化物メ
ソポア材料である。2. The metal hydroxide (silica) mesopore material and the metal oxide-supporting (silica) mesopore material are obtained by coating the entire surface of the (silica) mesopore material with another oxide thin film, and are different from silica and another type of inorganic oxide mesopore. It corresponds to the material. (Note that the inorganic hydroxide can be regarded as an inorganic oxide having a different surface oxidation state.) 3. The metal hydroxide-supported (silica) mesopore material and the metal oxide-supported (silica) mesopore material are inorganic oxide mesopore materials different from silica, which have a surface area of unprecedented size.
【００４２】４．焼成した金属酸化物担持（シリカ）メ
ソポア材料は、細孔（メソポア）の大きさと分布が均一
であり、かつ表面積が大きく耐熱性も良いので、優れた
触媒担体として期待される。 ５．金属水酸化物担持（シリカ）メソポア材料と金属酸
化物担持（シリカ）メソポア材料は、合成に用いる金属
ハロゲン化物の種類を代えることで、多様な金属の化合
物が容易に得られる。4. The calcined metal oxide-supporting (silica) mesopore material has uniform pores (mesopores) in size and distribution, and has a large surface area and good heat resistance, and thus is expected as an excellent catalyst carrier. 5. With respect to the metal hydroxide-supporting (silica) mesopore material and the metal oxide-supporting (silica) mesopore material, various metal compounds can be easily obtained by changing the kind of the metal halide used in the synthesis.
【００４３】６．水溶性金属塩と別種無機酸化物メソポ
ア材料を混合して仮焼成した後に還元又は熱分解して金
属担持触媒を調整する際に、本発明により得られる５種
類の異なる表面酸化物状態を有する別種無機酸化物メソ
ポア材料を用いることにより、水溶性金属塩との相互作
用を変えられるので、結果的に担持触媒中の金属分散状
態を制御できる。したがって、触媒活性を制御できる。6. When a water-soluble metal salt and another kind of inorganic oxide mesopore material are mixed and calcined and then reduced or thermally decomposed to prepare a metal-supported catalyst, another kind having five different surface oxide states obtained by the present invention is prepared. By using the inorganic oxide mesopore material, the interaction with the water-soluble metal salt can be changed, and as a result, the metal dispersion state in the supported catalyst can be controlled. Therefore, the catalyst activity can be controlled.
【００４４】７．本発明により得られた金属担持（シリ
カ）メソポア材料は、（シリカ）メソポア材料に共有結
合性の高い結合で固定・担持された無水金属ハロゲン化
物を還元または熱分解して調整したものである。したが
って、従来の水溶性金属塩を分散して調整するものに比
べて、還元または熱分解で金属の凝集が生じにくいため
に、触媒金属の分散が良い金属担持（シリカ）メソポア
材料が得られる。この金属担持（シリカ）メソポア材料
は、触媒反応の効率の向上が期待される。7. The metal-supported (silica) mesopore material obtained by the present invention is prepared by reducing or thermally decomposing an anhydrous metal halide fixed and supported on the (silica) mesopore material with a bond having a high covalent bond. Therefore, as compared with a conventional method in which a water-soluble metal salt is dispersed and prepared, metal aggregation is less likely to occur due to reduction or thermal decomposition, so that a metal-supported (silica) mesopore material in which the catalyst metal is well dispersed is obtained. This metal-supported (silica) mesopore material is expected to improve the efficiency of catalytic reaction.
【００４５】無水金属ハロゲン化物担持（シリカ）メソ
ポア材料を次の２つの方法で加水分解すると、状態また
は化学構造が異なる２種類の金属水酸化物担持（シリ
カ）メソポア材料を合成することができる。第一の方法
は、無水金属ハロゲン化物担持（シリカ）メソポア材料
を空気中の水分に接触させて加水分解させるものであ
る。無水金属ハロゲン化物は水に対する反応性が高く、
極く微量の水分でも容易に室温で加水分解される。した
がって、上記加水分解において、空気中の水分量は極く
微量から飽和蒸気量まで変えることができ、また反応温
度は０℃から１００℃まで変えることができる。このよ
うな反応条件の違いは、上記加水分解反応において、無
水金属ハロゲン化物担持（シリカ）メソポア材料の金属
原子上のハロゲン原子が、水酸基で置換される割合を調
整することができる。By hydrolyzing the anhydrous metal halide-supported (silica) mesopore material by the following two methods, two kinds of metal hydroxide-supported (silica) mesopore materials having different states or chemical structures can be synthesized. The first method is to bring an anhydrous metal halide-supported (silica) mesopore material into contact with water in the air to cause hydrolysis. Anhydrous metal halides have high reactivity with water,
It is easily hydrolyzed at room temperature even with a very small amount of water. Therefore, in the above hydrolysis, the amount of water in the air can be changed from a very small amount to the amount of saturated vapor, and the reaction temperature can be changed from 0 ° C to 100 ° C. Such a difference in the reaction conditions can adjust the ratio in which the halogen atom on the metal atom of the anhydrous metal halide-supported (silica) mesopore material is replaced with a hydroxyl group in the hydrolysis reaction.
【００４６】第二の方法は、無水金属ハロゲン化物担持
（シリカ）メソポア材料を水中で加水分解して生成物を
得るものである。この方法では、加水分解で生じる遊離
のアルミニウム化合物が除去される特徴があり、また担
体と金属ハロゲン化物との化学結合の切断が生じる。そ
の切断の程度は、用いる水の量や反応温度などの反応条
件に依存するが、これらについて特に限定はない。すな
わち、得られる金属水酸化物担持（シリカ）メソポア材
料の金属原子上の水酸基の割合および金属原子と担体中
の珪素原子の割合を、反応条件の違いによって制御する
ことができる。The second method is to hydrolyze the anhydrous metal halide-supported (silica) mesopore material in water to obtain the product. This method is characterized in that the free aluminum compound generated by hydrolysis is removed, and the chemical bond between the carrier and the metal halide is broken. The degree of cleavage depends on the reaction conditions such as the amount of water used and the reaction temperature, but these are not particularly limited. That is, the ratio of the hydroxyl groups on the metal atoms and the ratio of the metal atoms to the silicon atoms in the carrier of the obtained metal hydroxide-supported (silica) mesopore material can be controlled by the difference in the reaction conditions.
【００４７】無水金属ハロゲン化物担持（シリカ）メソ
ポア材料を空気中で焼成すると、金属原子上のハロゲン
が気体分子として脱離し同時に空気中の酸素分子が導入
される反応が生じると推察される。したがって、焼成温
度は、（シリカ）メソポア材料が熱的に安定な１０００
℃以下であれば問題はなく、焼成の温度と時間を変える
ことにより、得られる金属酸化物担持（シリカ）メソポ
ア材料の金属の酸化状態を制御できる。It is speculated that when anhydrous metal halide-supported (silica) mesopore material is calcined in air, a reaction occurs in which halogens on metal atoms are eliminated as gas molecules and oxygen molecules in the air are simultaneously introduced. Therefore, the firing temperature is 1000 when the (silica) mesopore material is thermally stable.
There is no problem if the temperature is not higher than 0 ° C., and the oxidation state of the metal of the obtained metal oxide-supported (silica) mesopore material can be controlled by changing the firing temperature and time.
【００４８】金属水酸化物担持（シリカ）メソポア材料
は酸化状態の異なる金属酸化物担持（シリカ）メソポア
材料と見做すことができる。この材料を焼成する場合に
は、金属原子上のハロゲンと水素がハロゲン化水素ガス
として脱離して酸化が進行する反応と推察される。した
がって、焼成温度は、（シリカ）メソポア材料が熱的に
安定な１０００℃以下であれば問題なく、焼成の温度と
時間を変えることにより、得られる金属酸化物担持（シ
リカ）メソポア材料の金属の酸化状態を制御できる。The metal hydroxide-supported (silica) mesopore material can be regarded as a metal oxide-supported (silica) mesopore material having a different oxidation state. When this material is fired, it is presumed that the halogen and hydrogen on the metal atom are desorbed as a hydrogen halide gas and the oxidation proceeds. Therefore, if the firing temperature is 1000 ° C. or less at which the (silica) mesopore material is thermally stable, there is no problem, and by changing the firing temperature and time, the metal of the metal oxide-supported (silica) mesopore material obtained is changed. The oxidation state can be controlled.
【００４９】無水金属ハロゲン化物担持（シリカ）メソ
ポア材料を還元雰囲気で加熱すると、無水金属ハロゲン
化物部分が金属に還元されて、金属担持（シリカ）メソ
ポア材料を調整できる。還元雰囲気としては、水素ガ
ス、アンモニアガス、ヒドラジン蒸気、またはその他の
還元性の有機化合物の共存下であればよい。反応温度
は、特に限定はなく、一般的な還元反応温度で良いが、
（シリカ）メソポア材料が熱的に安定な１０００℃以下
である必要がある。When the anhydrous metal halide-supported (silica) mesopore material is heated in a reducing atmosphere, the anhydrous metal halide moiety is reduced to a metal, and the metal-supported (silica) mesopore material can be prepared. The reducing atmosphere may be in the presence of hydrogen gas, ammonia gas, hydrazine vapor, or other reducing organic compound. The reaction temperature is not particularly limited and may be a general reduction reaction temperature,
The (silica) mesopore material must be thermally stable at 1000 ° C. or lower.
【００５０】金属が金、銀、白金、パラジウムなどであ
る無水金属ハロゲン化物担持（シリカ）メソポア材料を
空気中で加熱すると、金属ハロゲン化物部分が先ず比較
的不安定な酸化物になるために、更なる加熱で熱分解が
おこり金属担持（シリカ）メソポア材料が得られる。こ
の場合の加熱条件は、無水金属ハロゲン化物について知
られている条件でよい。When an anhydrous metal halide-supported (silica) mesopore material whose metal is gold, silver, platinum, palladium or the like is heated in air, the metal halide portion first becomes a relatively unstable oxide. Further heating causes thermal decomposition and a metal-supported (silica) mesopore material is obtained. The heating conditions in this case may be those known for anhydrous metal halides.
【００５１】[0051]
（実施例１）一定の大きさのメソポアを均一に有する
（シリカ）メソポア担体の合成方法。先ず粉末珪酸ソー
ダ（ＳｉＯ2 ／Ｎａ2 Ｏ＝２．００日本化学工業株製）
を７００℃空気中で６時間焼成した。５０ｇの焼成粉末
珪酸ソーダを粒径１ｍｍ以下に粉砕した後、５００ｍｌ
の水に分散させ、室温で３時間攪拌した。その後、ブフ
ナーロートを用い、固形分を濾別し、層状珪酸塩の一種
であるカネマイト（ＮａＨＳｉ2 Ｏ5 ・３Ｈ2 Ｏ）を合
成した。(Example 1) A method for synthesizing a (silica) mesopore carrier having a uniform size of mesopores. First, powdered sodium silicate (SiO 2 / Na 2 O = 2.00 manufactured by Nippon Kagaku Kogyo Co., Ltd.)
Was calcined in air at 700 ° C. for 6 hours. 50 g of fired powder sodium silicate is crushed to a particle size of 1 mm or less, then 500 ml
Was dispersed in water and stirred at room temperature for 3 hours. Then, the solid content was filtered off using a Buchner funnel to synthesize kanemite (NaHSi 2 O 5 .3H 2 O), which is a kind of layered silicate.
【００５２】このカネマイトを乾燥せずに、湿った状態
で、セチルトリメチルアンモニウム水溶液に分散させ
た。このセチルトリメチルアンモニウム水溶液は、０．
１モルのセチルトリメチルアンモニウムクロライドを１
０００ｍｌの水に溶解させることにより調製した。この
分散液を２０００ｍｌ容量のフラスコにいれた。先ず、
７０℃で３時間、攪拌モータで攪拌しながら湯浴中で加
熱した。その後、２Ｎ塩酸水溶液を滴下して、そのｐＨ
をゆっくり８．５に調製した。その後、更に７０℃で３
時間攪拌しながら加熱した。The kanemite was not dried but dispersed in a cetyltrimethylammonium aqueous solution in a wet state. This cetyltrimethylammonium aqueous solution contains 0.1 mL
1 mole of cetyltrimethylammonium chloride
Prepared by dissolving in 000 ml of water. This dispersion was placed in a 2000 ml volumetric flask. First,
The mixture was heated in a water bath at 70 ° C. for 3 hours while stirring with a stirring motor. After that, 2N hydrochloric acid aqueous solution is added dropwise to adjust the pH.
Was slowly adjusted to 8.5. After that, 3 more at 70 ℃
Heated with stirring for hours.
【００５３】この分散液を室温まで冷却した後、固形生
成物を濾別した。１０００ｍｌの脱イオン水で合計５回
洗浄した後、乾燥した。この粉末を、５５０℃、空気中
で６時間焼成し、（シリカ）メソポア担体を得た。この
生成物をＦ−１６Ｃと略記する。 （実施例２）実施例１で合成した（シリカ）メソポア担
体（Ｆ−１６Ｃ）の結晶構造を観察した。After cooling this dispersion to room temperature, the solid product was filtered off. It was washed with 1000 ml of deionized water for a total of 5 times and then dried. This powder was calcined in air at 550 ° C. for 6 hours to obtain a (silica) mesopore carrier. This product is abbreviated as F-16C. (Example 2) The crystal structure of the (silica) mesopore carrier (F-16C) synthesized in Example 1 was observed.
【００５４】（シリカ）メソポア担体（Ｆ−１６Ｃ）の
粉末Ｘ線回折パターンを図１に示した。回折角度が１０
°以下の範囲に、六方晶構造に指数付けされる３〜４本
の回折ピークが観測された。上記（シリカ）メソポア材
料の結晶構造を図２の透過型電子顕微鏡写真で示した。
この写真図２により、直径約３ｍｍの細孔が規則的に配
列した蜂の巣状の構造をしていることがわかる。 （実施例３）実施例１で合成した（シリカ）メソポア担
体（Ｆ−１６Ｃ）の細孔分布を測定した。その測定方法
を以下に説明する。The powder X-ray diffraction pattern of the (silica) mesopore carrier (F-16C) is shown in FIG. Diffraction angle is 10
In the range of ° or less, 3 to 4 diffraction peaks indexed to the hexagonal crystal structure were observed. The crystal structure of the (silica) mesopore material is shown in the transmission electron micrograph of FIG.
From FIG. 2 of this photograph, it can be seen that a honeycomb-like structure in which pores having a diameter of about 3 mm are regularly arranged is formed. (Example 3) The pore distribution of the (silica) mesopore carrier (F-16C) synthesized in Example 1 was measured. The measuring method will be described below.
【００５５】先ず、窒素吸着等温線を以下の装置および
方法により作成した。装置は、絶対圧型トランスヂュー
サー（日本エムケーエス（株）製Baratron 127AA）及び
コントロールバルブ（日本エムケーエス（株）製 248
A）を装着した真空ラインを用い、定量法で測定を行っ
た。約５０ｍｇの試料をサンプル管に計り取り、１５０
℃で２時間真空脱気した。２時間後の真空度は１０-3to
rrであった。その後、サンプル管を液体窒素に浸しなが
ら、窒素の吸着測定を行い、窒素吸着等温曲線を得た。First, a nitrogen adsorption isotherm was prepared by the following apparatus and method. The equipment is an absolute pressure type transducer (Baratron 127AA manufactured by Nippon MKS Co., Ltd.) and a control valve (manufactured by Nippon MKS Co., Ltd. 248).
The measurement was performed by a quantitative method using a vacuum line equipped with A). Weigh about 50 mg of sample into a sample tube and
Vacuum degassed at ℃ for 2 hours. The degree of vacuum after 2 hours is 10 -3 to
rr. Then, the nitrogen adsorption measurement was performed while immersing the sample tube in liquid nitrogen to obtain a nitrogen adsorption isotherm.
【００５６】この窒素吸着等温曲線からCranston-Incla
y 法により算出した細孔分布曲線を図３に示した。この
細孔分布曲線のピーク位置から求めた中心細孔直径は
２．８ｎｍであった。次に、Cranston-Inclay 法によ
り、上記（シリカ）メソポア担体の比表面積の細孔直径
に対する積分曲線を計算で求めた。中心細孔直径の±４
０％の範囲内にある比表面積の全表面積に対する比率
（±４０％細孔率とする）を求めたところ、９３％であ
った。なお、全表面積は１０３１ｍ2 ／ｇであった。 （実施例４）本例においては、有機溶媒易容性無水金属
ハロゲン化物から無水塩化アルミニウムを選び、実施例
１で合成した（シリカ）メソポア担体を用いて、無水塩
化アルミニウムとの反応を行い、塩化アルミニウム担持
（シリカ）メソポア担体を合成する方法説明する。From this nitrogen adsorption isotherm, Cranston-Incla
The pore distribution curve calculated by the y method is shown in FIG. The central pore diameter determined from the peak position of this pore distribution curve was 2.8 nm. Next, by the Cranston-Inclay method, an integral curve of the specific surface area of the (silica) mesopore carrier with respect to the pore diameter was calculated. ± 4 of central pore diameter
When the ratio of the specific surface area within the range of 0% to the total surface area (± 40% porosity) was determined, it was 93%. The total surface area was 1031 m 2 / g. (Example 4) In this example, anhydrous aluminum chloride was selected from an organic solvent-acceptable anhydrous metal halide, and the (silica) mesopore carrier synthesized in Example 1 was used to react with anhydrous aluminum chloride. A method for synthesizing an aluminum chloride-supported (silica) mesopore carrier will be described.
【００５７】先ず、酸処理による（シリカ）メソポア担
体の活性化を行った。冷却管を付けた１０００ｍｌ容量
のナス型フラスコに７０．０ｇの上記（シリカ）メソポ
ア材料と１Ｎ塩酸５２０ｍｌとを秤とり、水浴温度９８
℃で２時間、攪拌モータで攪拌しながら水浴中で加熱し
た。熱時濾過により濾別した固形生成物を、約７５〜９
５℃の温脱イオン水３５００ｍｌを用いて、ろーと上で
洗浄した後、１０５℃で４日間乾燥した。その粉末を粉
砕して、粒子径０．２１ｍｍ以下に整粒することによ
り、シラノール基を活性化した（シリカ）メソポア担体
６６．０ｇを得た。これを活性化（シリカ）メソポア担
体（ＤＨＦ−１６）と呼ぶことにする。First, the (silica) mesopore carrier was activated by acid treatment. 70.0 g of the (silica) mesopore material and 520 ml of 1N hydrochloric acid were weighed in a 1000 ml eggplant-shaped flask equipped with a cooling tube, and the water bath temperature was 98.
The mixture was heated in a water bath while stirring with a stirring motor at 2 ° C. for 2 hours. The solid product separated by hot filtration is about 75-9.
It was washed with 3500 ml of warm deionized water at 5 ° C. on the filter and then dried at 105 ° C. for 4 days. The powder was pulverized and sized to a particle size of 0.21 mm or less to obtain 66.0 g of a silanol group-activated (silica) mesopore carrier. This is referred to as activated (silica) mesopore carrier (DHF-16).
【００５８】次に、（シリカ）メソポア担体の分散用有
機溶媒及び無水塩化アルミニウムの溶解用有機溶媒とし
て、ニトロベンゼンを用いて、塩化アルミニウム担持
（シリカ）メソポア材料の合成を行った。上記活性化
（シリカ）メソポア材料１２．０ｇを３００ｍｌナスフ
ラスコにとり、真空ポンプで徐々に減圧にした後に、油
浴中で１１０℃に２時間加熱して、吸着水の除去を行っ
た。冷却後に、窒素導入により大気圧に戻してから、乾
燥ニトロベンゼン７０ｍｌと乾燥四塩化炭素７０ｍｌと
をナスフラスコに加えた。このナスフラスコに冷却管を
つなぎ、窒素気流下で、超音波分散を５分間おこなっ
た。アスピレータによる減圧で脱気した後に、再び窒素
導入により大気圧に戻した。その後、この分散液を窒素
気流下にスターラーで攪拌しながら油浴中で１００℃に
加熱した。Next, an aluminum chloride-supported (silica) mesopore material was synthesized by using nitrobenzene as an organic solvent for dispersing the (silica) mesopore carrier and an organic solvent for dissolving anhydrous aluminum chloride. 12.0 g of the activated (silica) mesopore material was placed in a 300 ml round-bottomed flask, the pressure was gradually reduced by a vacuum pump, and then heated at 110 ° C. for 2 hours in an oil bath to remove adsorbed water. After cooling, the pressure was returned to atmospheric pressure by introducing nitrogen, and 70 ml of dry nitrobenzene and 70 ml of dry carbon tetrachloride were added to the eggplant flask. A cooling tube was connected to the eggplant flask, and ultrasonic dispersion was performed for 5 minutes under a nitrogen stream. After deaeration under reduced pressure by an aspirator, the pressure was returned to atmospheric pressure by introducing nitrogen again. Then, this dispersion was heated to 100 ° C. in an oil bath while stirring with a stirrer under a nitrogen stream.
【００５９】一方、乾燥した２００ｍｌナスフラスコ
に、無水塩化アルミニウム２０．３ｇをとり、乾燥ニト
ロベンゼン６０ｍｌを加えて、窒素気流下でスターラー
で攪拌して溶解させた。この溶液を１００ｍｌのシリン
ジでとり、活性化（シリカ）メソポア担体の１００℃に
保たれた上記分散液に、１５分間かけて滴下して加え
た。この反応混合物を窒素気流下に１００℃で８時間加
熱・攪拌した。反応開始後９０分間は、冷却管上部に水
に濡らしたｐＨ紙を近付ける、酸性ガスの発生が確認で
きた。On the other hand, 20.3 g of anhydrous aluminum chloride was placed in a dry 200 ml round-bottomed flask, 60 ml of dry nitrobenzene was added, and the mixture was dissolved by stirring with a stirrer under a nitrogen stream. This solution was taken with a 100 ml syringe and added dropwise to the above dispersion of activated (silica) mesopore carrier kept at 100 ° C. over 15 minutes. The reaction mixture was heated and stirred under a nitrogen stream at 100 ° C. for 8 hours. For 90 minutes after the start of the reaction, generation of acid gas could be confirmed by bringing a pH paper wet with water close to the upper part of the cooling tube.
【００６０】反応混合物を窒素雰囲気下にテフロン濾紙
を用いて減圧濾過して固形分を取り出した。冷却管を備
えた５００ｍｌセパラブルフラスコに、この固形分を窒
素雰囲気下でとり、乾燥ニトロベンゼン１５０ｍｌと乾
燥四塩化炭素５０ｍｌを加えて、窒素気流下の油浴中で
スターラーにより１００℃で１時間加熱・攪拌した。冷
却後に固形分を窒素雰囲気下の吸引濾過により取り出し
た。上記と同じ装置を用いて、再度この固形分を乾燥四
塩化炭素２００ｍｌ中で１時間加熱・攪拌して還流洗浄
した。冷却後に窒素雰囲気下の減圧濾過により固形分を
取り出した。生成固形分を２００ｍｌの柱状フラスコに
いれ、室温で真空ポンプにより徐々に減圧した後、ゆっ
くり昇温して１７０℃で５時間保持して乾燥した。冷却
後に、窒素導入で大気圧に戻して、薄黄色粉体の塩化ア
ルミニウム担持（シリカ）メソポア材料１５．１ｇを得
た。この生成物をＦＡＣｌ−４と略記する。 （実施例５）本例においては、有機溶媒可溶性無水金属
ハロゲン化物から無水塩化第二鉄を選び、実施例１で合
成した（シリカ）メソポア担体を用いて、脱酸剤を含む
有機溶剤中で、無水塩化第二鉄との反応を行い、塩化第
二鉄担持（シリカ）メソポア材料を合成する方法を説明
する。The reaction mixture was filtered under a nitrogen atmosphere using Teflon filter paper under reduced pressure to remove solids. This solid content is placed in a 500 ml separable flask equipped with a cooling tube under a nitrogen atmosphere, 150 ml of dry nitrobenzene and 50 ml of dry carbon tetrachloride are added, and the mixture is heated at 100 ° C. for 1 hour by a stirrer in an oil bath under a nitrogen stream. -Agitated. After cooling, the solid content was taken out by suction filtration under a nitrogen atmosphere. Using the same apparatus as above, the solid content was again heated in 200 ml of dry carbon tetrachloride for 1 hour with stirring and reflux washing. After cooling, the solid content was taken out by vacuum filtration under a nitrogen atmosphere. The produced solid content was put into a 200 ml columnar flask, and the pressure was gradually reduced by a vacuum pump at room temperature, then the temperature was slowly raised and the temperature was maintained at 170 ° C. for 5 hours to dry. After cooling, the pressure was returned to atmospheric pressure by introducing nitrogen, and 15.1 g of aluminum chloride-supported (silica) mesopore material as a light yellow powder was obtained. This product is abbreviated as FACl-4. Example 5 In this example, anhydrous ferric chloride was selected from organic solvent-soluble anhydrous metal halides, and the (silica) mesopore carrier synthesized in Example 1 was used in an organic solvent containing a deoxidizing agent. A method for synthesizing a ferric chloride-supporting (silica) mesopore material by performing a reaction with anhydrous ferric chloride will be described.
【００６１】実施例４と同様にして調整した活性化（シ
リカ）メソポア担体の分散用有機溶媒にピリジンを用
い、かつ無水塩化第二鉄の溶解用有機溶媒にアセトンを
用いることにより、塩化第二鉄担持（シリカ）メソポア
材料の合成を行った。なお、ピリジンは、（シリカ）メ
ソポア担体の分散媒としてだけでなく、脱酸剤としての
作用も併せ持つものである。By using pyridine as the organic solvent for dispersing the activated (silica) mesopore carrier prepared in the same manner as in Example 4 and using acetone as the organic solvent for dissolving anhydrous ferric chloride, An iron-supported (silica) mesopore material was synthesized. Pyridine not only acts as a dispersion medium for the (silica) mesopore carrier, but also acts as a deoxidizing agent.
【００６２】活性化（シリカ）メソポア担体５．０ｇを
３００ｍｌナスフラスコにとり、真空ポンプで徐々に減
圧にした後、油浴中で１１０℃に２時間加熱して、吸着
水の除去をおこなった。冷却後に、窒素導入により大気
圧に戻してから、乾燥ピリジン３０ｍｌをナスフラスコ
に加えた。このナスフラスコに冷却管をつなぎ、窒素気
流下で、超音波分散を５分間行った。アスピレータによ
る減圧で脱気した後、再び窒素導入により大気圧に戻し
た。その後、この分散液を窒素気流下にスターラーで攪
拌しながら油浴中で１００℃に加熱した。5.0 g of the activated (silica) mesopore carrier was placed in a 300 ml round-bottomed flask, the pressure was gradually reduced by a vacuum pump, and the adsorbed water was removed by heating at 110 ° C. for 2 hours in an oil bath. After cooling, the pressure was returned to atmospheric pressure by introducing nitrogen, and 30 ml of dry pyridine was added to the eggplant flask. A cooling tube was connected to the eggplant flask, and ultrasonic dispersion was performed for 5 minutes under a nitrogen stream. After deaeration under reduced pressure by an aspirator, the pressure was returned to atmospheric pressure by introducing nitrogen again. Then, this dispersion was heated to 100 ° C. in an oil bath while stirring with a stirrer under a nitrogen stream.
【００６３】一方、乾燥した２００ｍｌナスフラスコ
に、無水塩化第二鉄１４．２ｇをとり、乾燥アセトン１
２０ｍｌを加えて、窒素気流下でスターラーで攪拌して
溶解させた。この溶液を２００ｍｌのシリンジでとり、
活性化（シリカ）メソポア担体の１００℃に保たれた上
記分散液に、１５分間かけて滴下して加えた。この反応
混合物を窒素気流下に１００℃で８時間加熱・攪拌し
た。On the other hand, 14.2 g of anhydrous ferric chloride was placed in a dry 200 ml eggplant-shaped flask, and dried acetone 1
20 ml was added and dissolved by stirring with a stirrer under a nitrogen stream. Take this solution with a 200 ml syringe,
To the above dispersion of activated (silica) mesopore carrier kept at 100 ° C. was added dropwise over 15 minutes. The reaction mixture was heated and stirred under a nitrogen stream at 100 ° C. for 8 hours.
【００６４】冷却後に、窒素雰囲気下にテフロン濾紙を
用いて減圧濾過して固形分を取り出した。冷却管を備え
た５００ｍｌセパラブルフラスコにこの固形分を窒素雰
囲気下でとり、乾燥アセトン２００ｍｌを加えて、窒素
気流下に油浴中で加熱して還流させながら、スターラー
により１時間攪拌した。冷却後に固形分を窒素雰囲気下
の吸引濾過により取り出した。生成固形分を２００ｍｌ
の柱状フラスコに入れ、室温で真空ポンプにより徐々に
減圧した後、ゆっくりと昇温して１７０℃で５時間保持
して乾燥した。冷却後に、窒素導入で大気圧に戻して、
薄茶色粉体の塩化第二鉄担持（シリカ）メソポア材料１
１．２ｇを得た。この生成物をＦＦＣｌ−５と略記す
る。 （実施例６）本例においては、有機溶媒可溶性無水金属
ハロゲン化物から無水塩化第二鉄を選び、実施例１で合
成した（シリカ）メソポア担体を用いて、脱酸剤を含ま
ない有機溶剤中で、無水塩化第二鉄との反応を行い、塩
化第二鉄担持（シリカ）メソポア材料を合成する方法を
説明する。After cooling, a solid content was taken out by vacuum filtration under nitrogen atmosphere using Teflon filter paper. The solid content was placed in a 500 ml separable flask equipped with a cooling tube under a nitrogen atmosphere, 200 ml of dry acetone was added, and the mixture was stirred with a stirrer for 1 hour while heating and refluxing in an oil bath under a nitrogen stream. After cooling, the solid content was taken out by suction filtration under a nitrogen atmosphere. 200 ml of produced solid content
The mixture was placed in a columnar flask of No. 1 and gradually depressurized at room temperature by a vacuum pump, then the temperature was slowly raised and the temperature was maintained at 170 ° C. for 5 hours to dry. After cooling, return to atmospheric pressure by introducing nitrogen,
Light brown powder of ferric chloride-supported (silica) mesopore material 1
1.2 g were obtained. This product is abbreviated as FFCl-5. (Example 6) In this example, anhydrous ferric chloride was selected from organic solvent-soluble anhydrous metal halides, and the (silica) mesopore carrier synthesized in Example 1 was used in an organic solvent containing no deoxidizing agent. Now, a method of synthesizing a ferric chloride-supporting (silica) mesopore material by performing a reaction with anhydrous ferric chloride will be described.
【００６５】実施例４と同様にして調製した活性化（シ
リカ）メソポア担体の分散用有機溶媒のニトロベンゼン
を用い、かつ無水塩化第二鉄の溶解有機溶媒にアセトン
を用いることにより、塩化第二鉄と（シリカ）メソポア
担体の反応を行った。活性化（シリカ）メソポア材料
５．１ｇを３００ｍｌナスフラスコにとり、真空ポンプ
で徐々に減圧にした後、油浴中で１１０℃２時間の加熱
をして、吸着水の除去を行った。冷却後、窒素導入によ
り大気圧に戻してから、乾燥ニトロベンゼン６０ｍｌを
ナスフラスコに加えた。このナスフラスコに冷却管をつ
なぎ、窒素気流下で、超音波分散を５分間おこなった。
アスピレータによる減圧で脱気した後、再び窒素導入に
より大気圧に戻した。その後、この分散液を窒素気流下
にスターラーで攪拌しながら油浴中で１００℃に加熱し
た。By using nitrobenzene as an organic solvent for dispersing the activated (silica) mesopore carrier prepared in the same manner as in Example 4 and using acetone as an organic solvent for dissolving anhydrous ferric chloride, ferric chloride was obtained. And (silica) mesopore carrier were reacted. 5.1 g of the activated (silica) mesopore material was placed in a 300 ml eggplant flask, and the pressure was gradually reduced by a vacuum pump, and then heated in an oil bath at 110 ° C. for 2 hours to remove adsorbed water. After cooling, the pressure was returned to atmospheric pressure by introducing nitrogen, and 60 ml of dry nitrobenzene was added to the eggplant flask. A cooling tube was connected to the eggplant flask, and ultrasonic dispersion was performed for 5 minutes under a nitrogen stream.
After deaeration under reduced pressure by an aspirator, the pressure was returned to atmospheric pressure by introducing nitrogen again. Then, this dispersion was heated to 100 ° C. in an oil bath while stirring with a stirrer under a nitrogen stream.
【００６６】一方、乾燥した２００ｍｌナスフラスコ
に、無水塩化第二鉄１４．２ｇをとり、乾燥アセトン１
００ｍｌを加えて、窒素気流下でスターラーで攪拌して
溶解させた。この溶液を２００ｍｌのシリンジでとり、
活性化（シリカ）メソポア担体の１００℃に保たれた上
記分散液に、１５分間かけて滴下して加えた。この反応
混合物を窒素気流下に１００℃で８時間加熱・攪拌し
た。反応中に、冷却管上部に水に濡らしたｐＨ紙を近付
けたが、酸性ガスの発生は確認できなかった。On the other hand, 14.2 g of anhydrous ferric chloride was placed in a dry 200 ml eggplant-shaped flask, and dried acetone 1
00 ml was added and dissolved by stirring with a stirrer under a nitrogen stream. Take this solution with a 200 ml syringe,
To the above dispersion of activated (silica) mesopore carrier kept at 100 ° C. was added dropwise over 15 minutes. The reaction mixture was heated and stirred under a nitrogen stream at 100 ° C. for 8 hours. During the reaction, a pH paper wet with water was brought close to the upper part of the cooling tube, but generation of acid gas could not be confirmed.
【００６７】冷却後に、窒素雰囲気下にテフロン濾紙を
用いて減圧濾過して固形分を取り出した。冷却管を備え
た５００ｍｌセパラブルフラスコに、この固形分を窒素
雰囲気下で取り、乾燥アセトン２００ｍｌを加えて、窒
素気流下に油浴中で加熱して還流させながら、スターラ
ーにより１時間攪拌した。冷却後に固形分を窒素雰囲気
下の吸引濾過により取り出した。生成固形分を２００ｍ
ｌの柱状フラスコに入れ、室温で真空ポンプにより徐々
に減圧にした後、ゆっくり昇温して１７０℃で５時間保
持して乾燥した。冷却後、窒素導入で大気圧に戻し、白
色粉体の固形生成物８．１ｇを得た。この生成物をＦＦ
Ｃｌ−６と略記する。 （実施例７）有機溶媒可溶性無水金属ハロゲン化物から
無水塩化第二白金を選び、実施例１で合成した（シリ
カ）メソポア担体を用いて、脱酸剤を含む有機溶媒中
で、無水塩化第二白金との反応をおこない、塩化第二白
金担持（シリカ）メソポア材料を合成した。After cooling, the solid content was taken out by vacuum filtration under nitrogen atmosphere using Teflon filter paper. The solid content was taken in a nitrogen atmosphere in a 500 ml separable flask equipped with a cooling tube, 200 ml of dry acetone was added, and the mixture was stirred with a stirrer for 1 hour while being refluxed by heating in an oil bath under a nitrogen stream. After cooling, the solid content was taken out by suction filtration under a nitrogen atmosphere. Generated solid content is 200m
The mixture was placed in a 1-L columnar flask, the pressure was gradually reduced by a vacuum pump at room temperature, the temperature was slowly raised, and the temperature was maintained at 170 ° C. for 5 hours to dry. After cooling, the pressure was returned to atmospheric pressure by introducing nitrogen to obtain 8.1 g of a white powder solid product. FF this product
It is abbreviated as Cl-6. (Example 7) Anhydrous platinum chloride was selected from organic solvent-soluble anhydrous metal halides, and the (silica) mesopore carrier synthesized in Example 1 was used to remove anhydrous platinum chloride in an organic solvent containing a deoxidizing agent. By reacting with platinum, a chloroplatinum-supported (silica) mesopore material was synthesized.
【００６８】実施例４と同様にして調製した活性化（シ
リカ）メソポア担持の分散用有機溶媒にピリジンを用
い、かつ無水塩化第二白金の溶解用有機溶媒にアセトン
を用いることにより、塩化第二白金担持（シリカ）メソ
ポア材料の合成をおこなった。なお、ピリジンは、（シ
リカ）メソポア材料の分散溶媒としてだけでなく、脱酸
剤としての作用も併せ持つものである。By using pyridine as an organic solvent for dispersion supporting activated (silica) mesopores prepared in the same manner as in Example 4 and acetone as an organic solvent for dissolving anhydrous platinum chloride, the second chloride A platinum-supported (silica) mesopore material was synthesized. Pyridine not only acts as a dispersion solvent for the (silica) mesopore material, but also acts as a deoxidizing agent.
【００６９】活性化（シリカ）メソポア材料１．０ｇを
２００ｍｌナスフラスコにとり、真空ポンプで徐々に減
圧にした後、油浴中で１１０℃に２時間加熱して、吸着
水の除去をおこなった。冷却後、窒素導入により大気圧
に戻してから、乾燥ピリジン２０ｍｌをナスフラスコに
加えた。このナスフラスコに冷却管をつなぎ、窒素気流
下で、超音波分散を５分間おこなった。アスピレータに
よる減圧で脱揮した後に、再び窒素導入により大気圧に
戻した。その後、この分散液を窒素気流下にスターラー
で攪拌しながら油浴中で１００℃に加熱した。1.0 g of the activated (silica) mesopore material was placed in a 200 ml round-bottomed flask, the pressure was gradually reduced by a vacuum pump, and then heated at 110 ° C. for 2 hours in an oil bath to remove adsorbed water. After cooling, the pressure was returned to atmospheric pressure by introducing nitrogen, and then 20 ml of dry pyridine was added to the eggplant flask. A cooling tube was connected to the eggplant flask, and ultrasonic dispersion was performed for 5 minutes under a nitrogen stream. After devolatilization under reduced pressure by an aspirator, the pressure was returned to atmospheric pressure by introducing nitrogen again. Then, this dispersion was heated to 100 ° C. in an oil bath while stirring with a stirrer under a nitrogen stream.
【００７０】一方、乾燥した１００ｍｌナスフラスコ
に、無水塩化第二白金５．０ｇをとり、乾燥アセトン６
０ｍｌを加えて、窒素気流下でスターラーで攪拌して溶
解させた。この溶液を１００ｍｌのシリンジでとり、活
性化（シリカ）メソポア材料の１００℃に保たれた上記
分散液に、１５分間かけて滴下して加えた。この反応混
合物を窒素気流下に１００℃で８時間加熱・攪拌した。On the other hand, 5.0 g of anhydrous platinum (II) chloride was placed in a dry 100 ml eggplant-shaped flask, and dried acetone 6 was added.
0 ml was added and dissolved by stirring with a stirrer under a nitrogen stream. This solution was taken with a 100 ml syringe and added dropwise to the above dispersion of activated (silica) mesopore material kept at 100 ° C. over 15 minutes. The reaction mixture was heated and stirred under a nitrogen stream at 100 ° C. for 8 hours.
【００７１】冷却後、窒素雰囲気下にテフロン濾紙を用
いて反応混合物を吸引濾過して固形分を取り出した。冷
却管を備えた５００ｍｌセパラブルフラスコに、この固
形分を窒素雰囲気下でとり、乾燥アセトン２００ｍｌを
加えて、窒素気流下に油浴中で加熱して還流させなが
ら、スターラーにより１時間攪拌した。冷却後に固形分
を窒素雰囲気下の吸引濾過により取り出した。生成固形
分を２００ｍｌの柱状フラスコに入れ、室温で真空ポン
プにより徐々に減圧にした後、ゆっくりと昇温して１７
０℃で５時間保持して乾燥した。冷却後、窒素導入で大
気圧に戻して、赤褐色粉体の塩化第二白金担持（シリ
カ）メソポア材料１．６ｇを得た。この生成物をＦＰＣ
ｌ−７と略記する。 （実施例８）実施例４で合成した塩化アルミニウム担持
（シリカ）メソポア材料を加水分解して、金属水酸化物
担持（シリカ）メソポア材料を合成した。なお、加水分
解は、飽和水蒸気中および水中で実施した。After cooling, the reaction mixture was suction-filtered using a Teflon filter paper under a nitrogen atmosphere to take out solids. This solid content was placed in a 500 ml separable flask equipped with a cooling tube under a nitrogen atmosphere, 200 ml of dry acetone was added, and the mixture was stirred with a stirrer for 1 hour while heating and refluxing in an oil bath under a nitrogen stream. After cooling, the solid content was taken out by suction filtration under a nitrogen atmosphere. The produced solid content was put into a 200 ml columnar flask, and the pressure was gradually reduced by a vacuum pump at room temperature, and then the temperature was slowly raised to 17
It was kept at 0 ° C. for 5 hours to be dried. After cooling, the pressure was returned to atmospheric pressure by introducing nitrogen to obtain 1.6 g of a reddish brown powder of platinum (II) chloride-supporting (silica) mesopore material. This product is FPC
It is abbreviated as 1-7. (Example 8) The aluminum chloride-supporting (silica) mesopore material synthesized in Example 4 was hydrolyzed to synthesize a metal hydroxide-supporting (silica) mesopore material. The hydrolysis was carried out in saturated steam and water.
【００７２】飽和水蒸気中での加水分解は、７０ｍｌの
水を含む１００ｍｌビーカを入れた箱型デシケータ（３
０×２０×１０ｃｍ3 ）に、上記塩化アルミニウム担持
（シリカ）メソポア材料（ＦＡＣｌ−４）３．０ｇを入
れたシャーレを室温で２４時間放置しておこなった。生
成粉体を５０ｍｌナスフラスコにとり、室温で真空ポン
プにより徐々に減圧にした後、毎時１０〜２０℃の昇温
速度で７５℃まで加熱して乾燥させ、冷却後に窒素導入
で大気圧に戻して、白色粉体の生成物を得た。この生成
物をＦＡＯＨ−４Ａと略記する。Hydrolysis in saturated steam was performed by a box type desiccator (3 ml containing 100 ml beaker containing 70 ml of water).
A petri dish containing 3.0 g of the above aluminum chloride-supporting (silica) mesopore material (FACl-4) in (0 × 20 × 10 cm 3 ) was left standing at room temperature for 24 hours. The resulting powder is placed in a 50 ml eggplant-shaped flask, and the pressure is gradually reduced by a vacuum pump at room temperature. Then, it is heated to 75 ° C. at a heating rate of 10 to 20 ° C. per hour to be dried, and after cooling, it is returned to atmospheric pressure by introducing nitrogen. A white powder product was obtained. This product is abbreviated as FAOH-4A.
【００７３】水中での加水分解は、上記塩化アルミニウ
ム担持（シリカ）メソポア材料（ＦＡＣｌ−４）３．０
ｇを２００ｍｌナスフラスコにとり水１００ｍｌを加え
て、アスピレータで脱気した後、１分間超音波分散し
て、その後室温で３０分間静置することによりおこなっ
た。固形分を濾別しロート上で４００ｍｌの水で洗浄し
た後、５０ｍｌナスフラスコにとり、室温で真空ポンプ
により徐々に減圧にした後、毎時１０〜２０℃の昇温速
度で７５℃まで加熱して乾燥させ、冷却後に窒素導入し
て大気圧に戻して、白色粉体の生成物２．２ｇを得た。
この生成物をＦＡＯＨ−４Ｗと略記する。 （実施例９）実施例８で合成した２種類の金属水酸化物
担持（シリカ）メソポア材料を焼成して、金属酸化物担
持（シリカ）メソポア材料を合成した。Hydrolysis in water is carried out by using the above-mentioned aluminum chloride-supported (silica) mesopore material (FACl-4) 3.0.
100 g of water was added to a 200 ml eggplant flask, deaerated with an aspirator, ultrasonically dispersed for 1 minute, and then left standing at room temperature for 30 minutes. The solid content was separated by filtration, washed with 400 ml of water on a funnel, placed in a 50 ml eggplant flask, and gradually depressurized at room temperature by a vacuum pump, and then heated to 75 ° C. at a heating rate of 10 to 20 ° C. per hour. After drying and cooling, nitrogen was introduced and the pressure was returned to atmospheric pressure to obtain 2.2 g of a white powder product.
This product is abbreviated as FAOH-4W. (Example 9) The two kinds of metal hydroxide-supporting (silica) mesopore materials synthesized in Example 8 were fired to synthesize the metal oxide-supporting (silica) mesopore material.
【００７４】上記２種類の金属水酸化物担持（シリカ）
メソポア材料、すなわち、１．４ｇのＦＡＯＨ−４Ａと
１．２ｇのＦＡＯＨ−４Ｗを、それぞれ５０ｍｌの磁製
ルツボにとり、電気炉中６５０℃で４時間焼成した。な
お、昇温および降温はそれぞれ２時間おこなった。白色
粉体の生成物をそれぞれ１．１ｇづつ得た。これらの生
成物を、ＦＡＯ−４ＡおよびＦＡＯ−４Ｗと略記する。 （実施例１０）実施例４で合成した塩化アルミニウム担
持（シリカ）メソポア材料、および実施例５で合成した
塩化第二鉄担持（シリカ）メソポア材料を焼成して、金
属酸化物担持（シリカ）メソポア材料を合成した。The above two types of metal hydroxide supported (silica)
The mesopore material, that is, 1.4 g of FAOH-4A and 1.2 g of FAOH-4W was placed in a 50 ml porcelain crucible and fired at 650 ° C. for 4 hours in an electric furnace. The temperature rising and the temperature lowering were each performed for 2 hours. 1.1 g of each white powder product was obtained. These products are abbreviated as FAO-4A and FAO-4W. (Example 10) The aluminum chloride-supported (silica) mesopore material synthesized in Example 4 and the ferric chloride-supported (silica) mesopore material synthesized in Example 5 were calcined to give a metal oxide-supported (silica) mesopore. The material was synthesized.
【００７５】上記の塩化アルミニウム担持（シリカ）メ
ソポア材料１．４ｇおよび上記の塩化第二鉄担持（シリ
カ）メソポア材料（ＦＦＣｌ−５）２．０ｇを、それぞ
れ５０ｍｌの磁製ルツボにとり、電気炉中６５０℃で４
時間焼成した。なお、昇温及び降温はそれぞれ２時間お
こなった。ＦＡＣＬ−４からは白色粉体の生成物１．０
ｇを、またＦＦＣｌ−５からは赤茶色粉体の生成物１．
３ｇを得た。これらの生成物を、それぞれＦＡＯ−４Ｃ
ｌおよびＦＦＯ−５Ｃｌと略記する。 （実施例１１）実施例７で合成した塩化第二白金担持
（シリカ）メソポア材料を熱分解して、金属担持（シリ
カ）メソポア材料を合成した。1.4 g of the aluminum chloride-supporting (silica) mesopore material and 2.0 g of the ferric chloride-supporting (silica) mesopore material (FFCl-5) were placed in a 50 ml porcelain crucible and placed in an electric furnace. 4 at 650 ° C
Fired for hours. The temperature rise and temperature fall were each performed for 2 hours. White powder product 1.0 from FACL-4
g, and from FFCl-5, the product 1.
3 g were obtained. FAO-4C was obtained from each of these products.
1 and FFO-5Cl. (Example 11) The platinum (II) chloride-supporting (silica) mesopore material synthesized in Example 7 was thermally decomposed to synthesize a metal-supporting (silica) mesopore material.
【００７６】上記塩化第二白金担持（シリカ）メソポア
材料（ＦＰＣｌ−７）１．０ｇを５０ｍｌの磁製ルツボ
にとり、電気炉中６００℃で４時間加熱して熱分解をお
こなった。なお、昇温および降温はそれぞれ２時間おこ
なった。灰色粉体の生成物０．８ｇを得た。生成物をＦ
Ｐｔ−７Ｃｌと略記する。 （実施例１２）実施例４〜１１で合成した（シリカ）メ
ソポア材料の各種担持誘導体について、窒素吸着による
ＢＥＴ法で比表面積を求めた。1.0 g of the platinum chloride-supporting (silica) mesopore material (FPCl-7) was placed in a 50 ml porcelain crucible and heated in an electric furnace at 600 ° C. for 4 hours for thermal decomposition. The temperature rising and the temperature lowering were each performed for 2 hours. 0.8 g of a gray powder product was obtained. The product is F
It is abbreviated as Pt-7Cl. Example 12 Specific surface areas of various supported derivatives of (silica) mesopore materials synthesized in Examples 4 to 11 were determined by the BET method by nitrogen adsorption.
【００７７】[0077]
【表１】 それぞれの比表面積（ｍ2 ／ｇ）の値を表１に示す。[Table 1] Table 1 shows the values of the specific surface areas (m 2 / g).
【００７８】実施例４、５、７の方法にしたがって、活
性化（シリカ）メソポア材料（ＤＨＦ−１６）と無水金
属ハロゲン化物を反応させると、得られた生成物の比表
面積は原料ＤＨＦ−１６の値の半分以下となった。しか
し、実施例６の方法で反応させた場合には、得られた生
成物（ＦＦＣｌ−６）の比表面積は原料ＤＨＦ−１６の
値と変わらなかったので、無水塩化第二鉄と活性化（シ
リカ）メソポア材料のシラノール基との反応が十分に起
きなかったことがわかる。When the activated (silica) mesopore material (DHF-16) was reacted with the anhydrous metal halide according to the method of Examples 4, 5, and 7, the specific surface area of the obtained product was determined to be the raw material DHF-16. It became less than half of the value of. However, when the reaction was carried out by the method of Example 6, the specific surface area of the obtained product (FFCl-6) was not different from the value of the raw material DHF-16, and thus the activated ferric chloride and activated ( It can be seen that the reaction with the silanol groups of the (silica) mesopore material did not sufficiently occur.
【００７９】金属ハロゲン化物担持（シリカ）メソポア
材料から得られる各種担持誘導体は、少なくとも４００
ｍ2 ／ｇ以上の十分に大きい比表面積を持つが、その値
は出発原料の（シリカ）メソポア材料の比表面積より小
さいことがわかる。 （実施例１３）実施例４で合成した塩化アルミニウム担
持（シリカ）メソポア材料の微細構造をＮＭＲ測定によ
り観察した。Various supported derivatives obtained from metal halide supported (silica) mesopore materials are at least 400.
Although it has a sufficiently large specific surface area of m 2 / g or more, it can be seen that the value is smaller than the specific surface area of the starting (silica) mesopore material. (Example 13) The fine structure of the aluminum chloride-supported (silica) mesopore material synthesized in Example 4 was observed by NMR measurement.
【００８０】活性化（シリカ）メソポア材料（ＤＨＦ−
１６）と塩化アルミニウム担持（シリカ）メソポア材料
（ＦＡＣｌ−４）について、29ＳｉＭＡＳ−ＮＭＲスペ
クトルを図４に示した。ＦＡＣｌ−４のスペクトルで
は、ＤＨＦ−１６のスペクトルに比べて、−１００ｐｐ
ｍ付近のシラノール基によるＱ3 ピーク強度が減少し
て、−１０５ｐｐｍ付近のＳｉ（１Ａｌ）ピーク強度が
増加したが、シリカ骨格内部のＳｉ−Ｏ−Ｓｉ結合に基
づく−１１０ｐｐｍ付近のＱ4 ピーク強度に変化は無か
った。したがって、無水塩化アルミニウムが活性化（シ
リカ）メソポア材料のシラノール基と反応したことがわ
かる。Activated (silica) mesopore material (DHF-
16) and aluminum chloride-supporting (silica) mesopore material (FACl-4), the 29 SiMAS-NMR spectrum is shown in FIG. The FACl-4 spectrum is -100 pp compared to the DHF-16 spectrum.
Although the Q 3 peak intensity due to the silanol group near m decreased and the Si (1Al) peak intensity around −105 ppm increased, the Q 4 peak intensity around −110 ppm due to the Si—O—Si bond inside the silica skeleton. There was no change. Therefore, it can be seen that the anhydrous aluminum chloride reacted with the silanol groups of the activated (silica) mesopore material.
【００８１】塩化アルミニウム担持（シリカ）メソポア
材料（ＦＡＣｌ−４）の27ＡｌＭＡＳ−ＮＭＲスペクト
ルを図５に示した。未反応のＡｌＣｌ3 による１０５ｐ
ｐｍのピークはほとんど見られず、Ｓｉ−Ｏ−Ａｌ（Ｃ
ｌ）2 に基づくピークが８０ｐｐｍ付近に観測された。 （実施例１４）実施例４〜１１で合成した金属ハロゲン
化物担持（シリカ）メソポア材料およびその誘導体の元
素分析から求めた元素組成を説明する。The 27 AlMAS-NMR spectrum of the aluminum chloride-supported (silica) mesopore material (FACl-4) is shown in FIG. 105p due to unreacted AlCl 3
Almost no peak of pm is seen, and Si-O-Al (C
1) A peak based on 2 was observed around 80 ppm. (Example 14) The elemental composition obtained by elemental analysis of the metal halide-supported (silica) mesopore materials and their derivatives synthesized in Examples 4 to 11 will be described.
【００８２】各種担持（シリカ）メソポア材料につい
て、金属原子と珪素原子の比および塩素原子と金属原子
の比を表２にまとめた。各種誘導体の金属含有量は金属
ハロゲン化物担持（シリカ）メソポア材料と変わらなか
ったが、塩化アルミニウム担持（シリカ）メソポア材料
を水中で加水分解・濾別したものはアルミニウム含有量
が減少した。Table 2 shows the ratio of metal atoms to silicon atoms and the ratio of chlorine atoms to metal atoms for various supported (silica) mesopore materials. The metal content of the various derivatives was not different from that of the metal halide-supported (silica) mesopore material, but the aluminum content of the aluminum chloride-supported (silica) mesopore material hydrolyzed and filtered in water decreased.
【００８３】[0083]
【表２】 （実施例１５）実施例３と同様の方法により、実施例４
で合成した塩化アルミニウム担持（シリカ）メソポア材
料の細孔径を測定した。[Table 2] (Example 15) Example 4 was carried out in the same manner as in Example 3.
The pore size of the aluminum chloride-supported (silica) mesopore material synthesized in 1. was measured.
【００８４】図６に、窒素吸着等温曲線からCranston-I
nclay 法により算出した細孔分布曲線を示した。この細
孔分布曲線のピーク位置から求めて中心細孔直径は２．
０ｎｍであった。なお、全表面積は５５３ｍ2 ／ｇであ
った。 （実施例１６）実施例１１で合成した白金担持（シリ
カ）メソポア材料（ＦＰｔ−７Ｃｌ）のＸＰＳ観察の結
果を説明する。FIG. 6 shows Cranston-I from the nitrogen adsorption isotherm.
The pore distribution curve calculated by the nclay method is shown. The diameter of the central pore is 2. determined from the peak position of this pore distribution curve.
It was 0 nm. The total surface area was 553 m 2 / g. (Example 16) The results of XPS observation of the platinum-supported (silica) mesopore material (FPt-7Cl) synthesized in Example 11 will be described.
【００８５】図７に、ＦＰｔ−７ＣｌをＸＰＳで測定し
た結果を示した。担体である（シリカ）メソポア材料の
Ｓｉを標準としたＰｔ４ｆ5/2 とＰｔ４ｆ7/2 のスペク
トルから白金が金属原子として存在することがわかる。 （実施例１７）実施例４、８、９、１０で合成した塩化
アルミニウム担持（シリカ）メソポア材料およびその誘
導体の粉末Ｘ線回折パターンを観察した。FIG. 7 shows the result of measurement of FPt-7Cl by XPS. It can be seen from the spectra of Pt4f 5/2 and Pt4f 7/2 with Si as the support (silica) mesopore material that platinum is present as a metal atom. (Example 17) The powder X-ray diffraction patterns of the aluminum chloride-supported (silica) mesopore material and its derivative synthesized in Examples 4, 8, 9, and 10 were observed.
【００８６】活性化（シリカ）メソポア材料（ＤＨＦ−
１６）とＦＡＣｌ−４の粉末Ｘ線回折パターンを図８に
示した。ＦＡＣｌ−４においても、六方晶構造に指数付
けされる３〜４本の回折ピークが、回折角度が１０°以
下の範囲に観測されたが、それらは強度が低下して高角
側に若干シフトしていた。したがって、上記塩化アルミ
ニウム担持（シリカ）メソポア材料は、細孔径が若干減
少すること、および規則的な構造をある程度保持してい
ることがわかる。Activated (silica) mesopore material (DHF-
16) and the powder X-ray diffraction pattern of FACl-4 are shown in FIG. Also in FACl-4, 3 to 4 diffraction peaks indexed to the hexagonal crystal structure were observed in the range where the diffraction angle was 10 ° or less, but they decreased in intensity and slightly shifted to the high angle side. Was there. Therefore, it can be seen that the aluminum chloride-supported (silica) mesopore material has a slightly reduced pore size and retains a regular structure to some extent.
【００８７】ＦＡＣｌ−４を加水分解したＦＡＯＨ−４
ＡとＦＡＯＨ−４Ｗの粉末Ｘ線回折パターンを図９に示
した。これらも、規則的な構造をある程度保持してお
り、その細孔径はＦＡＣｌ−４のものとほぼ同じである
ことがわかる。焼成して得られた金属酸化物担持（シリ
カ）メソポア材料であるＦＡＯ−４Ｃｌ、ＦＡＯ−４
Ａ、ＦＡＯ−４Ｗの粉末Ｘ線回折パターンを図１０に示
した。これらも、規則的な構造をある程度保持していた
が、その細孔径は焼成原料のものより若干減少している
ことがわかる。FAOH-4 obtained by hydrolyzing FACl-4
The powder X-ray diffraction patterns of A and FAOH-4W are shown in FIG. It can be seen that these also have a regular structure to some extent and their pore diameters are almost the same as those of FACl-4. FAO-4Cl and FAO-4, which are metal oxide-supported (silica) mesopore materials obtained by firing.
The powder X-ray diffraction patterns of A and FAO-4W are shown in FIG. These also retained a regular structure to some extent, but it was found that the pore size was slightly smaller than that of the calcined raw material.
【００８８】ＦＦＣｌ−５、ＦＦＯ−５Ｃｌ、ＦＰＣｌ
−７、ＦＰｔ−７Ｃｌの粉末Ｘ線回折パターンにおいて
も、六方晶構造に指数付けされる３〜４本の回折ピーク
が回折角度１０°以下の範囲に若干高角側にシフトして
観測された。 （実施例１８）実施例４で合成した塩化アルミニウム担
持（シリカ）メソポア材料（ＦＡＣｌ−４）が、分子径
の大きい悪臭物であるトリメチルアミンを除去する脱臭
効果を有することを説明する。なお、比較材料として、
シリカ／アルミナ比が１．２であるＸゼオライトとシリ
カ／アルミナ比が６３０であるＨＹゼオライトを用い
た。FFCl-5, FFO-5Cl, FPCl
Also in the powder X-ray diffraction patterns of -7 and FPt-7Cl, 3 to 4 diffraction peaks indexed to the hexagonal crystal structure were observed with a slight shift to the high angle side in the range of the diffraction angle of 10 ° or less. (Example 18) It will be described that the aluminum chloride-supported (silica) mesopore material (FACl-4) synthesized in Example 4 has a deodorizing effect of removing trimethylamine, which is a malodorous substance having a large molecular diameter. As a comparative material,
X zeolite with a silica / alumina ratio of 1.2 and HY zeolite with a silica / alumina ratio of 630 were used.
【００８９】２つの密封袋内に上記の各試料とトリメチ
ルアミンガス（窒素バランス）および同量のトリメチル
アミンガスのみを入れ、２４時間静置した後に、トリメ
チルアミンの残留濃度をガスクロマトグラフにより定量
した。トリメチルアミンガスの供給量（初期濃度）は、
袋による吸着を考慮して、トリメチルアミンガスのみを
２４時間静置した際の濃度を用いた。したがって、試料
によるトリメチルアミンガスの除去量は、上記残留濃度
からの減少量として算出した。Each of the above samples, trimethylamine gas (nitrogen balance) and the same amount of trimethylamine gas were placed in two sealed bags, allowed to stand for 24 hours, and the residual concentration of trimethylamine was quantified by gas chromatography. The supply amount (initial concentration) of trimethylamine gas is
Considering the adsorption by the bag, the concentration when only trimethylamine gas was allowed to stand for 24 hours was used. Therefore, the amount of trimethylamine gas removed by the sample was calculated as the amount of decrease from the residual concentration.
【００９０】比較試料のゼオライトでは、トリメチルア
ミンガスの除去量は１０ｍｇ／ｇ未満であり、固体酸量
が増えても大きな変化はみられなかった。一方、ＦＡＣ
ｌ−４によるトリメチルアミンガスの除去量は２０ｍｇ
／ｇ以上であり、ゼオライトの２倍以上の脱臭効果が見
られた。 （実施例１９）塩化アルミニウム担持（シリカ）メソポ
ア材料（ＦＡＣｌ−４）を固体酸触媒として用いて、そ
の固体酸触媒とポリエチレンの混合物を加熱して油化反
応をおこなった結果について説明する。なお、比較のた
めに、三塩化アルミニウム六水和物を空気中３５０℃で
１時間焼成したものを比較触媒として用いた場合と、無
触媒で上記油化反応をおこなった結果を示す。In the comparative sample zeolite, the amount of trimethylamine gas removed was less than 10 mg / g, and no significant change was observed even if the amount of solid acid was increased. On the other hand, FAC
The amount of trimethylamine gas removed by 1-4 is 20 mg
/ G or more, and the deodorizing effect more than twice that of zeolite was observed. (Example 19) An explanation will be given of the result of performing an oil conversion reaction by heating a mixture of a solid acid catalyst and polyethylene using aluminum chloride-supported (silica) mesopore material (FACl-4) as a solid acid catalyst. For comparison, the results of the case where the aluminum trichloride hexahydrate calcined in air at 350 ° C. for 1 hour is used as a comparative catalyst and the case where the above oilification reaction is carried out without a catalyst are shown.
【００９１】図１４に示した反応装置は、ガラス器具、
攪拌用電動モータ、および加熱用の電気炉とリボンヒー
タからなり、生成ガス捕集用のアルミニウムラミネート
袋を備えたものである。なお、高温雰囲気に置かれるガ
ラス器具の接続部分は針金で固定した。５０ｍｌのフラ
スコに、高密度ポリエチレン・ペレット１０．０ｇと粉
末状触媒１．０ｇとを窒素気流下でとり、図１４の反応
装置を組立てた。この混合物を電動モータでゆっくりと
攪拌しながら、電気炉内の温度が４００℃に、およびリ
ボンヒータの内側の温度が３５０℃になるように加熱し
て、ポリエチレンの接触分解油化をおこなった。The reactor shown in FIG. 14 is a glass instrument,
It is composed of an electric motor for stirring, an electric furnace for heating and a ribbon heater, and is provided with an aluminum laminate bag for collecting generated gas. In addition, the connection part of the glass instrument placed in a high temperature atmosphere was fixed with a wire. In a 50 ml flask, 10.0 g of high-density polyethylene pellets and 1.0 g of powdered catalyst were placed under a nitrogen stream, and the reactor shown in FIG. 14 was assembled. While slowly stirring this mixture with an electric motor, the temperature in the electric furnace was heated to 400 ° C. and the temperature inside the ribbon heater was heated to 350 ° C. to effect catalytic cracking of polyethylene.
【００９２】生成油の収率は、無触媒で７２％であった
が、ＦＡＣｌ−４を油化触媒に用いた場合は５２％であ
り、比較触媒では１２％であった。図１５には、上記反
応装置により無触媒でポリエチレンを熱分解して得た熱
分解油と上記ＦＡＣｌ−４による生成油とをガスクロマ
トグラフ（ＧＣ）法およびＧＣ−ＭＳ法で分析してもと
めた、生成炭化水素油の炭素数別の組成分布図を示し
た。熱分解油の組成は炭素数４〜２８の広い分布であっ
たが、ＦＡＣｌ−４による生成油の組成は炭素数６と７
を主成分とした炭素数３〜１２の狭い分布であり、低沸
点の炭化水素油からなる組成であった。なお、ＦＡＣｌ
−４による生成油と比較触媒による生成油には、有機ハ
ロゲン化物の２−クロロ−２メチルプロパンが少量（共
に０．３％）含まれていた。このことから、塩化アルミ
ニウム担持（シリカ）メソポア材料は有機ハロゲン化物
の副生を抑えながら低沸点炭化水素油を高収率で与えう
る廃プラスチックの油化触媒であることがわかる。The yield of the product oil was 72% without a catalyst, but was 52% when FACl-4 was used as an oilification catalyst, and 12% with the comparative catalyst. In FIG. 15, the pyrolysis oil obtained by pyrolyzing polyethylene without a catalyst by the reactor and the oil produced by FACl-4 were analyzed by gas chromatography (GC) method and GC-MS method. The composition distribution chart of the produced hydrocarbon oil by carbon number is shown. The composition of pyrolysis oil had a wide distribution of 4 to 28 carbons, but the composition of oil produced by FACl-4 had 6 and 7 carbons.
It had a narrow distribution of 3 to 12 carbon atoms and was composed of a low boiling point hydrocarbon oil. In addition, FACl
The oil produced by -4 and the oil produced by the comparative catalyst contained a small amount (both 0.3%) of the organic halide 2-chloro-2-methylpropane. From this, it is understood that the aluminum chloride-supported (silica) mesopore material is an oilification catalyst for waste plastics that can give a low boiling point hydrocarbon oil in a high yield while suppressing the by-product of organic halides.
【００９３】[0093]
【発明の効果】本発明の金属ハロゲン化物担持メソポア
材料は、特定の大きさの細孔（メソポア）を均一に有す
る無機酸化物を担体とした新規な金属ハロゲン化物担持
化合物を供給できる。この化合物は、大きい比表面積を
もつルイス酸担持触媒として、反応触媒や脱臭剤などに
利用できる。この化合物は、その細孔径がゼオライトな
どの従来の結晶性固体酸よりも大きいので、従来型固体
酸の細孔内に侵入できなかった比較的大きいな分子（反
応基質）と、反応や吸着を行うことができる。この化合
物は、有機溶媒にたいする分散性がよいので、液相反応
に用いる固体酸触媒としての利用が可能である。INDUSTRIAL APPLICABILITY The metal halide-supporting mesopore material of the present invention can supply a novel metal halide-supporting compound having an inorganic oxide as a carrier, which has uniformly pores (mesopores) of a specific size. This compound can be used as a Lewis acid-supported catalyst having a large specific surface area, such as a reaction catalyst or a deodorant. Since the pore size of this compound is larger than that of conventional crystalline solid acids such as zeolite, it does not react or adsorb with relatively large molecules (reactive substrates) that could not penetrate into the pores of conventional solid acids. It can be carried out. Since this compound has good dispersibility in an organic solvent, it can be used as a solid acid catalyst used in a liquid phase reaction.
【００９４】本発明の金属ハロゲン化物担持メソポア材
料の製造方法では、特定の大きさの細孔（メソポア）を
均一に有する無機酸化物と金属ハロゲン化物がより均一
に反応した新規な金属ハロゲン化合物を製造できる。ま
た、金属ハロゲン化物が有機溶媒可溶性かつ無機酸化物
に対して有機溶媒中で非反応性である場合には、有機溶
媒に脱酸剤を添加することによって、金属ハロゲン化物
担持化合物の合成を可能とした。In the method for producing a metal halide-supporting mesopore material of the present invention, a novel metal halide compound in which an inorganic oxide uniformly having pores (mesopores) of a specific size and a metal halide react more uniformly is provided. Can be manufactured. In addition, when the metal halide is soluble in the organic solvent and non-reactive with the inorganic oxide in the organic solvent, it is possible to synthesize the metal halide-supported compound by adding a deoxidizing agent to the organic solvent. And
【００９５】本発明の金属ハロゲン化物担持メソポア材
料の第２の製造方法では、無機酸化物の官能基が分解す
る温度未満の温度で、昇華または蒸発により蒸気となる
金属ハロゲン化物を、特定の大きさの細孔（メソポア）
を均一に有する無機酸化物に担持した新規な金属ハロゲ
ン化物担持化合物を製造することができる。本発明の金
属水酸化物担持メソポア材料は、特定の大きさの細孔
（メソポア）を均一に有する無機酸化物を担体とした新
規な金属水酸化物を提供できる。この化合物は、大きい
比表面積を持つ新規な金属水酸化物担持化合物であるの
で、新規触媒担体としての利用が可能である。In the second method for producing a metal halide-supporting mesopore material of the present invention, a metal halide which becomes vapor by sublimation or evaporation at a temperature below the temperature at which the functional group of the inorganic oxide decomposes has a specific size. Pores of Mesopore
It is possible to produce a novel metal halide-supporting compound that is supported on an inorganic oxide having uniformly. INDUSTRIAL APPLICABILITY The metal hydroxide-supporting mesopore material of the present invention can provide a novel metal hydroxide having an inorganic oxide having pores (mesopores) of a specific size uniformly as a carrier. Since this compound is a novel metal hydroxide-supporting compound having a large specific surface area, it can be used as a novel catalyst carrier.
【００９６】本発明の金属水酸化物担持メソポア材料の
製造方法は、特定の大きさの細孔（メソポア）を均一に
有する無機酸化物が均一した新規な金属水酸化物担持化
合物を製造できる。金属ハロゲン化物担持化合物の加水
分解を空気中また水中で行うことにより、状態が異なる
金属水酸化物担持化合物を製造できる。本発明の金属酸
化物担持メソポア材料は、特定の大きさの細孔（メソポ
ア）を均一に有する無機酸化物を担持した新規な金属酸
化物を提供できる。この化合物は、大きい比表面積を持
つ新規な金属酸化物担持化合物であり、かつ新規複合酸
化物であるので、新規触媒担持および新規触媒として利
用が可能である。The method for producing a metal hydroxide-supporting mesopore material of the present invention can produce a novel metal hydroxide-supporting compound in which an inorganic oxide having pores (mesopores) of a specific size is uniform. By hydrolyzing the metal halide-supporting compound in air or in water, metal hydroxide-supporting compounds in different states can be produced. INDUSTRIAL APPLICABILITY The metal oxide-supporting mesopore material of the present invention can provide a novel metal oxide carrying an inorganic oxide having pores (mesopores) of a specific size uniformly. Since this compound is a novel metal oxide-supporting compound having a large specific surface area and a novel composite oxide, it can be used as a new catalyst support and a new catalyst.
【００９７】本発明の金属酸化物担持メソポア材料の製
造方法は、特定の大きさの細孔（メソポア）を均一に有
する無機酸化物に金属酸化物が均一に結合した新規な金
属酸化物担持化合物（新規複合酸化物）を、金属ハロゲ
ン化物担持化合物または金属酸化物担持化合物から製造
できる。本発明の金属担持メソポア材料は、特定の大き
さの細孔（メソポア）を均一に有する無機酸化物を担体
とした金属担持化合物が提供できる。この化合物は、大
きい比表面積を持つ金属担持化合物であるので、触媒と
して利用が可能である。The method for producing a metal oxide-supporting mesopore material of the present invention is a novel metal oxide-supporting compound in which a metal oxide is uniformly bonded to an inorganic oxide having pores (mesopores) of a specific size. The (new composite oxide) can be produced from a metal halide-supporting compound or a metal oxide-supporting compound. The metal-supporting mesopore material of the present invention can provide a metal-supporting compound having an inorganic oxide as a carrier, which has pores (mesopores) having a specific size uniformly. Since this compound is a metal-supporting compound having a large specific surface area, it can be used as a catalyst.
【００９８】本発明の金属担持メソポア材料の製造方法
は、特定の大きさの細孔（メソポア）を均一に有する無
機酸化物を担体とした金属担持化合物を、金属ハロゲン
化物担持化合物から製造できる。In the method for producing a metal-supporting mesopore material of the present invention, a metal-supporting compound having an inorganic oxide as a carrier, which has pores (mesopores) having a specific size uniformly, can be produced from a metal-halide-supporting compound.
【図１】実施例２における（シリカ）メソポア材料（Ｆ
−１６Ｃ）の粉末Ｘ線回折パターンを示す特性図であ
る。FIG. 1 is a (silica) mesopore material (F in Example 2).
It is a characteristic view showing a powder X-ray diffraction pattern of -16C).
【図２】実施例２における（シリカ）メソポア材料（Ｆ
−１６Ｃ）の結晶構造を示す透過型電子顕微鏡写真図で
ある。FIG. 2 shows a (silica) mesopore material (F in Example 2).
FIG. 16 is a transmission electron micrograph showing a crystal structure of −16C).
【図３】実施例３における（シリカ）メソポア材料（Ｆ
−１６Ｃ）の窒素吸着等温線から算出した細孔分布曲線
を示す特性図である。FIG. 3 is a (silica) mesopore material (F in Example 3).
FIG. 16 is a characteristic diagram showing a pore distribution curve calculated from the nitrogen adsorption isotherm of −16 C).
【図４】実施例１３における活性化（シリカ）メソポア
材料（ＤＨＦ−１６）と塩化アルミニウム担持（シリ
カ）メソポア材料（ＦＡＣｌ−４）の29ＳｉＭＡＳ−Ｎ
ＭＲスペクトルを示す特性図である。FIG. 4 29 SiMAS-N of activated (silica) mesopore material (DHF-16) and aluminum chloride supported (silica) mesopore material (FACl-4) in Example 13.
It is a characteristic view which shows MR spectrum.
【図５】実施例１３における塩化アルミニウム担持（シ
リカ）メソポア材料（ＦＡＣｌ−４）の27ＡｌＭＡＳ−
ＮＭＲスペクトルを示す特性図である。FIG. 5: 27 AlMAS- of aluminum chloride-supported (silica) mesopore material (FACl-4) in Example 13.
It is a characteristic view which shows an NMR spectrum.
【図６】実施例１５における塩化アルミニウム担持（シ
リカ）メソポア材料（ＦＡＣｌ−４）の窒素吸着等温線
から算出した細孔分布曲線を示す特性図である。FIG. 6 is a characteristic diagram showing a pore distribution curve calculated from a nitrogen adsorption isotherm of an aluminum chloride-supported (silica) mesopore material (FACl-4) in Example 15.
【図７】実施例１６における白金担持（シリカ）メソポ
ア材料（ＦＰｔ−７Ｃｌ）のＸＰＳ測定によるＰｔ４ｆ
5/2 とＰｔ４ｆ7/2 のスペクトルを示す特性図である。7 is a Pt4f obtained by XPS measurement of a platinum-supported (silica) mesopore material (FPt-7Cl) in Example 16. FIG.
It is a characteristic diagram showing a spectrum of a 5/2 and Pt 4f 7/2.
【図８】実施例１７における活性化（シリカ）メソポア
材料（ＤＨＦ−１６）と塩化アルミニウム担持（シリ
カ）メソポア材料（ＦＡＣｌ−４）の粉末Ｘ線回折パタ
ーンを示す特性図である。FIG. 8 is a characteristic diagram showing powder X-ray diffraction patterns of an activated (silica) mesopore material (DHF-16) and an aluminum chloride-supported (silica) mesopore material (FACl-4) in Example 17.
【図９】実施例１７における２種類の水酸化アルミニウ
ム担持（シリカ）メソポア材料（ＦＡＯＨ−４Ａ、ＦＡ
ＯＨ−４Ｗ）の粉末Ｘ線回折パターンを示す特性図であ
る。FIG. 9: Two types of aluminum hydroxide-supporting (silica) mesopore materials (FAOH-4A, FA) in Example 17
It is a characteristic view showing a powder X-ray diffraction pattern of (OH-4W).
【図１０】実施例１７における３種類の酸化アルミニウ
ム担持（シリカ）メソポア材料（ＦＡＯ−４Ｃｌ、ＦＡ
Ｏ−４Ａ、ＦＯＡ−４Ｗ）の粉末Ｘ線回折パターンを示
す特性図である。FIG. 10 shows three types of aluminum oxide-supported (silica) mesopore materials (FAO-4Cl, FA) in Example 17.
It is a characteristic view showing a powder X-ray diffraction pattern of O-4A, FOA-4W).
【図１１】実施例１８における塩化アルミニウム担持
（シリカ）メソポア材料（ＦＡＣｌ−４）、Ｘゼオライ
トおよびＨＹゼオライトによるトリエチルアミンの除去
量を示す特性図である。11 is a characteristic diagram showing the amount of triethylamine removed by an aluminum chloride-supported (silica) mesopore material (FACl-4), X zeolite, and HY zeolite in Example 18. FIG.
【図１２】（シリカ）メソポア材料ＦＳＭ−１６の生成
機構の模式図である。FIG. 12 is a schematic diagram of a production mechanism of (silica) mesopore material FSM-16.
【図１３】（ａ）は（シリカ）メソポア材料の表面構造
の模式図である。（ｂ）は活性化（シリカ）メソポア材
料の表面構造の模式図である。（ｃ）は金属ハロゲン化
物担持（シリカ）メソポア材料の金属ハロゲン化物（塩
化アルミニウム）が一分子層担持された場合の表面構造
の模式図である。（ｄ）は金属ハロゲン化物担持（シリ
カ）メソポア材料の金属ハロゲン化物（塩化アルミニウ
ム）が二分子層担持された場合の表面構造の模式図であ
る。FIG. 13 (a) is a schematic view of the surface structure of a (silica) mesopore material. (B) is a schematic diagram of the surface structure of an activated (silica) mesopore material. (C) is a schematic diagram of a surface structure when a metal halide (aluminum chloride) of a metal halide-supported (silica) mesopore material is supported as a monolayer. (D) is a schematic diagram of a surface structure when a metal halide (aluminum chloride) of a metal halide-supported (silica) mesopore material is supported as a bilayer.
【図１４】熱分解工程で使用する場合の油化反応装置の
説明図である。FIG. 14 is an explanatory diagram of an oilification reaction device when used in a thermal decomposition step.
【図１５】無触媒および油化触媒ＦＡＣｌ−４を用い
て、ポリエチレンから生成した炭化水素油の炭素数別の
組成分布を示すグラフである。FIG. 15 is a graph showing the composition distribution by the number of carbon atoms in a hydrocarbon oil produced from polyethylene using a catalyst-free catalyst and an oil conversion catalyst FACl-4.
【手続補正書】[Procedure amendment]
【提出日】平成８年５月２９日[Submission date] May 29, 1996
【手続補正１】[Procedure amendment 1]
【補正対象書類名】図面[Document name to be amended] Drawing
【補正対象項目名】図２[Correction target item name] Figure 2
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【図２】 [Fig. 2]
【手続補正２】[Procedure amendment 2]
【補正対象書類名】図面[Document name to be amended] Drawing
【補正対象項目名】図１２[Correction target item name] FIG.
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【図１２】 FIG.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０４Ｂ 41/85 Ｃ０４Ｂ 41/85 Ｃ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication C04B 41/85 C04B 41/85 C
Claims (22)
孔を多数有する無機酸化物の多孔体であって、少なくと
も前記細孔内表面に備えた官能基に金属ハロゲン化物が
結合した金属ハロゲン化物担持メソポア材料。1. A porous body of an inorganic oxide having a large number of pores having a uniform diameter within a range of 2 to 10 nm, wherein a metal halide is bonded to at least a functional group provided on the inner surface of the pores. Metal halide supported mesopore material.
囲内である請求項１に記載の金属ハロゲン化物担持メソ
ポア材料。2. The metal halide-supporting mesopore material according to claim 1, wherein the pore size of the inorganic oxide is in the range of 2 to 6 nm.
曲線における最大ピークを示す細孔直径が２〜１０ｎｍ
の範囲にあり、かつこれらの細孔の６０％以上が前記細
孔径分布曲線における最大ピークを示す細孔直径の±４
０％の範囲の細孔径を有する請求項１に記載の金属ハロ
ゲン化物担持メソポア材料。3. The pores of the inorganic oxide porous body have a pore diameter of 2 to 10 nm, which shows the maximum peak in a pore distribution curve.
, And 60% or more of these pores show the maximum peak in the pore diameter distribution curve ± 4 of the pore diameter.
The metal halide-supporting mesopore material according to claim 1, which has a pore size in the range of 0%.
体の少なくとも細孔内表面に均一に一分子層または二分
子層以上に結合した請求項１から３のいずれかに記載の
金属ハロゲン化物担持メソポア材料。4. The metal halogen according to any one of claims 1 to 3, wherein the metal halide is uniformly bonded to at least the inner surface of the pores of the inorganic oxide porous body in a monolayer or bilayer or more. Compound-supporting mesopore material.
ハロゲン化物の反応率は、単量体換算で３０〜３００％
である請求項１から４のいずれかに記載の金属ハロゲン
化物担持メソポア材料。5. The reaction rate of the metal halide with respect to the functional group on the surface of the inorganic oxide is 30 to 300% in terms of monomer.
The metal halide-supporting mesopore material according to any one of claims 1 to 4, which is
VIII族あるいはＩｂ族遷移金属のハロゲン化物、または
Ia,IIa,IIb〜VIb の金属のハロゲン化物である請求項１
から５のいずれかに記載の金属ハロゲン化物担持メソポ
ア材料。6. The metal halide is represented by IVa to
Halides of group VIII or Ib transition metals, or
A halide of a metal of Ia, IIa, IIb to VIb.
6. The metal halide-supporting mesopore material according to any one of 1 to 5.
用するものである請求項１から７のいずれかに記載の金
属ハロゲン化物担持メソポア材料。7. The metal halide-supporting mesopore material according to claim 1, wherein the metal halide acts as a Lewis acid.
ウム（AlCl3)または無水塩化第二鉄(FeCl3) である請求
項１から６のいずれかに記載の金属ハロゲン化物担持メ
ソポア材料。8. The metal halide-supporting mesopore material according to claim 1, wherein the metal halide is anhydrous aluminum chloride (AlCl 3 ) or anhydrous ferric chloride (FeCl 3 ).
数の細孔を有し、少なくとも該細孔内表面には金属ハロ
ゲン化物が結合できる官能基を有する無機酸化物の多孔
体と、金属ハロゲン化物とを有機溶媒中で反応させ、該
金属ハロゲン化物と該無機酸化物の官能基との結合を形
成することを特徴とする金属ハロゲン化物担持メソポア
材料の製造方法。9. A porous body of an inorganic oxide having a large number of pores having a uniform diameter within a range of 2 to 10 nm and having a functional group capable of binding a metal halide on at least the inner surface of the pores. A method for producing a metal halide-supporting mesopore material, which comprises reacting a metal halide with an organic solvent to form a bond between the metal halide and a functional group of the inorganic oxide.
は、予め脱水処理され、該結合反応が非水雰囲気下でお
こなわれる請求項９に記載の金属ハロゲン化物担持メソ
ポア材料の製造方法。10. The method for producing a metal halide-supporting mesopore material according to claim 9, wherein the organic solvent and the inorganic halide are dehydrated in advance and the binding reaction is performed in a non-aqueous atmosphere.
過型電子顕微鏡写真下での粒子直径が０．０２〜５μｍ
の範囲にあり、かつ６０％以上の粒子が粒子直径の比で
１：１０の範囲内にある請求項９から１０のいずれかに
記載の金属ハロゲン化物担持メソポア材料の製造方法。11. The porous body of the inorganic oxide has a particle diameter distribution of 0.02 to 5 μm as measured under a transmission electron microscope.
The method for producing a metal halide-supporting mesopore material according to any one of claims 9 to 10, wherein 60% or more of the particles have a particle diameter ratio of 1:10.
のである場合には、該有機溶媒は、ハロゲン系溶媒、ニ
トロ化物溶媒、芳香族溶媒の少なくとも１種から選ばれ
る請求項９に記載の金属ハロゲン化物担持メソポア材料
の製造方法。12. The organic solvent according to claim 9, when the metal halide is easily soluble in an organic solvent, the organic solvent is selected from at least one of a halogen solvent, a nitrate solvent and an aromatic solvent. A method for producing a metal halide-supporting mesopore material.
かつ無機酸化物に対して有機溶媒中で非反応性である場
合には、有機溶媒に脱酸剤を添加する。ここで、有機溶
媒可溶性の金属ハロゲン化物とは、ハロゲン系溶媒、ニ
トロ化物溶媒、または芳香族溶媒に溶解するものである
請求項９から１０のいずれかに記載の金属ハロゲン化物
担持メソポア材料の製造方法。13. When the metal halide is easily soluble in an organic solvent and non-reactive with an inorganic oxide in the organic solvent, a deoxidizing agent is added to the organic solvent. Here, the organic solvent-soluble metal halide is a solvent that dissolves in a halogen-based solvent, a nitrate solvent, or an aromatic solvent, and the method for producing a metal halide-supporting mesopore material according to claim 9. Method.
下であり、室温で液体のものである請求項９から１０の
いずれかに記載の金属ハロゲン化物担持メソポア材料の
製造方法。14. The method for producing a metal halide-supporting mesopore material according to claim 9, wherein the metal halide has a melting point of 25 ° C. or lower and is liquid at room temperature.
ポアの細孔径が均一で、少なくとも細孔内表面に金属ハ
ロゲン化物が結合できる無機酸化物に対して金属ハロゲ
ン化物の蒸気を接触させる金属ハロゲン化物担持メソポ
ア材料の製造方法。15. A metal having a mesopore of 2 to 10 nm, a pore diameter of each mesopore being uniform, and a metal halide vapor being brought into contact with an inorganic oxide capable of binding a metal halide to at least the inner surface of the pore. Method for producing halide-supporting mesopore material.
ポアの細孔径が均一で、少なくとも細孔内表面に金属水
酸化物が結合された官能基を有する無機酸化物からなる
金属水酸化物担持メソポア材料。16. A metal hydroxide having a mesopore of 2 to 10 nm, a uniform pore size of each mesopore, and an inorganic oxide having a functional group having a metal hydroxide bonded to at least the inner surface of the pore. Supported mesopore material.
加水分解する請求項１６に記載の金属水酸化物担持メソ
ポア材料の製造方法。17. The method for producing a metal hydroxide-supporting mesopore material according to claim 16, wherein the metal halide-supporting mesopore material is hydrolyzed.
ポアの細孔径が均一で、少なくとも細孔内表面に金属酸
化物が結合された官能基を有する無機酸化物からなる金
属酸化物担持メソポア材料。18. A metal oxide-supporting mesopore having a mesopore of 2 to 10 nm, a uniform pore size of each mesopore, and at least an inorganic oxide having a functional group having a metal oxide bonded to the inner surface of the pore. material.
焼成する請求項１８に記載の金属酸化物担持メソポア材
料の製造方法。19. The method for producing a metal oxide-supporting mesopore material according to claim 18, wherein the metal halide-supporting mesopore material is fired.
する請求項１８に記載の金属酸化物担持メソポア材料。20. The metal oxide-supporting mesopore material according to claim 18, wherein the metal hydroxide-supporting mesopore material is fired.
ポアの細孔径が均一で、少なくとも細孔内表面に金属が
固定された官能基を有する無機酸化物からなる金属酸化
物担持メソポア材料。21. A metal oxide-supporting mesopore material having a mesopore of 2 to 10 nm, a uniform pore size of each mesopore, and at least an inorganic oxide having a functional group having a metal fixed on the inner surface of the pore.
還元または熱分解する請求項２１に記載の金属酸化物担
持メソポア材料の製造方法。22. The method for producing a metal oxide-supporting mesopore material according to claim 21, wherein the metal halide-supporting mesopore material is reduced or thermally decomposed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12746596A JP3902260B2 (en) | 1996-05-22 | 1996-05-22 | Metal halide-supported mesopore material, metal hydroxide-supported mesopore material, metal oxide-supported mesopore material, metal-supported mesopore material, and production methods thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12746596A JP3902260B2 (en) | 1996-05-22 | 1996-05-22 | Metal halide-supported mesopore material, metal hydroxide-supported mesopore material, metal oxide-supported mesopore material, metal-supported mesopore material, and production methods thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09313950A true JPH09313950A (en) | 1997-12-09 |
| JP3902260B2 JP3902260B2 (en) | 2007-04-04 |
Family
ID=14960608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12746596A Expired - Fee Related JP3902260B2 (en) | 1996-05-22 | 1996-05-22 | Metal halide-supported mesopore material, metal hydroxide-supported mesopore material, metal oxide-supported mesopore material, metal-supported mesopore material, and production methods thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3902260B2 (en) |
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| JP2001335312A (en) * | 2000-05-22 | 2001-12-04 | Toyota Central Res & Dev Lab Inc | Method of producing porous body |
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| JP2001232205A (en) * | 2000-01-31 | 2001-08-28 | Solvay & Cie | Composition containing antimony trifluoride and silica |
| JP2001335312A (en) * | 2000-05-22 | 2001-12-04 | Toyota Central Res & Dev Lab Inc | Method of producing porous body |
| JP2006306707A (en) * | 2005-03-30 | 2006-11-09 | Toyota Central Res & Dev Lab Inc | Oxide composite material and its production method |
| JP2009046372A (en) * | 2007-08-23 | 2009-03-05 | Tochigi Prefecture | Metal nanoparticle, zeolite with dispersed metal nanoparticle and method for producing zeolite with dispersed metal nanoparticle |
| JP2009242170A (en) * | 2008-03-31 | 2009-10-22 | Hiroshima Univ | Composite and its producing method |
| CN102015594A (en) * | 2008-04-25 | 2011-04-13 | 旭硝子株式会社 | Method for purifying tetrafluoroethylene |
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