JP2006159057A - Method for manufacturing titanium-containing silicon oxide catalyst and catalyst - Google Patents
Method for manufacturing titanium-containing silicon oxide catalyst and catalyst Download PDFInfo
- Publication number
- JP2006159057A JP2006159057A JP2004352357A JP2004352357A JP2006159057A JP 2006159057 A JP2006159057 A JP 2006159057A JP 2004352357 A JP2004352357 A JP 2004352357A JP 2004352357 A JP2004352357 A JP 2004352357A JP 2006159057 A JP2006159057 A JP 2006159057A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- mold
- titanium
- solvent
- solid
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000010936 titanium Substances 0.000 title claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 54
- 239000007787 solid Substances 0.000 claims abstract description 34
- -1 oxirane compound Chemical class 0.000 claims abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 150000001336 alkenes Chemical class 0.000 claims description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 14
- 238000006884 silylation reaction Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- 238000000638 solvent extraction Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 8
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- 238000000605 extraction Methods 0.000 description 20
- 238000006467 substitution reaction Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
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- 239000007788 liquid Substances 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
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- 238000000465 moulding Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
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- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 6
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
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- 238000006735 epoxidation reaction Methods 0.000 description 4
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- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
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- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
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- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- KWYZNESIGBQHJK-UHFFFAOYSA-N chloro-dimethyl-phenylsilane Chemical compound C[Si](C)(Cl)C1=CC=CC=C1 KWYZNESIGBQHJK-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
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- 229910052736 halogen Inorganic materials 0.000 description 2
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
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- 239000000376 reactant Substances 0.000 description 2
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
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- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HIMXYMYMHUAZLW-UHFFFAOYSA-N [[[dimethyl(phenyl)silyl]amino]-dimethylsilyl]benzene Chemical compound C=1C=CC=CC=1[Si](C)(C)N[Si](C)(C)C1=CC=CC=C1 HIMXYMYMHUAZLW-UHFFFAOYSA-N 0.000 description 1
- KOOADCGQJDGAGA-UHFFFAOYSA-N [amino(dimethyl)silyl]methane Chemical compound C[Si](C)(C)N KOOADCGQJDGAGA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- ABHNFDUSOVXXOA-UHFFFAOYSA-N benzyl-chloro-dimethylsilane Chemical compound C[Si](C)(Cl)CC1=CC=CC=C1 ABHNFDUSOVXXOA-UHFFFAOYSA-N 0.000 description 1
- WGQKYBSKWIADBV-UHFFFAOYSA-O benzylaminium Chemical compound [NH3+]CC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-O 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- VMYTYUVXHJVTTL-UHFFFAOYSA-N bromo-chloro-dimethylsilane Chemical compound C[Si](C)(Cl)Br VMYTYUVXHJVTTL-UHFFFAOYSA-N 0.000 description 1
- CAURZYXCQQWBJO-UHFFFAOYSA-N bromomethyl-chloro-dimethylsilane Chemical compound C[Si](C)(Cl)CBr CAURZYXCQQWBJO-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- MXOSTENCGSDMRE-UHFFFAOYSA-N butyl-chloro-dimethylsilane Chemical compound CCCC[Si](C)(C)Cl MXOSTENCGSDMRE-UHFFFAOYSA-N 0.000 description 1
- OAFIHQYAADHJED-UHFFFAOYSA-N butyl-iodo-dimethylsilane Chemical compound CCCC[Si](C)(C)I OAFIHQYAADHJED-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical compound CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 description 1
- 229960004830 cetylpyridinium Drugs 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- YIGRKKJIRPDASV-UHFFFAOYSA-N chloro(dimethoxymethyl)silane Chemical compound COC(OC)[SiH2]Cl YIGRKKJIRPDASV-UHFFFAOYSA-N 0.000 description 1
- YCITZMJNBYYMJO-UHFFFAOYSA-N chloro(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](Cl)C1=CC=CC=C1 YCITZMJNBYYMJO-UHFFFAOYSA-N 0.000 description 1
- JEZFASCUIZYYEV-UHFFFAOYSA-N chloro(triethoxy)silane Chemical compound CCO[Si](Cl)(OCC)OCC JEZFASCUIZYYEV-UHFFFAOYSA-N 0.000 description 1
- WZQSBCHNVPAYOC-UHFFFAOYSA-N chloro(trihexyl)silane Chemical compound CCCCCC[Si](Cl)(CCCCCC)CCCCCC WZQSBCHNVPAYOC-UHFFFAOYSA-N 0.000 description 1
- ACTAPAGNZPZLEF-UHFFFAOYSA-N chloro(tripropyl)silane Chemical compound CCC[Si](Cl)(CCC)CCC ACTAPAGNZPZLEF-UHFFFAOYSA-N 0.000 description 1
- BJLJNLUARMMMLW-UHFFFAOYSA-N chloro-(3-chloropropyl)-dimethylsilane Chemical compound C[Si](C)(Cl)CCCCl BJLJNLUARMMMLW-UHFFFAOYSA-N 0.000 description 1
- ITKVLPYNJQOCPW-UHFFFAOYSA-N chloro-(chloromethyl)-dimethylsilane Chemical compound C[Si](C)(Cl)CCl ITKVLPYNJQOCPW-UHFFFAOYSA-N 0.000 description 1
- SXSNZRHGAMVNJE-UHFFFAOYSA-N chloro-[[[chloromethyl(dimethyl)silyl]amino]-dimethylsilyl]methane Chemical compound ClC[Si](C)(C)N[Si](C)(C)CCl SXSNZRHGAMVNJE-UHFFFAOYSA-N 0.000 description 1
- GZGREZWGCWVAEE-UHFFFAOYSA-N chloro-dimethyl-octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](C)(C)Cl GZGREZWGCWVAEE-UHFFFAOYSA-N 0.000 description 1
- DBKNGKYVNBJWHL-UHFFFAOYSA-N chloro-dimethyl-octylsilane Chemical compound CCCCCCCC[Si](C)(C)Cl DBKNGKYVNBJWHL-UHFFFAOYSA-N 0.000 description 1
- YCXVDEMHEKQQCI-UHFFFAOYSA-N chloro-dimethyl-propan-2-ylsilane Chemical compound CC(C)[Si](C)(C)Cl YCXVDEMHEKQQCI-UHFFFAOYSA-N 0.000 description 1
- HXVPUKPVLPTVCQ-UHFFFAOYSA-N chloro-dimethyl-propylsilane Chemical compound CCC[Si](C)(C)Cl HXVPUKPVLPTVCQ-UHFFFAOYSA-N 0.000 description 1
- PLMTWHZZBPGADP-UHFFFAOYSA-N chloro-ethenyl-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=C)(Cl)C1=CC=CC=C1 PLMTWHZZBPGADP-UHFFFAOYSA-N 0.000 description 1
- AVDUEHWPPXIAEB-UHFFFAOYSA-N chloro-ethyl-dimethylsilane Chemical compound CC[Si](C)(C)Cl AVDUEHWPPXIAEB-UHFFFAOYSA-N 0.000 description 1
- ZIFXYFOVERKZLG-UHFFFAOYSA-N chloro-methyl-(2-phenylethenyl)silane Chemical compound C[SiH](Cl)C=CC1=CC=CC=C1 ZIFXYFOVERKZLG-UHFFFAOYSA-N 0.000 description 1
- OJZNZOXALZKPEA-UHFFFAOYSA-N chloro-methyl-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](Cl)(C)C1=CC=CC=C1 OJZNZOXALZKPEA-UHFFFAOYSA-N 0.000 description 1
- YGHUUVGIRWMJGE-UHFFFAOYSA-N chlorodimethylsilane Chemical compound C[SiH](C)Cl YGHUUVGIRWMJGE-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000005131 dialkylammonium group Chemical group 0.000 description 1
- QQJDHWMADUVRDL-UHFFFAOYSA-N didodecyl(dimethyl)azanium Chemical compound CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC QQJDHWMADUVRDL-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical compound CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- LULXBAGMGMJJRW-UHFFFAOYSA-N n,2-bis(trimethylsilyl)acetamide Chemical compound C[Si](C)(C)CC(=O)N[Si](C)(C)C LULXBAGMGMJJRW-UHFFFAOYSA-N 0.000 description 1
- ZSMNRKGGHXLZEC-UHFFFAOYSA-N n,n-bis(trimethylsilyl)methanamine Chemical compound C[Si](C)(C)N(C)[Si](C)(C)C ZSMNRKGGHXLZEC-UHFFFAOYSA-N 0.000 description 1
- QHUOBLDKFGCVCG-UHFFFAOYSA-N n-methyl-n-trimethylsilylacetamide Chemical compound CC(=O)N(C)[Si](C)(C)C QHUOBLDKFGCVCG-UHFFFAOYSA-N 0.000 description 1
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 description 1
- LWFWUJCJKPUZLV-UHFFFAOYSA-N n-trimethylsilylacetamide Chemical compound CC(=O)N[Si](C)(C)C LWFWUJCJKPUZLV-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NVQGUGFHTHIDRH-UHFFFAOYSA-N oxotitanium(2+) pentane-2,4-dione Chemical compound O=[Ti++].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NVQGUGFHTHIDRH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 1
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- UTXPCJHKADAFBB-UHFFFAOYSA-N tribenzyl(chloro)silane Chemical compound C=1C=CC=CC=1C[Si](CC=1C=CC=CC=1)(Cl)CC1=CC=CC=C1 UTXPCJHKADAFBB-UHFFFAOYSA-N 0.000 description 1
- JSQJUDVTRRCSRU-UHFFFAOYSA-N tributyl(chloro)silane Chemical compound CCCC[Si](Cl)(CCCC)CCCC JSQJUDVTRRCSRU-UHFFFAOYSA-N 0.000 description 1
- LAJGDBSSLQUXMC-UHFFFAOYSA-N trimethyl(nitro)silane Chemical compound C[Si](C)(C)[N+]([O-])=O LAJGDBSSLQUXMC-UHFFFAOYSA-N 0.000 description 1
- WLADIVUISABQHN-UHFFFAOYSA-N trimethyl(piperidin-1-yl)silane Chemical compound C[Si](C)(C)N1CCCCC1 WLADIVUISABQHN-UHFFFAOYSA-N 0.000 description 1
- WNHFEQWRHXLCMK-UHFFFAOYSA-N trimethyl(pyrrol-1-yl)silane Chemical compound C[Si](C)(C)N1C=CC=C1 WNHFEQWRHXLCMK-UHFFFAOYSA-N 0.000 description 1
- NQLVIKZJXFGUET-UHFFFAOYSA-N trimethyl(pyrrolidin-1-yl)silane Chemical compound C[Si](C)(C)N1CCCC1 NQLVIKZJXFGUET-UHFFFAOYSA-N 0.000 description 1
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
本発明は、チタン含有珪素酸化物触媒の製造方法及び触媒に関するものである。更に詳しくは、本発明は、たとえばハイドロパーオキサイドとオレフィン型化合物からオキシラン化合物を得る反応に用いることができ、高い活性と選択性を発揮し得るチタン含有珪素酸化物触媒の製造方法及び該製造方法により得られる触媒に関するものである。 The present invention relates to a method for producing a titanium-containing silicon oxide catalyst and a catalyst. More specifically, the present invention can be used, for example, in a reaction for obtaining an oxirane compound from hydroperoxide and an olefin type compound, and a method for producing a titanium-containing silicon oxide catalyst capable of exhibiting high activity and selectivity, and the method for producing the same. It is related with the catalyst obtained by this.
触媒の存在下、ハイドロパーオキサイドとオレフィン型化合物からオキシラン化合物を得る方法は公知である。ここで用いられる触媒としてチタン含有珪素化物触媒があげられ、高性能触媒を得るために疎水性の向上を図る試みがなされている。 A method for obtaining an oxirane compound from a hydroperoxide and an olefin type compound in the presence of a catalyst is known. Examples of the catalyst used here include a titanium-containing silicide catalyst, and attempts have been made to improve hydrophobicity in order to obtain a high-performance catalyst.
たとえば特許文献１および２、非特許文献１〜４には、炭化水素基が珪素原子に直接結合した珪素化合物を触媒原料として用いることにより疎水性が向上した特定のチタン含有珪素酸化物触媒が開示されている。しかしながら、これらの触媒は、より高い活性と選択性を発現させるという観点からは、十分に満足し得るものとは言い難いものであった。 For example, Patent Documents 1 and 2 and Non-Patent Documents 1 to 4 disclose specific titanium-containing silicon oxide catalysts having improved hydrophobicity by using, as a catalyst raw material, a silicon compound in which a hydrocarbon group is directly bonded to a silicon atom. Has been. However, these catalysts are hardly satisfactory from the viewpoint of developing higher activity and selectivity.
かかる現状において本発明が解決しようとする課題は、たとえばハイドロパーオキサイドとオレフィンからオレフィンオキサイドを得る反応に用いることができ、高い活性と選択性を発揮し得るチタン含有珪素酸化物触媒の製造方法及び該製造方法により得られる触媒を提供する点にある。 The problems to be solved by the present invention under such circumstances are, for example, a method for producing a titanium-containing silicon oxide catalyst that can be used in a reaction for obtaining olefin oxide from hydroperoxide and olefin, and that can exhibit high activity and selectivity, and It is in the point which provides the catalyst obtained by this manufacturing method.
すなわち、本発明のうち第一の発明は、下記（１）〜（４）の全ての条件を充足するチタン含有珪素酸化物触媒の製造方法であって、下記の第一工程〜第二工程を含む製造方法に係るものである。
（１）：平均細孔径が１０Å以上であること
（２）：全細孔容量の９０％以上が５〜２００Åの細孔径を有すること
（３）：比細孔容量が０．２ｃｍ3／ｇ以上であること
（４）：原料として用いるシリカ源の一部又は全部が、炭化水素基が珪素原子に直接結合した珪素化合物であること
第一工程：シリカ源、チタン源及び型剤（テンプレート）を溶媒中で混合・攪拌することにより触媒成分及び型剤を含有する固体を得る工程であって、該溶媒中の水の割合が５０重量％以下である工程
第二工程：第一工程で得た固体から型剤を除去する工程
That is, the first invention of the present invention is a method for producing a titanium-containing silicon oxide catalyst that satisfies all the following conditions (1) to (4), and includes the following first to second steps. It is related to the manufacturing method including.
(1): The average pore diameter is 10 mm or more (2): 90% or more of the total pore volume has a pore diameter of 5 to 200 mm (3): The specific pore volume is 0.2 cm 3 / g (4): Part or all of the silica source used as a raw material is a silicon compound in which a hydrocarbon group is directly bonded to a silicon atom. First step: Silica source, titanium source and mold (template) Is a step of obtaining a solid containing a catalyst component and a mold agent by mixing and stirring in a solvent, wherein the proportion of water in the solvent is 50% by weight or less. Second step: obtained in the first step Removing mold from solid
また、本発明のうち第二の発明は、上記の製造方法により得られるチタン含有珪素酸化物触媒に係るものである。 Moreover, 2nd invention among this invention concerns on the titanium containing silicon oxide catalyst obtained by said manufacturing method.
さらに、本発明のうち第三の発明は、上記の製造方法により得られるチタン含有珪素酸化物触媒の存在下、オレフィン型化合物とハイドロパーオキサイドを反応させることを特徴とするオキシラン化合物の製造方法に係るものである。 Furthermore, the third invention of the present invention is a method for producing an oxirane compound characterized by reacting an olefin type compound and hydroperoxide in the presence of a titanium-containing silicon oxide catalyst obtained by the above production method. It is concerned.
本発明により、たとえばハイドロパーオキサイドとオレフィン型化合物からオキシラン化合物を得る反応に用いることができ、高い活性と選択性を発揮し得るチタン含有珪素酸化物触媒の製造方法及び該製造方法により得られる触媒を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, for example, a method for producing a titanium-containing silicon oxide catalyst that can be used in a reaction for obtaining an oxirane compound from a hydroperoxide and an olefin type compound and can exhibit high activity and selectivity, and a catalyst obtained by the production method Can be provided.
本発明の触媒は、下記（１）〜（４）の全ての条件を充足するチタン含有珪素酸化物からなる触媒である。 The catalyst of the present invention is a catalyst comprising a titanium-containing silicon oxide that satisfies all the following conditions (1) to (4).
条件の（１）は平均細孔径が１０Å以上であることである。 The condition (1) is that the average pore diameter is 10 mm or more.
条件の（２）は、全細孔容量の９０％以上が５〜２００Åの細孔径を有することである。 Condition (2) is that 90% or more of the total pore volume has a pore diameter of 5 to 200 mm.
条件の（３）は、比細孔容量が０．２ｃｍ3／ｇ以上であることである。ここで、比細孔容量とは触媒１ｇ当りの細孔容量を意味している。 The condition (3) is that the specific pore volume is 0.2 cm 3 / g or more. Here, the specific pore volume means the pore volume per 1 g of catalyst.
条件の（４）は、原料として用いるシリカ源の一部又は全部が、炭化水素基が珪素原子に直接結合した珪素化合物であることである。 Condition (4) is that a part or all of the silica source used as a raw material is a silicon compound in which a hydrocarbon group is directly bonded to a silicon atom.
上記の条件（１）〜（３）についての測定は、窒素、アルゴン等の気体の物理吸着法を用い、通常の方法により測定することができる。 The measurement about said conditions (1)-(3) can be measured by a normal method using the physical adsorption method of gas, such as nitrogen and argon.
本発明の触媒は、Ｘ線回折（ＸＲＤ）において、面間隔ｄを示すピークが存在してもよいし、存在しなくてよい。ここでいう面間隔ｄを示すピークとは、固体が有する結晶性や規則性に由来するピークのことであり、アモルファスな部分に由来するブロードなピークは存在していてもかまわない。 The catalyst of the present invention may or may not have a peak indicating an interplanar distance d in X-ray diffraction (XRD). The peak indicating the interplanar spacing d here is a peak derived from the crystallinity or regularity of the solid, and there may be a broad peak derived from an amorphous part.
本発明の触媒は、高活性であるという観点から、赤外線吸収スペクトルにおいて９６０±５ｃｍ-1の領域に吸収ピークを有するものであることが好ましい。このピークはシリカ骨格内に導入されたチタンに対応するものであると考えられる。 From the viewpoint of high activity, the catalyst of the present invention preferably has an absorption peak in the region of 960 ± 5 cm −1 in the infrared absorption spectrum. This peak is considered to correspond to titanium introduced into the silica skeleton.
本発明の触媒は下記の工程を有する製造方法によって製造される。
第一工程：シリカ源、チタン源及び型剤（テンプレート）を溶媒中で混合・攪拌することにより触媒成分及び型剤を含有する固体を得る工程であって、該溶媒中の水の割合が５０重量％以下である工程
第二工程：第一工程で得た固体から型剤を除去する工程
The catalyst of the present invention is produced by a production method having the following steps.
First step: A step of obtaining a solid containing a catalyst component and a mold agent by mixing and stirring a silica source, a titanium source and a mold agent (template) in a solvent, and the proportion of water in the solvent is 50 Step that is not more than% by weight Second step: Step of removing the mold from the solid obtained in the first step
第一工程は、シリカ源、チタン源及び型剤（テンプレート）を溶媒中で混合・攪拌することにより触媒成分及び型剤を含有する固体を得る工程であって、該溶媒中の水の割合が５０重量％以下である工程である。用いる試薬は固体状の場合は溶媒に溶解又は分散した溶液として用いるとよい。 The first step is a step of obtaining a solid containing a catalyst component and a mold agent by mixing and stirring a silica source, a titanium source and a mold agent (template) in a solvent, and the proportion of water in the solvent is This is a step of 50% by weight or less. When the reagent to be used is a solid, it may be used as a solution dissolved or dispersed in a solvent.
本発明では原料として用いるシリカ源の一部あるいは全部に、炭化水素基が珪素原子に直接結合した珪素化合物が用いられ、モノアルキルトリアルコキシシラン、ジアルキルジアルコキシシラン、トリアルキルモノアルコキシシラン、ビス（トリアルコキシシリル）アルカン、モノアリールトリアルコキシシラン、ジアリールジアルコキシシラン、ビス（トリアルコキシシリル）アリールなどが挙げられる。それらは単独で用いることも出来るし、数種を混合させて用いても良い。なかでもモノアルキルトリアルコキシシラン及び／又はモノアリールトリアルコキシシランが好適に用いられ、たとえばアルキル基又はアリール基としてはメチル、エチル、プロピル、ブチル、ビニル、プロペニル、シクロペンテニル、シクロヘキセニル、フェニル、トリル、キシリル、ナフチル等などの炭素数１〜１６の炭化水素基があげられる。また上記のアルキル基、アリール基はＮ、Ｏ、Ｐ、ハロゲンなどを含む置換基を有していても良い。アルコキシ基としてはメトキシ、エトキシ、プロポキシ、ブトキシなどの炭素数１〜６の炭化水素基があげられる。 In the present invention, a silicon compound in which a hydrocarbon group is directly bonded to a silicon atom is used for a part or all of a silica source used as a raw material, and a monoalkyltrialkoxysilane, a dialkyldialkoxysilane, a trialkylmonoalkoxysilane, bis ( Trialkoxysilyl) alkane, monoaryltrialkoxysilane, diallyldialkoxysilane, bis (trialkoxysilyl) aryl and the like. They can be used alone or in a mixture of several kinds. Of these, monoalkyltrialkoxysilane and / or monoaryltrialkoxysilane are preferably used. For example, as alkyl group or aryl group, methyl, ethyl, propyl, butyl, vinyl, propenyl, cyclopentenyl, cyclohexenyl, phenyl, tolyl C 1-16 hydrocarbon groups such as xylyl, naphthyl and the like. The above alkyl group and aryl group may have a substituent containing N, O, P, halogen or the like. Examples of the alkoxy group include C1-C6 hydrocarbon groups such as methoxy, ethoxy, propoxy and butoxy.
触媒中のシリカ骨格を強固にするために、上記シリカ源とともにアモルファスシリカやアルコキシシラン、たとえばテトラメチルオルトシリケート、テトラエチルオルトシリケート、テトラプロピルオルトシリケートなどをシリカ源として用いることが好ましく、通常、上記シリカ源と混合して使用する。 In order to strengthen the silica skeleton in the catalyst, it is preferable to use amorphous silica or alkoxysilane, such as tetramethylorthosilicate, tetraethylorthosilicate, tetrapropylorthosilicate, etc. as the silica source together with the above silica source. Mix with source.
チタン源としては、チタンアルコキサイド、たとえばチタン酸テトラメチル、チタン酸テトラエチル、チタン酸テトラプロピル、チタン酸テトライソプロピル、チタン酸テトラブチル、チタン酸テトライソブチル、チタン酸テトラ−２−エチルヘキシル、チタン酸テトラオクタデシルやチタニウム（IV）オキシアセチルアセトナート、チタニウム（IV）ジイシプロポキシビスアセチルアセトナート等が、又はハロゲン化チタン、たとえば四塩化チタン、四臭化チタン、四沃化チタン等や硫酸チタニル等があげられる。 Titanium alkoxides such as tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, tetra-2-ethylhexyl titanate, tetra titanate Octadecyl, titanium (IV) oxyacetylacetonate, titanium (IV) di-propoxy bisacetylacetonate, etc., or titanium halides such as titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, etc. can give.
型剤としてはアルキルアンモニウム、ジアルキルアンモニウム、トリアルキルアンモニウム、ベンジルアンモニウムなどのカチオン界面活性剤、アルキル硫酸イオン、アルキルリン酸イオンなどのアニオン界面活性剤、ポリアルキレンオキサイドやそれらのブロックコポリマー、アルキルアミンなどのノニオン界面活性剤のいずれも適用可能である。なかでも下記の一般式（I）で表される第４級アンモニウムイオンが好適に用いられる。
［ＮＲ1Ｒ2Ｒ3Ｒ4］+ （I）
（式中、Ｒ1は炭素数２〜３６の直鎖状又は分岐状の炭化水素基を表し、Ｒ2〜Ｒ4は炭素数１〜６のアルキル基を表す。）
As the type agent, cationic surfactants such as alkylammonium, dialkylammonium, trialkylammonium and benzylammonium, anionic surfactants such as alkylsulfate ions and alkylphosphate ions, polyalkylene oxides and their block copolymers, alkylamines, etc. Any of the above nonionic surfactants can be applied. Among these, quaternary ammonium ions represented by the following general formula (I) are preferably used.
[NR 1 R 2 R 3 R 4 ] + (I)
(In the formula, R 1 represents a linear or branched hydrocarbon group having 2 to 36 carbon atoms, and R 2 to R 4 represent an alkyl group having 1 to 6 carbon atoms.)
Ｒ1は炭素数２〜３６の直鎖状又は分岐状の炭化水素基であり、好ましくは炭素数１０〜１８のものである。Ｒ2〜Ｒ4は炭素数１〜６のアルキル基であり、Ｒ2〜Ｒ4の全てがメチル基であることが好ましい。一般式（I）で表される第４級アンモニウムイオンの具体例としては、ヘキサデシルトリメチルアンモニウム、ドデシルトリメチルアンモニウム、ベンジルトリメチルアンモニウム、ジメチルジドデシルアンモニウム、ヘキサデシルピリジニウム等のカチオンをあげることができる。 R 1 is a linear or branched hydrocarbon group having 2 to 36 carbon atoms, preferably 10 to 18 carbon atoms. R 2 to R 4 are each an alkyl group having 1 to 6 carbon atoms, and all of R 2 to R 4 are preferably methyl groups. Specific examples of the quaternary ammonium ion represented by the general formula (I) include cations such as hexadecyltrimethylammonium, dodecyltrimethylammonium, benzyltrimethylammonium, dimethyldidodecylammonium, hexadecylpyridinium and the like.
また、これらの一般式（I）で表される第４級アンモニウムイオンは単独で用いることもできるし、数種を混合させて用いてもよい。 Moreover, the quaternary ammonium ion represented by these general formula (I) can also be used independently, and several types may be mixed and used for it.
型剤を溶解させる溶媒の例としては、水やアルコール、たとえばメタノール、エタノール、ｎ−プロパノール、２−プロパノール、ｎ−ブタノール、ｓｅｃ−ブタノール、ｔ−ブタノール、ビニルアルコール、アリルアルコール、シクロヘキサノール、ベンジルアルコール等やジオール、またそれらの混合物などをあげることができる。 Examples of solvents for dissolving the mold include water and alcohols such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, sec-butanol, t-butanol, vinyl alcohol, allyl alcohol, cyclohexanol, benzyl Examples thereof include alcohols, diols, and mixtures thereof.
本発明においては型剤を溶解させている溶媒中の水の割合が５０重量％以下であることが肝要であり、５〜４０重量％であることが好ましく、１０〜３０重量％であることが更に好ましい。それにより高活性と高選択性を実現できる触媒を得るという本発明の目的を達成しうる。 In the present invention, it is important that the ratio of water in the solvent in which the mold is dissolved is 50% by weight or less, preferably 5 to 40% by weight, and preferably 10 to 30% by weight. Further preferred. Thereby, the object of the present invention of obtaining a catalyst capable of realizing high activity and high selectivity can be achieved.
シリカ源に対するチタン源の使用量はモル比で１０-5〜１であり、好ましくは０．００００８〜０．４である。また、これらのシリカ源及びチタン源の合計量に対する第４級アンモニウムイオンの使用量はモル比で１０-2〜２とすることが好ましい。 The amount of titanium source used relative to the silica source is 10-5 to 1, preferably 0.00008 to 0.4, in molar ratio. Moreover, it is preferable that the usage-amount of the quaternary ammonium ion with respect to the total amount of these silica sources and titanium sources shall be 10 <-2 > -2 by molar ratio.
また、シリカ源とチタン源の反応を促進するために、混合溶液にアルカリ性又は酸性を付与させることが好ましい。アルカリ源としては第４級アンモニウムヒドロキシドが好ましく、例としてはテトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド等があげられるが、一般式（I）で表される第４級アンモニウムイオンの水酸化物を用いるのがより好ましい。また酸の例としては塩酸、硫酸、硝酸等の無機酸及び蟻酸、酢酸、プロピオン酸等の有機酸があげられる。 Moreover, in order to accelerate | stimulate reaction of a silica source and a titanium source, it is preferable to provide alkalinity or acidity to a mixed solution. The alkali source is preferably a quaternary ammonium hydroxide, and examples thereof include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, etc., and the quaternary represented by the general formula (I) It is more preferable to use ammonium ion hydroxide. Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and propionic acid.
混合・攪拌の温度は通常−３０〜１００℃である。混合・攪拌により固体が生成するが、更に固体を成長させるためにこれを熟成してもよい。熟成時間は通常１８０時間以下であり、熟成温度は通常０〜２００℃である。熟成時に加熱を要する場合は、溶媒の気化を避けるために耐圧容器に移して密閉して行うのが好ましい。 The mixing / stirring temperature is usually -30 to 100 ° C. A solid is produced by mixing and stirring, and this may be aged in order to further grow the solid. The aging time is usually 180 hours or less, and the aging temperature is usually 0 to 200 ° C. When heating is required at the time of aging, it is preferably carried out by transferring to a pressure vessel and sealing in order to avoid vaporization of the solvent.
本発明の第二工程は、固体から型剤を除去する工程である。 The second step of the present invention is a step of removing the mold from the solid.
型剤の除去は第一工程で得た触媒成分及び型剤を含有する固体を溶媒抽出操作又は焼成操作に付すことにより達成できるが、なかでも抽出除去が好ましい。 The removal of the mold can be achieved by subjecting the solid containing the catalyst component and the mold obtained in the first step to a solvent extraction operation or a calcination operation, and extraction removal is particularly preferable.
溶媒による型剤を抽出する技術は、Whitehurstらによって報告されている（米国特許5143879号公報参照。）。抽出に用いる溶媒は、型剤に用いた化合物を溶解し得るものであればよく、一般に炭素数１から約１２の常温で液状のオキサ及び／又はオキソ置換炭化水素を用いることができる。この種類の好適な溶媒としては、アルコール類、ケトン類、エーテル類（非環式及び環式のもの）及びエステル類を用いることができ、たとえば、メタノール、エタノール、エチレングリコール、プロピレングリコール、イソプロパノール、ｎ−ブタノール及びオクタノールのようなヒドロキシ置換炭化水素；アセトン、ジエチルケトン、メチルエチルケトン及びメチルイソブチルケトンのようなオキソ置換炭化水素；ジイソブチルエーテルやテトラヒドロフランのような炭化水素エーテル；及び酢酸メチル、酢酸エチル、酢酸ブチル及びプロピオン酸ブチルのような炭化水素エステル等があげられるが、型剤の溶解能という観点からアルコール類が好ましく、なかでもメタノールが更に好ましい。これらの抽出溶媒の触媒成分及び型剤を含有する固体に対する重量比は、通常１〜１０００であり、好ましくは５〜３００である。また、抽出効果を向上させるために、これらの溶媒に酸又はそれらの塩を添加してもよい。用いる酸の例としては、塩酸、硫酸、硝酸、臭酸等の無機酸や有機酸であるぎ酸、酢酸、プロピオン酸などがあげられる。また、それらの塩の例としては、アルカリ金属塩、アルカリ土類金属塩、アンモニウム塩等があげられる。添加する酸又はそれらの塩の溶媒中の濃度は１０ｍｏｌ／ｌ以下が好ましく、５ｍｏｌ／ｌ以下が更に好ましい。添加する酸又はそれらの塩の溶媒中の濃度が過大であると触媒成分中に存在するチタンが溶出し、触媒活性が低下する場合がある。 A technique for extracting a template with a solvent has been reported by Whitehurst et al. (See US Pat. No. 5,143,879). The solvent used for the extraction is not particularly limited as long as it can dissolve the compound used in the mold, and oxa- and / or oxo-substituted hydrocarbons that are liquid at room temperature having 1 to about 12 carbon atoms can be used. Suitable solvents of this type can include alcohols, ketones, ethers (acyclic and cyclic) and esters such as methanol, ethanol, ethylene glycol, propylene glycol, isopropanol, Hydroxy-substituted hydrocarbons such as n-butanol and octanol; oxo-substituted hydrocarbons such as acetone, diethyl ketone, methyl ethyl ketone and methyl isobutyl ketone; hydrocarbon ethers such as diisobutyl ether and tetrahydrofuran; and methyl acetate, ethyl acetate, acetic acid Examples thereof include hydrocarbon esters such as butyl and butyl propionate, and alcohols are preferable from the viewpoint of the solubility of the mold, and methanol is more preferable. The weight ratio of these extraction solvents to the solid containing the catalyst component and the mold is usually 1 to 1000, preferably 5 to 300. Moreover, in order to improve the extraction effect, an acid or a salt thereof may be added to these solvents. Examples of the acid used include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and odorous acid, and organic acids such as formic acid, acetic acid, and propionic acid. Examples of such salts include alkali metal salts, alkaline earth metal salts, ammonium salts and the like. The concentration of the acid to be added or a salt thereof in the solvent is preferably 10 mol / l or less, more preferably 5 mol / l or less. If the concentration of the acid to be added or the salt thereof in the solvent is excessive, titanium present in the catalyst component may be eluted and the catalytic activity may be lowered.
溶媒と触媒成分及び型剤を含有する固体を十分に混合した後、液相部をろ過又はデカンテーションなどの方法により分離する。この操作を必要回数繰り返す。また触媒成分及び型剤を含有する固体を反応管等に充填し、抽出溶媒を流通させる方法により型剤を抽出することも可能である。溶媒抽出の終了はたとえば液相部の分析により知ることができる。抽出温度は０〜２００℃が好ましく２０〜１００℃が更に好ましい。抽出溶媒の沸点が低い場合は、加圧して抽出を行ってもよい。 After thoroughly mixing the solvent, the solid containing the catalyst component and the mold, the liquid phase part is separated by a method such as filtration or decantation. This operation is repeated as many times as necessary. It is also possible to extract the mold by a method of filling a solid containing the catalyst component and the mold into a reaction tube and circulating an extraction solvent. The completion of the solvent extraction can be known, for example, by analyzing the liquid phase part. The extraction temperature is preferably 0 to 200 ° C, more preferably 20 to 100 ° C. When the boiling point of the extraction solvent is low, the extraction may be performed by applying pressure.
抽出処理後に得られた溶液中の型剤は回収して第一工程の型剤原料として再使用することもできる。また同様に抽出溶媒も通常の蒸留操作などにより精製して再使用することもできる。 The mold in the solution obtained after the extraction treatment can be recovered and reused as the mold raw material in the first step. Similarly, the extraction solvent can be purified and reused by a normal distillation operation or the like.
抽出操作後に固体に含まれる抽出溶媒は乾燥操作によって除去することもできるし、続けてシリル化を行う場合は、シリル化工程で用いるシリル化剤に対して実質上不活性な溶媒で置換除去することができる。 The extraction solvent contained in the solid after the extraction operation can be removed by a drying operation, and when subsequent silylation is performed, it is replaced with a solvent that is substantially inert to the silylating agent used in the silylation step. be able to.
乾燥除去の場合、乾燥装置としては温風もしくは減圧装置を装着したコニカル乾燥機や棚段乾燥機をあげることができる。 In the case of drying and removing, examples of the drying device include a conical dryer and a shelf dryer equipped with hot air or a decompression device.
置換除去の場合、固体に含まれる抽出溶媒を、続くシリル化工程で用いるシリル化剤に対して実質上不活性な溶媒で置換する。置換工程で用いられる置換溶媒はシリル化剤に対して実質上不活性で、かつ第二工程で用いた抽出溶媒を溶解させ得るという条件を満たすものであれば良い。 In the case of displacement removal, the extraction solvent contained in the solid is replaced with a solvent that is substantially inert to the silylating agent used in the subsequent silylation step. The substitution solvent used in the substitution step is not particularly limited as long as it is substantially inert to the silylating agent and satisfies the condition that the extraction solvent used in the second step can be dissolved.
置換操作に好適に用いられる溶媒は一般に炭素数１から約１２の常温で液状の炭化水素類、ハロゲン化炭化水素類、ケトン類、エーテル類、エステル類、N，N−二置換アミド類、ニトリル類、三級アミン類などであり、たとえばヘキサン、シクロヘキサン、クロロホルム、ベンゼン、トルエン、キシレン、アセトン、ジエチルケトン、メチルエチルケトン、メチルイソブチルケトン、ジエチルエーテル、ジイソブチルエーテル、テトラヒドロフラン、ジオキサン、酢酸メチル、酢酸エチル、ジメチルホルムアミド、アセトニトリル、ピリジン、トリエチルアミン、ジメチルスルフォキシドなどがあげられる。続くシリル化工程との関係から好ましい置換溶媒は炭化水素類で、なかでもトルエンが更に好ましい。これらの溶媒は単独で用いることもできるし、数種類を混合した溶液を用いることもできる。 Solvents preferably used for the substitution operation are generally hydrocarbons, halogenated hydrocarbons, ketones, ethers, esters, N, N-disubstituted amides, nitriles having a carbon number of 1 to about 12 at room temperature. Such as hexane, cyclohexane, chloroform, benzene, toluene, xylene, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether, diisobutyl ether, tetrahydrofuran, dioxane, methyl acetate, ethyl acetate, Examples include dimethylformamide, acetonitrile, pyridine, triethylamine, dimethyl sulfoxide and the like. In view of the subsequent silylation step, preferred substitution solvents are hydrocarbons, and among these, toluene is more preferred. These solvents can be used alone, or a mixed solution of several kinds can be used.
置換操作では置換溶媒と第二工程で得られた抽出溶媒を含有する固体を十分に混合した後、液相部をろ過又はデカンテーションなどの方法により分離する。この操作を必要回数繰り返す。また抽出溶媒を含有する固体を反応管等に充填し、置換溶媒を流通させる方法により置換することも可能である。触媒の生産性という観点から、本発明の第二工程からシリル化工程までを同一の反応器で行うことが好ましい。本置換操作の終了はたとえば液相部の分析により知ることができる。置換温度は０〜２００℃が好ましく２０〜１００℃が更に好ましい。本操作で用いる溶媒の沸点が低い場合は、加圧して置換を行ってもよい。 In the substitution operation, the substitution solvent and the solid containing the extraction solvent obtained in the second step are sufficiently mixed, and then the liquid phase part is separated by a method such as filtration or decantation. This operation is repeated as many times as necessary. Moreover, it is also possible to replace by a method in which a solid containing an extraction solvent is filled in a reaction tube or the like and a replacement solvent is passed. From the viewpoint of catalyst productivity, it is preferable to carry out the second step to the silylation step of the present invention in the same reactor. The completion of this replacement operation can be known by, for example, analyzing the liquid phase part. The substitution temperature is preferably 0 to 200 ° C, more preferably 20 to 100 ° C. When the boiling point of the solvent used in this operation is low, substitution may be performed by applying pressure.
また置換工程に用いた置換溶媒は蒸留や抽出などの通常の方法により抽出溶媒を除去し、再使用することができる。 The substitution solvent used in the substitution step can be reused after removing the extraction solvent by a usual method such as distillation or extraction.
本発明の第一工程および第二工程を経て得られた固体は高い疎水性を有し、高活性・高選択性触媒として作用するが、更に性能を改善するために上記固体をシリル化処理を付すことによりシリル化された触媒を得ることができる。 The solid obtained through the first step and the second step of the present invention has high hydrophobicity and acts as a highly active and highly selective catalyst. However, in order to further improve the performance, the solid is subjected to silylation treatment. By attaching, a silylated catalyst can be obtained.
シリル化は第二工程で得られた固体にガス状のシリル化剤を反応させる気相法で行ってもよいし、溶媒中でシリル化剤と固体とを反応させる液相法で行ってもよいが、本発明においては液相法がより好ましい。通常、シリル化を液相法で行う場合は炭化水素類が好適に用いられる。抽出溶媒を置換操作によって除去した場合、シリル化溶媒は置換溶媒と必ずしも同一である必要はないが、溶媒の再使用の観点から同一であることが好ましい。 Silylation may be performed by a gas phase method in which a gaseous silylating agent is reacted with the solid obtained in the second step, or by a liquid phase method in which a silylating agent and a solid are reacted in a solvent. In the present invention, the liquid phase method is more preferable. Usually, when silylation is performed by a liquid phase method, hydrocarbons are preferably used. When the extraction solvent is removed by a substitution operation, the silylation solvent is not necessarily the same as the substitution solvent, but is preferably the same from the viewpoint of reuse of the solvent.
シリル化剤の例には、有機シラン、有機シリルアミン、有機シリルアミドとその誘導体、及び有機シラザン及びその他のシリル化剤があげられる。 Examples of silylating agents include organic silanes, organic silylamines, organic silylamides and derivatives thereof, and organic silazanes and other silylating agents.
有機シランの例としては、クロロトリメチルシラン、ジクロロジメチルシラン、クロロブロモジメチルシラン、ニトロトリメチルシラン、クロロトリエチルシラン、ヨードジメチルブチルシラン、クロロジメチルフェニルシラン、クロロジメチルシラン、ジメチルn-プロピルクロロシラン、ジメチルイソプロピルクロロシラン、t-ブチルジメチルクロロシラン、トリプロピルクロロシラン、ジメチルオクチルクロロシラン、トリブチルクロロシラン、トリヘキシルクロロシラン、ジメチルエチルクロロシラン、ジメチルオクタデシルクロロシラン、n-ブチルジメチルクロロシラン、ブロモメチルジメチルクロロシラン、クロロメチルジメチルクロロシラン、３-クロロプロピルジメチルクロロシラン、ジメトキシメチルクロロシラン、メチルフェニルクロロシラン、トリエトキシクロロシラン、ジメチルフェニルクロロシラン、メチルフェニルビニルクロロシラン、ベンジルジメチルクロロシラン、ジフェニルクロロシラン、ジフェニルメチルクロロシラン、ジフェニルビニルクロロシラン、トリベンジルクロロシラン、３-シアノプロピルジメチルクロロシランがあげられる。 Examples of organic silanes include chlorotrimethylsilane, dichlorodimethylsilane, chlorobromodimethylsilane, nitrotrimethylsilane, chlorotriethylsilane, iododimethylbutylsilane, chlorodimethylphenylsilane, chlorodimethylsilane, dimethyl n-propylchlorosilane, dimethylisopropyl Chlorosilane, t-butyldimethylchlorosilane, tripropylchlorosilane, dimethyloctylchlorosilane, tributylchlorosilane, trihexylchlorosilane, dimethylethylchlorosilane, dimethyloctadecylchlorosilane, n-butyldimethylchlorosilane, bromomethyldimethylchlorosilane, chloromethyldimethylchlorosilane, 3-chloro Propyldimethylchlorosilane, dimethoxymethylchlorosilane, methylphenol Examples thereof include nylchlorosilane, triethoxychlorosilane, dimethylphenylchlorosilane, methylphenylvinylchlorosilane, benzyldimethylchlorosilane, diphenylchlorosilane, diphenylmethylchlorosilane, diphenylvinylchlorosilane, tribenzylchlorosilane, and 3-cyanopropyldimethylchlorosilane.
有機シリルアミンの例としては、N−トリメチルシリルイミダゾール、N−t−ブチルジメチルシリルイミダゾール、N-ジメチルエチルシリルイミダゾール、N−ジメチルn−プロピルシリルイミダゾール、N−ジメチルイソプロピルシリルイミダゾール、N−トリメチルシリルアミン、N−トリメチルシリルジメチルアミン、N−トリメチルシリルジエチルアミン、N−トリメチルシリルピロール、N−トリメチルシリルピロリジン、N−トリメチルシリルピペリジン、１−シアノエチル（ジエチルアミノ）ジメチルシラン、ペンタフルオロフェニルジメチルシリルアミンがあげられる。 Examples of organic silylamines include N-trimethylsilylimidazole, Nt-butyldimethylsilylimidazole, N-dimethylethylsilylimidazole, N-dimethyln-propylsilylimidazole, N-dimethylisopropylsilylimidazole, N-trimethylsilylamine, N -Trimethylsilyldimethylamine, N-trimethylsilyldiethylamine, N-trimethylsilylpyrrole, N-trimethylsilylpyrrolidine, N-trimethylsilylpiperidine, 1-cyanoethyl (diethylamino) dimethylsilane, pentafluorophenyldimethylsilylamine.
有機シリルアミド及び誘導体の例としては、N,O−ビストリメチルシリルアセトアミド、N,O−ビストリメチルシリルトリフルオロアセトアミド、N−トリメチルシリルアセトアミド、N−メチル−N−トリメチルシリルアセトアミド、N−メチル−N−トリメチルシリルトリフルオロアセトアミド、N−メチル−N−トリメチルシリルヘプタフルオロブチルアミド、N-(t-ブチルジメチルシリル)−N−トリフルオロアセトアミド,N,O−ビス（ジエチルハイドロシリル）トリフルオロアセトアミドがあげられる。 Examples of organic silylamides and derivatives include N, O-bistrimethylsilylacetamide, N, O-bistrimethylsilyltrifluoroacetamide, N-trimethylsilylacetamide, N-methyl-N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltrifluoro Examples include acetamide, N-methyl-N-trimethylsilylheptafluorobutyramide, N- (t-butyldimethylsilyl) -N-trifluoroacetamide, N, O-bis (diethylhydrosilyl) trifluoroacetamide.
有機シラザンの例としては、ヘキサメチルジシラザン、ヘプタメチルジシラザン、１,１,３,３−テトラメチルジシラザン,１,３−ビス（クロロメチル）テトラメチルジシラザン、１,３-ジビニル-１,１,３,３−テトラメチルジシラザン、１,３−ジフェニルテトラメチルジシラザンがあげられる。 Examples of organic silazanes include hexamethyldisilazane, heptamethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,3-bis (chloromethyl) tetramethyldisilazane, 1,3-divinyl- Examples include 1,1,3,3-tetramethyldisilazane and 1,3-diphenyltetramethyldisilazane.
その他のシリル化剤としては、N−メトキシ−N,O−ビストリメチルシリルトリフルオロアセトアミド、N−メトキシ−N,O−ビストリメチルシリルカーバメート、N,O−ビストリメチルシリルスルファメート、トリメチルシリルトリフルオロメタンスルホナート、N,N'−ビストリメチルシリル尿素があげられる。
好ましいシリル化剤はヘキサメチルジシラザンである。
Other silylating agents include N-methoxy-N, O-bistrimethylsilyl trifluoroacetamide, N-methoxy-N, O-bistrimethylsilyl carbamate, N, O-bistrimethylsilylsulfamate, trimethylsilyl trifluoromethanesulfonate, N, N′-bistrimethylsilylurea is exemplified.
A preferred silylating agent is hexamethyldisilazane.
本発明の触媒は、通常、触媒成分を含む固体を成型する工程により触媒成型体として用いられる。成型工程は、上述した型剤除去工程の前後、溶媒置換工程後及びシリル化工程後のいずれの段階で行ってもよいが、比表面積や細孔容量などの触媒物性の劣化を抑制するという観点から、型剤除去工程の前に行うことが好ましい。成型方法は圧縮成型、押し出し成型などのいずれの方法を用いてもよい。押し出し成型においては一般的に用いられる有機および無機バインダーを用いることができるが、バインダーの添加により触媒活性の低下が引き起こされる場合がある。本触媒成型体の製造にあたり、触媒強度及び触媒物性の観点から圧縮成型法が最も好ましい。 The catalyst of the present invention is usually used as a catalyst molded body by a step of molding a solid containing a catalyst component. The molding process may be carried out at any stage before or after the above-mentioned mold removing process, after the solvent replacement process, or after the silylation process, but the viewpoint of suppressing deterioration of catalyst physical properties such as specific surface area and pore volume. Therefore, it is preferably performed before the mold removing step. As the molding method, any method such as compression molding or extrusion molding may be used. In extrusion molding, commonly used organic and inorganic binders can be used, but the addition of the binder may cause a decrease in catalytic activity. In producing the catalyst molded body, the compression molding method is most preferable from the viewpoint of catalyst strength and catalyst physical properties.
圧縮成型法としてはロールプレス成型（ブリケッティング、コンパクティング）、油圧プレス成型、打錠成型などをあげることができる。圧縮の圧力は通常０．１〜１０トン／ｃｍ2であり、好ましくは０．２〜５トン／ｃｍ2であり、更に好しくは０．５〜２トン／ｃｍ2である。圧力が低すぎると成型体の強度が不十分となる場合があり、一方圧力が高すぎると細孔が破壊され触媒物性が不十分なものとなる場合がある。圧縮成型を行うにあたり、触媒成分を含む固体が適当量の水分を含んでいることが好ましく、これにより低い圧縮圧力でも充分な強度の成型体をつくることができる。圧縮成型に付す材の含水率は１〜７０重量％が好ましく、５〜４０重量％が更に好ましい。水分量は湿った固体を乾燥させる際の乾燥度で調整してもよいし、十分乾燥させた固体に水を加えて調整してもよい。また、所望の性能に支障をきたさない範囲で、一般に用いられるバインダー等を加えてもよい。 Examples of the compression molding method include roll press molding (briquetting and compacting), hydraulic press molding, tableting molding and the like. The compression pressure is usually 0.1 to 10 ton / cm 2 , preferably 0.2 to 5 ton / cm 2 , more preferably 0.5 to 2 ton / cm 2 . If the pressure is too low, the strength of the molded body may be insufficient. On the other hand, if the pressure is too high, the pores may be destroyed and the physical properties of the catalyst may be insufficient. In performing compression molding, it is preferable that the solid containing the catalyst component contains an appropriate amount of moisture, so that a molded body having sufficient strength can be produced even at a low compression pressure. The water content of the material subjected to compression molding is preferably 1 to 70% by weight, more preferably 5 to 40% by weight. The amount of moisture may be adjusted by the degree of drying when the damp solid is dried, or may be adjusted by adding water to the sufficiently dried solid. In addition, a generally used binder or the like may be added as long as desired performance is not hindered.
成型体の形状は錠剤、球、リングなどいずれの形状であってもよい。そのままの形状で反応などに用いてもよいし、適当な大きさに破砕して用いてもよい。 The shape of the molded body may be any shape such as a tablet, a sphere, or a ring. It may be used in the reaction as it is, or may be crushed to an appropriate size.
本発明の触媒は、高い表面積と高度に分散したチタン活性点および高い疎水性を有することから、選択的酸化反応、たとえばオレフィンのエポキシ化反応の他、有機化合物の各種酸化反応に用いることが可能である。また所望により、アルミナ等の第三成分の添加で触媒の酸点をより強化することも可能であり、アルキル化反応や接触改質反応等にも使用することが可能である。 Since the catalyst of the present invention has a high surface area, highly dispersed titanium active sites and high hydrophobicity, it can be used for various oxidation reactions of organic compounds in addition to selective oxidation reactions such as olefin epoxidation reactions. It is. If desired, the acid point of the catalyst can be further strengthened by adding a third component such as alumina, and can be used for an alkylation reaction, a catalytic reforming reaction, or the like.
本発明の触媒は特にオレフィン型化合物とハイドロパーオキサイドを反応させるオキシラン化合物の製造方法に最適に使用され得る。 In particular, the catalyst of the present invention can be optimally used in a method for producing an oxirane compound in which an olefin type compound and a hydroperoxide are reacted.
オレフィン型化合物は、非環式、単環式、二環式又は多環式化合物であってよく、モノオレフィン型、ジオレフィン型又はポリオレフィン型のものであってよい。オレフィン結合が２以上ある場合には、これは共役結合又は非共役結合であってよい。炭素原子２〜６０個のオレフィン型化合物が一般に好ましい。置換基を有していてもよいが、置換基は比較的安定な基であることが好ましい。このような炭化水素の例にはエチレン、プロピレン、ブテン−１、イソブチレン、ヘキセン−１、ヘキセン−２、ヘキセン−３、オクテン−１、デセン−１、スチレン、シクロヘキセン等があげられる。適当なジオレフィン型化合物の例にはブタジエン、イソプレンがあげられる。置換基が存在してもよく、その例にはハロゲン原子があげられ、更にまた、酸素、硫黄、窒素原子を、水素及び/又は炭素原子と共に含有する種々の置換基が存在してもよい。特に好ましいオレフィン型化合物はオレフィン型不飽和アルコール、及びハロゲンで置換されたオレフィン型不飽和炭化水素であり、その例にはアリルアルコール、クロチルアルコール、塩化アリルがあげられる。特に好適なものは炭素原子３〜４０個のアルケンであって、これはヒドロキシル基又はハロゲン原子で置換されていてもよい。 The olefinic compound may be an acyclic, monocyclic, bicyclic or polycyclic compound, and may be of monoolefin type, diolefin type or polyolefin type. If there are two or more olefinic bonds, this may be a conjugated bond or a non-conjugated bond. Olefin type compounds having 2 to 60 carbon atoms are generally preferred. Although it may have a substituent, the substituent is preferably a relatively stable group. Examples of such hydrocarbons include ethylene, propylene, butene-1, isobutylene, hexene-1, hexene-2, hexene-3, octene-1, decene-1, styrene, cyclohexene and the like. Examples of suitable diolefin type compounds are butadiene and isoprene. Substituents may be present, examples include halogen atoms, and various substituents containing oxygen, sulfur, and nitrogen atoms together with hydrogen and / or carbon atoms may also be present. Particularly preferred olefin type compounds are olefin type unsaturated alcohols and olefin type unsaturated hydrocarbons substituted with halogen. Examples thereof include allyl alcohol, crotyl alcohol and allyl chloride. Particularly preferred are alkenes having 3 to 40 carbon atoms, which may be substituted with hydroxyl groups or halogen atoms.
ハイドロパーオキサイドの例として、有機ハイドロパーオキサイドをあげることができる。有機ハイドロパーオキサイドは、一般式
Ｒ−Ｏ−Ｏ−Ｈ
（ここにＲは１価のヒドロカルビル基である。）
を有する化合物であって、これはオレフィン型化合物と反応して、オキシラン化合物及び化合物Ｒ−ＯＨを生成する。好ましくは、基Ｒは炭素原子を３〜２０個を有する基である。最も好ましくは、これは炭素原子３〜１０個のヒドロカルビル基、特に、第２又は第３アルキル基又はアラルキル基である。これらの基のうちで特に好ましい基は第３アルキル基、及び第２又は第３アラルキル基であって、その具体例には第３ブチル基、第３ペンチル基、シクロペンチル基、２−フェニルプロピル−２基があげられ、更にまた、テトラリン分子の脂肪族側鎖から水素原子を除去することによって生じる種々のテトラニリル基もあげられる。
An organic hydroperoxide can be mention | raise | lifted as an example of a hydroperoxide. Organic hydroperoxides have the general formula R—O—O—H
(Where R is a monovalent hydrocarbyl group.)
Which reacts with an olefinic compound to produce an oxirane compound and a compound R—OH. Preferably, the group R is a group having 3 to 20 carbon atoms. Most preferably this is a hydrocarbyl group of 3 to 10 carbon atoms, in particular a secondary or tertiary alkyl group or an aralkyl group. Among these groups, particularly preferred groups are a tertiary alkyl group and a second or third aralkyl group, and specific examples thereof include a tertiary butyl group, a tertiary pentyl group, a cyclopentyl group, 2-phenylpropyl- 2 groups, and various tetranyl groups generated by removing hydrogen atoms from the aliphatic side chain of the tetralin molecule.
有機ハイドロパーオキサイドとしてクメンハイドロパーオキサイドを使用した場合には、その結果得られるヒドロキシル化合物は２−フェニル-２-プロパノールである。これは脱水反応によってα−メチルスチレンに変換できる。α−メチルスチレンは工業的に有用な物質である。 When cumene hydroperoxide is used as the organic hydroperoxide, the resulting hydroxyl compound is 2-phenyl-2-propanol. This can be converted to α-methylstyrene by a dehydration reaction. α-Methylstyrene is an industrially useful substance.
有機ハイドロパーオキサイドとして第３ペンチルハイドロパーオキサイドを使用したときに得られる第３ペンチルアルコールの脱水反応によって生じる第３アミレンは、イソプレンの前駆体として有用な物質である。第３ペンチルアルコールはオクタン価向上剤であるメチル第３ペンチルエーテルの前駆体としても有用である。 The third amylene produced by the dehydration reaction of the third pentyl alcohol obtained when the third pentyl hydroperoxide is used as the organic hydroperoxide is a substance useful as a precursor of isoprene. Tertiary pentyl alcohol is also useful as a precursor of methyl tertiary pentyl ether which is an octane improver.
有機ハイドロパーオキサイドとしてt-ブチルハイドロパーオキサイドを使用したときに得られるt-ブチルアルコールはオクタン価向上剤であるメチル-t-ブチルエーテルの前駆体として有用な物質である。 T-Butyl alcohol obtained when t-butyl hydroperoxide is used as the organic hydroperoxide is a useful substance as a precursor of methyl-t-butyl ether which is an octane number improver.
有機ハイドロパーオキサイド以外のハイドロパーオキサイドの例として過酸化水素をあげることができる。 Hydrogen peroxide can be given as an example of hydroperoxide other than organic hydroperoxide.
過酸化水素は化学式ＨＯＯＨの化合物であって、通常水溶液の形で得ることができる。これはオレフィン型化合物と反応して、オキシラン化合物及び水を生成する。 Hydrogen peroxide is a compound of the chemical formula HOOH and can usually be obtained in the form of an aqueous solution. This reacts with the olefinic compound to produce an oxirane compound and water.
原料物質として使用される有機ハイドロパーオキサイド及び過酸化水素は、希薄又は濃厚な精製物又は非精製物であってよい。 The organic hydroperoxide and hydrogen peroxide used as raw materials may be a diluted or concentrated purified product or non-purified product.
エポキシ化反応は、溶媒及び／又は希釈剤を用いて液相中で実施できる。溶媒及び希釈剤は、反応時の温度及び圧力のもとで液体であり、かつ、反応体及び生成物に対して実質的に不活性なものでなければならない。溶媒は使用されるハイドロパーオキサイド溶液中に存在する物質からなるものであってよい。たとえばクメンハイドロパーオキサイドがクメンハイドロパーオキサイドとその原料であるクメンとからなる混合物である場合には、特に溶媒を添加することなく、これを溶媒の代用とすることも可能である。 The epoxidation reaction can be carried out in the liquid phase using a solvent and / or diluent. The solvent and diluent must be liquid under the temperature and pressure during the reaction and be substantially inert to the reactants and products. The solvent may consist of substances present in the hydroperoxide solution used. For example, when cumene hydroperoxide is a mixture of cumene hydroperoxide and cumene, which is a raw material thereof, it can be used as a substitute for a solvent without particularly adding a solvent.
エポキシ化反応温度は一般に０〜２００℃であるが、２５〜２００℃の温度が好ましい。圧力は、反応混合物を液体の状態に保つのに充分な圧力でよい。一般に圧力は１００〜１００００ｋＰａであることが有利である。 The epoxidation reaction temperature is generally 0 to 200 ° C, but a temperature of 25 to 200 ° C is preferable. The pressure may be sufficient to keep the reaction mixture in a liquid state. In general, the pressure is advantageously between 100 and 10000 kPa.
エポキシ化反応の終了後に、所望生成物を含有する液状混合物が触媒組成物から容易に分離できる。次いで液状混合物を適当な方法によって精製できる。精製は分別蒸留、選択抽出、濾過、洗浄等を含む。溶媒、触媒、未反応オレフィン型化合物、未反応ハイドロパーオキサイドは再循環して再び使用することもできる。 After completion of the epoxidation reaction, the liquid mixture containing the desired product can be easily separated from the catalyst composition. The liquid mixture can then be purified by a suitable method. Purification includes fractional distillation, selective extraction, filtration, washing and the like. The solvent, catalyst, unreacted olefin type compound and unreacted hydroperoxide can be recycled and reused.
本発明の触媒を用いた反応は、スラリー、固定床の形で行うことができ、大規模な工業的操作の場合には固定床を用いることが好ましい。本反応は、回分法、半連続法又は連続法によって実施できる。反応体を含有する液を固定床に通した場合には、反応帯域から出た液状混合物には、触媒が全く含まれていないか又は実質的に含まれていない。 The reaction using the catalyst of the present invention can be carried out in the form of a slurry or a fixed bed. In the case of a large-scale industrial operation, it is preferable to use a fixed bed. This reaction can be carried out by a batch method, a semi-continuous method or a continuous method. When the liquid containing the reactants is passed through a fixed bed, the liquid mixture exiting the reaction zone contains no or substantially no catalyst.
以下に実施例により本発明を説明する。
実施例１
触媒粉の調製
１６重量％ヘキサデシルトリメチルアンモニウムヒドロキシド、６４重量％メタノール、２０重量％水で構成された型剤溶液１２５．０ｇ（溶媒中の水は２０／（６４＋２０）＝２４重量％）を撹拌し、これに５０℃でチタン酸テトライソプロピル１．８５ｇと２−プロパノール１０．０ｇの混合溶液を滴下して加えた。３０分間撹拌した後、テトラメチルオルトシリケート３０．５ｇとメチルトリメトキシシラン６．８ｇとの混合溶液を滴下した。その後、５０℃で３時間攪拌を続けた。生じた沈殿をろ別した。
得られた沈殿を減圧下、７０℃で８時間乾燥した。
The following examples illustrate the invention.
Example 1
Preparation of catalyst powder 125.0 g of a mold solution composed of 16% by weight hexadecyltrimethylammonium hydroxide, 64% by weight methanol and 20% by weight water (water in the solvent is 20 / (64 + 20) = 24% by weight) The mixture was stirred and a mixed solution of 1.85 g of tetraisopropyl titanate and 10.0 g of 2-propanol was added dropwise thereto at 50 ° C. After stirring for 30 minutes, a mixed solution of 30.5 g of tetramethylorthosilicate and 6.8 g of methyltrimethoxysilane was added dropwise. Thereafter, stirring was continued at 50 ° C. for 3 hours. The resulting precipitate was filtered off.
The obtained precipitate was dried at 70 ° C. under reduced pressure for 8 hours.
成型体の作製
乾燥して得られた白色固体３０．０ｇに４．５ｇの水を霧吹きで加え良く混合したものを、錠剤成型器で圧縮成型した。得られた固体を破砕し、篩を用いて１．０〜２．０ｍｍの触媒成型体を得た。１．０ｍｍ以下の固体はリサイクルして、再度圧縮成型した。
Production of molded body A mixture of 30.0 g of a white solid obtained by drying and well mixed with 4.5 g of water by spraying was compression molded with a tablet molding machine. The obtained solid was crushed, and a 1.0 to 2.0 mm catalyst molded body was obtained using a sieve. Solids of 1.0 mm or less were recycled and compression molded again.
型剤の抽出除去
次に、上記のとおり得られた成型体１１．５ｇを内径１６ｍｍφのガラス製カラムに充填し、ＬＨＳＶ＝６ｈ-1で（１）室温下、１００ｍｌのメタノール、（２）４５℃加熱下、２００ｍｌのメタノールと濃塩酸（含量３６重量％）４ｇとの混合溶液、（３）４５℃加熱下、２００ｍｌのメタノールをアップフローで順次カラムに通液した。通液終了後、カラム内のメタノールをカラム下部より抜き出し、８０℃加熱下、１０ｍｍＨｇで１．５時間、触媒成型体を減圧乾燥した。
Extracting and removing the mold agents Next, the molded body 11.5g obtained as described above was packed into a glass column having an inner diameter diameter of 16 mm, LHSV = at 6h -1 (1) at room temperature, 100 ml of methanol, (2) 45 Under heating at 0 ° C., a mixed solution of 200 ml of methanol and 4 g of concentrated hydrochloric acid (content 36% by weight), (3) Under heating at 45 ° C., 200 ml of methanol was sequentially passed through the column in an up flow. After completion of the flow, methanol in the column was extracted from the lower part of the column, and the catalyst molded body was dried under reduced pressure at 10 mmHg for 1.5 hours under heating at 80 ° C.
プロピレンオキサイド（ＰＯ）の合成
上記のとおり得られた触媒成型体を２５％クメンハイドロパーオキサイド（ＣＨＰＯ）とプロピレン（Ｃ3’）を用いてバッチ反応装置（オートクレーブ）で評価した。触媒１．０ｇ、ＣＨＰＯ３０．０ｇ、Ｃ3’１６．６ｇをオートクレーブに仕込み、自生圧力下、反応温度８５℃、反応時間１．５時間（昇温込み）で反応させた。反応成績を表１に示す。
Synthesis of Propylene Oxide (PO) The molded catalyst obtained as described above was evaluated in a batch reactor (autoclave) using 25% cumene hydroperoxide (CHPO) and propylene (C 3 '). 1.0 g of catalyst, 30.0 g of CHPO, and 16.6 g of C 3 ′ were charged into an autoclave and reacted at a reaction temperature of 85 ° C. and a reaction time of 1.5 hours (temperature increase) under autogenous pressure. The reaction results are shown in Table 1.
実施例２
シリル化
実施例１で得られた触媒成型体３．０ｇを冷却管の装着されたガラス製フラスコに入れ、ヘキサメチルジシラザン２．０ｇとトルエン３０．０ｇを加え１１０℃加熱下、１．５時間シリル化を行った。液分離後、１１０℃加熱下、１０ｍｍＨｇで１．５時間、触媒成型体を減圧乾燥した。
得られたシリル化触媒を実施例１と同様の方法でバッチ反応装置で評価を行った。反応成績を表１に示す。
Example 2
3.0 g of the molded catalyst obtained in silylation Example 1 was placed in a glass flask equipped with a cooling tube, 2.0 g of hexamethyldisilazane and 30.0 g of toluene were added, and heated at 110 ° C. for 1.5. Time silylation was performed. After the liquid separation, the molded catalyst was dried under reduced pressure at 10 mmHg for 1.5 hours under heating at 110 ° C.
The obtained silylation catalyst was evaluated by a batch reactor in the same manner as in Example 1. The reaction results are shown in Table 1.
比較例１
１６重量％ヘキサデシルトリメチルアンモニウムヒドロキシド、１１重量％メタノール、７３重量％水で構成された型剤溶液１２５．０ｇ（溶媒中の水は７３／（１１＋７３）＝８７重量％）を用いた以外は、実施例１と同様に触媒成型体を調製しバッチ反応装置で評価した。反応成績を表１に示す。
Comparative Example 1
Except for using 125.0 g of a mold solution composed of 16% by weight hexadecyltrimethylammonium hydroxide, 11% by weight methanol, and 73% by weight water (the water in the solvent is 73 / (11 + 73) = 87% by weight). A catalyst molded body was prepared in the same manner as in Example 1 and evaluated with a batch reactor. The reaction results are shown in Table 1.
比較例２
比較例１で得られた触媒成型体を実施例２と同様にシリル化しバッチ反応装置で評価した。反応成績を表１に示す。
Comparative Example 2
The molded catalyst obtained in Comparative Example 1 was silylated in the same manner as in Example 2 and evaluated with a batch reactor. The reaction results are shown in Table 1.
＊１：ＰＯ/Ｃ3’選択率＝生成ＰＯモル/反応Ｃ3’モル*１００
* 1: PO / C 3 'selectivity = product PO mole / reaction C 3 ' mol * 100
Claims (7)
（１）：平均細孔径が１０Å以上であること
（２）：全細孔容量の９０％以上が５〜２００Åの細孔径を有すること
（３）：比細孔容量が０．２ｃｍ3／ｇ以上であること
（４）：原料として用いるシリカ源の一部又は全部が、炭化水素基が珪素原子に直接結合した珪素化合物であること
第一工程：シリカ源、チタン源及び型剤（テンプレート）を溶媒中で混合・攪拌することにより触媒成分及び型剤を含有する固体を得る工程であって、該溶媒中の水の割合が５０重量％以下である工程
第二工程：第一工程で得た固体から型剤を除去する工程 A method for producing a titanium-containing silicon oxide catalyst that satisfies all of the following conditions (1) to (4), comprising the following first step to second step.
(1): The average pore diameter is 10 mm or more (2): 90% or more of the total pore volume has a pore diameter of 5 to 200 mm (3): The specific pore volume is 0.2 cm 3 / g (4): Part or all of the silica source used as a raw material is a silicon compound in which a hydrocarbon group is directly bonded to a silicon atom. First step: Silica source, titanium source and mold (template) Is a step of obtaining a solid containing a catalyst component and a mold agent by mixing and stirring in a solvent, wherein the proportion of water in the solvent is 50% by weight or less. Second step: obtained in the first step Removing mold from solid
［ＮＲ1Ｒ2Ｒ3Ｒ4］+ （I）
（式中、Ｒ1は炭素数２〜３６の直鎖状又は分岐状の炭化水素基を表し、Ｒ2〜Ｒ4は炭素数１〜６のアルキル基を表す。） The production method according to claim 1, wherein the mold used in the first step is a quaternary ammonium ion represented by the following general formula (I).
[NR 1 R 2 R 3 R 4 ] + (I)
(In the formula, R 1 represents a linear or branched hydrocarbon group having 2 to 36 carbon atoms, and R 2 to R 4 represent an alkyl group having 1 to 6 carbon atoms.)
The manufacturing method of the oxirane compound which makes an olefin type compound and a hydroperoxide react in presence of the catalyst of Claim 6.
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| JP2004352357A JP4834982B2 (en) | 2004-12-06 | 2004-12-06 | Method for producing titanium-containing silicon oxide catalyst and catalyst |
| KR1020077014960A KR101254352B1 (en) | 2004-12-06 | 2005-11-30 | Process for producing titanium-containing silicon oxide catalyst, the catalyst, and process for producing olefin oxide compound with the catalyst |
| CN2012100482679A CN102600820A (en) | 2004-12-06 | 2005-11-30 | Process for producing titanium-containing silicon oxide catalyst, the catalyst, and process for producing olefin compound with the catalyst |
| CN2005800477950A CN101115561B (en) | 2004-12-06 | 2005-11-30 | Method for manufacturing titanium-containing silicon oxide catalyst, catalyst and method for manufacturing alkylene oxide using the catalyst |
| US11/720,649 US7875570B2 (en) | 2004-12-06 | 2005-11-30 | Process for producing titanium-containing silicon oxide catalyst, the catalyst, and process for producing olefin compound with the catalyst |
| PCT/JP2005/022417 WO2006062111A1 (en) | 2004-12-06 | 2005-11-30 | Process for producing titanium-containing silicon oxide catalyst, the catalyst, and process for producing olefin oxide compound with the catalyst |
| EP05814429A EP1839750A4 (en) | 2004-12-06 | 2005-11-30 | Process for producing titanium-containing silicon oxide catalyst, the catalyst, and process for producing olefin oxide compound with the catalyst |
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Cited By (5)
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| JP2018511462A (en) * | 2015-02-17 | 2018-04-26 | ライオンデル ケミカル テクノロジー、エル．ピー． | Epoxidation catalyst based on metal alkoxide pretreated support |
| WO2018186491A1 (en) * | 2017-04-07 | 2018-10-11 | 住友化学株式会社 | Method for producing titanium-containing silicon oxide, method for producing epoxide, and titanium-containing silicon oxide |
| WO2019176951A1 (en) | 2018-03-15 | 2019-09-19 | 住友化学株式会社 | Production method for titanium-containing silicon oxide molded article, and titanium-containing silicon oxide molded article |
| WO2020241052A1 (en) * | 2019-05-29 | 2020-12-03 | 住友化学株式会社 | Method for producing titanium-containing silicon oxide, method for producing epoxide, and titanium-containing silicon oxide |
| RU2805109C2 (en) * | 2019-05-29 | 2023-10-11 | Сумитомо Кемикал Компани, Лимитед | Method for producing titanium-containing silicon oxide, method for producing epoxide and titanium-containing silicon oxide |
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| TWI698398B (en) * | 2019-03-22 | 2020-07-11 | 東聯化學股份有限公司 | Method and application of synthesizing titanium-containing silicon oxide material using biopolymer |
| CN111905707B (en) * | 2020-08-04 | 2023-05-12 | 长江大学 | Amorphous mesoporous TiO 2 -SiO 2 Catalyst and preparation method thereof |
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| JP2018511462A (en) * | 2015-02-17 | 2018-04-26 | ライオンデル ケミカル テクノロジー、エル．ピー． | Epoxidation catalyst based on metal alkoxide pretreated support |
| WO2018186491A1 (en) * | 2017-04-07 | 2018-10-11 | 住友化学株式会社 | Method for producing titanium-containing silicon oxide, method for producing epoxide, and titanium-containing silicon oxide |
| CN110475748A (en) * | 2017-04-07 | 2019-11-19 | 住友化学株式会社 | The Si oxide of the manufacturing method of the Si oxide of titaniferous, the manufacturing method of epoxides and titaniferous |
| KR20190138653A (en) * | 2017-04-07 | 2019-12-13 | 스미또모 가가꾸 가부시끼가이샤 | Method for producing titanium-containing silicon oxide, method for producing epoxide, and titanium-containing silicon oxide |
| JPWO2018186491A1 (en) * | 2017-04-07 | 2020-02-27 | 住友化学株式会社 | Method for producing titanium-containing silicon oxide, method for producing epoxide, and titanium-containing silicon oxide |
| CN110475748B (en) * | 2017-04-07 | 2022-12-30 | 住友化学株式会社 | Method for producing titanium-containing silicon oxide, method for producing epoxide, and titanium-containing silicon oxide |
| KR102493560B1 (en) | 2017-04-07 | 2023-01-30 | 스미또모 가가꾸 가부시끼가이샤 | Method for producing titanium-containing silicon oxide, method for producing epoxide, and titanium-containing silicon oxide |
| WO2019176951A1 (en) | 2018-03-15 | 2019-09-19 | 住友化学株式会社 | Production method for titanium-containing silicon oxide molded article, and titanium-containing silicon oxide molded article |
| KR20200131306A (en) | 2018-03-15 | 2020-11-23 | 스미또모 가가꾸 가부시키가이샤 | Method for producing a titanium-containing silicon oxide molded article, and a titanium-containing silicon oxide molded article |
| WO2020241052A1 (en) * | 2019-05-29 | 2020-12-03 | 住友化学株式会社 | Method for producing titanium-containing silicon oxide, method for producing epoxide, and titanium-containing silicon oxide |
| RU2805109C2 (en) * | 2019-05-29 | 2023-10-11 | Сумитомо Кемикал Компани, Лимитед | Method for producing titanium-containing silicon oxide, method for producing epoxide and titanium-containing silicon oxide |
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| CN101115561A (en) | 2008-01-30 |
| CN101115561B (en) | 2012-05-30 |
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