CN108262030A - The preparation method and application of titanium-containing silicon oxide material with high thermal stability - Google Patents
The preparation method and application of titanium-containing silicon oxide material with high thermal stability Download PDFInfo
- Publication number
- CN108262030A CN108262030A CN201710004451.6A CN201710004451A CN108262030A CN 108262030 A CN108262030 A CN 108262030A CN 201710004451 A CN201710004451 A CN 201710004451A CN 108262030 A CN108262030 A CN 108262030A
- Authority
- CN
- China
- Prior art keywords
- titanium
- silicon oxide
- oxide material
- containing silicon
- preparation
- Prior art date
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000010936 titanium Substances 0.000 title claims abstract description 117
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 117
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000000463 material Substances 0.000 title claims abstract description 107
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 238000001354 calcination Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000002978 peroxides Chemical class 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 150000002118 epoxides Chemical class 0.000 claims abstract 6
- -1 titanate ester Chemical class 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 239000002585 base Substances 0.000 claims description 15
- 238000002444 silanisation Methods 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 13
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 150000001451 organic peroxides Chemical class 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229910052723 transition metal Inorganic materials 0.000 claims description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 150000003624 transition metals Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 8
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical compound CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 claims description 8
- 229960004830 cetylpyridinium Drugs 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000002210 silicon-based material Substances 0.000 claims description 5
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- GQNOPVSQPBUJKQ-UHFFFAOYSA-N 1-hydroperoxyethylbenzene Chemical compound OOC(C)C1=CC=CC=C1 GQNOPVSQPBUJKQ-UHFFFAOYSA-N 0.000 claims description 4
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 4
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- XLJOZOQVNCBJMT-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 XLJOZOQVNCBJMT-UHFFFAOYSA-M 0.000 claims description 4
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 4
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 4
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- CBGJVTWSEUIWJY-UHFFFAOYSA-N hydrogen peroxide 1-methylcyclohexene Chemical compound OO.CC1=CCCCC1 CBGJVTWSEUIWJY-UHFFFAOYSA-N 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- SFBHPFQSSDCYSL-UHFFFAOYSA-N n,n-dimethyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)C SFBHPFQSSDCYSL-UHFFFAOYSA-N 0.000 claims description 4
- 150000007530 organic bases Chemical group 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 239000002563 ionic surfactant Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 3
- UFOUZYGUZNQTBR-UHFFFAOYSA-M tributyl(hexadecyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](CCCC)(CCCC)CCCC UFOUZYGUZNQTBR-UHFFFAOYSA-M 0.000 claims description 3
- BJAARRARQJZURR-UHFFFAOYSA-N trimethylazanium;hydroxide Chemical compound O.CN(C)C BJAARRARQJZURR-UHFFFAOYSA-N 0.000 claims description 3
- BVOSSZSHBZQJOI-UHFFFAOYSA-N 1-Hexen-3-ol Chemical compound CCCC(O)C=C BVOSSZSHBZQJOI-UHFFFAOYSA-N 0.000 claims description 2
- YWBMNCRJFZGXJY-UHFFFAOYSA-N 1-hydroperoxy-1,2,3,4-tetrahydronaphthalene Chemical compound C1=CC=C2C(OO)CCCC2=C1 YWBMNCRJFZGXJY-UHFFFAOYSA-N 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 2
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical group [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 2
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical class CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 2
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 2
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 235000019504 cigarettes Nutrition 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- QQJDHWMADUVRDL-UHFFFAOYSA-N didodecyl(dimethyl)azanium Chemical compound CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC QQJDHWMADUVRDL-UHFFFAOYSA-N 0.000 claims description 2
- KZOIWQKIVZDOGH-UHFFFAOYSA-M didodecyl(dimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC KZOIWQKIVZDOGH-UHFFFAOYSA-M 0.000 claims description 2
- 229940075933 dithionate Drugs 0.000 claims description 2
- QCCKPZOPTXCJPL-UHFFFAOYSA-N dodecyl(dimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCC[NH+](C)C QCCKPZOPTXCJPL-UHFFFAOYSA-N 0.000 claims description 2
- KHFDEVIBCVSUAD-UHFFFAOYSA-N ethaneperoxoic acid Chemical compound CC(=O)OO.CC(=O)OO KHFDEVIBCVSUAD-UHFFFAOYSA-N 0.000 claims description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N hex-2-ene Chemical class CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 claims description 2
- QSGDGGWTDYSGCY-UHFFFAOYSA-N hexadecaneperoxoic acid Chemical compound CCCCCCCCCCCCCCCC(=O)OO QSGDGGWTDYSGCY-UHFFFAOYSA-N 0.000 claims description 2
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 2
- TWNQSCQMNSSPFZ-UHFFFAOYSA-N hydrogen peroxide;1,2,3,4-tetrahydronaphthalene Chemical compound OO.C1=CC=C2CCCCC2=C1 TWNQSCQMNSSPFZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 claims description 2
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 2
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 claims description 2
- IHFXMTOFDQKABX-UHFFFAOYSA-N n-methylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCNC IHFXMTOFDQKABX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- WYGPDWILEZEDGS-UHFFFAOYSA-N peroxyformic acid Chemical compound OOC=O.OOC=O WYGPDWILEZEDGS-UHFFFAOYSA-N 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- WVNCFODWDVYKCA-UHFFFAOYSA-N tetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN.CCCCCCCCCCCCCCN WVNCFODWDVYKCA-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- MTAYDNKNMILFOK-UHFFFAOYSA-K titanium(3+);tribromide Chemical compound Br[Ti](Br)Br MTAYDNKNMILFOK-UHFFFAOYSA-K 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- FLXZVVQJJIGXRS-UHFFFAOYSA-M trimethyl(octadecyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C FLXZVVQJJIGXRS-UHFFFAOYSA-M 0.000 claims description 2
- UIZVMOZAXAMASY-UHFFFAOYSA-N vinyl butanol Natural products OCCCCC=C UIZVMOZAXAMASY-UHFFFAOYSA-N 0.000 claims description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims 2
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 claims 1
- VMMLSBKCZPHAEO-UHFFFAOYSA-N N.C(CCCCCCCCCCCCCCCCC)[N+](C)(C)C Chemical compound N.C(CCCCCCCCCCCCCCCCC)[N+](C)(C)C VMMLSBKCZPHAEO-UHFFFAOYSA-N 0.000 claims 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- MRIZMKJLUDDMHF-UHFFFAOYSA-N cumene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1 MRIZMKJLUDDMHF-UHFFFAOYSA-N 0.000 claims 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- UNSNMTDKCNDZBL-UHFFFAOYSA-N dodecyl(trimethyl)azanium Chemical compound C(CCCCCCCCCCC)[N+](C)(C)C.C(CCCCCCCCCCC)[N+](C)(C)C UNSNMTDKCNDZBL-UHFFFAOYSA-N 0.000 claims 1
- 150000002432 hydroperoxides Chemical class 0.000 claims 1
- 239000000347 magnesium hydroxide Substances 0.000 claims 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical class [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims 1
- HUYLAMJIPCOVOM-UHFFFAOYSA-K triiodotitanium Chemical compound [Ti+3].[I-].[I-].[I-] HUYLAMJIPCOVOM-UHFFFAOYSA-K 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 238000006735 epoxidation reaction Methods 0.000 abstract description 15
- 150000001336 alkenes Chemical class 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- RWGFKTVRMDUZSP-UHFFFAOYSA-N isopropyl-benzene Natural products CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 12
- 150000002924 oxiranes Chemical class 0.000 description 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 8
- 150000003608 titanium Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009415 formwork Methods 0.000 description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 125000005131 dialkylammonium group Chemical group 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 238000006884 silylation reaction Methods 0.000 description 2
- 125000005208 trialkylammonium group Chemical group 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- BDCFWIDZNLCTMF-UHFFFAOYSA-N 2-phenylpropan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1 BDCFWIDZNLCTMF-UHFFFAOYSA-N 0.000 description 1
- LULSEYFKPZZWTR-UHFFFAOYSA-N 4-[dodecyl(methyl)amino]butane-1-sulfonic acid Chemical compound C[NH+](CCCCS(=O)(=O)[O-])CCCCCCCCCCCC LULSEYFKPZZWTR-UHFFFAOYSA-N 0.000 description 1
- JYQFCNHJHVEAFO-UHFFFAOYSA-N CCCCCCCCCCCC[N+](C)(C)C.CN(C)C Chemical compound CCCCCCCCCCCC[N+](C)(C)C.CN(C)C JYQFCNHJHVEAFO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- VAUCILWNLYXVIS-UHFFFAOYSA-N [dimethyl-(trimethylsilylamino)silyl]methane Chemical compound C[Si](C)(C)N[Si](C)(C)C.C[Si](C)(C)N[Si](C)(C)C VAUCILWNLYXVIS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002521 alkyl halide group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000003442 catalytic alkylation reaction Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- QDYLMAYUEZBUFO-UHFFFAOYSA-N cetalkonium chloride Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 QDYLMAYUEZBUFO-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- BHATUINFZWUDIX-UHFFFAOYSA-O dimethyl-(3-sulfopropyl)-tetradecylazanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)CCCS(O)(=O)=O BHATUINFZWUDIX-UHFFFAOYSA-O 0.000 description 1
- JVQOASIPRRGMOS-UHFFFAOYSA-M dodecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCC[N+](C)(C)C JVQOASIPRRGMOS-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Chemical group C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- PFLPYJQIUSNZEC-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)C.CCCCCCCCCCCCCCCCCC[N+](C)(C)C PFLPYJQIUSNZEC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epoxy Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation method and applications of the titanium-containing silicon oxide material with high thermal stability, being will be by titanium source, silicon source, alkali source, template molecule and the prepared aqueous solution of peroxide, separation of solid and liquid and drying are carried out after agitated, then, the titanium-containing silicon oxide material with high-specific surface area can be obtained by simple calcination procedure；Since the titanium-containing silicon oxide material prepared by the present invention has higher thermal stability, after calcining still there is outstanding catalytic activity, can be used to catalyzed alkene class compound and carry out epoxidation reaction, contribute to the production of epoxides.
Description
Technical field
The present invention relates to a kind of preparation method and application of the titanium-containing silicon oxide material with high thermal stability, more particularly to
It is a kind of using Template synthesis have high thermal stability titanium-containing silicon oxide material, and using calcining manners remove template molecule and
Make the material that there is the preparation method of high-specific surface area；And using this titanium-containing silicon oxide material as catalyst, to make olefines
Compound (olefin) reacts the application of production epoxides through direct oxidation.
Background technology
Titanium-containing silicon oxide material often have high surface area pore space structure, can as excellent adsorbent, catalyst or
Catalyst carrier.Existing document in 1992, which is delivered, to be prepared the research of earth silicon material using template and (refers to periodical Nature
Volume 359 (1992)：Page 710), the earth silicon material tool which is formed after organic formwork is removed by calcining manners
There is high specific surface area, it may have catalytic activity.And extraction mode can also be used other than using calcining manners in organic formwork
It removes it and (please refers to periodical J.Catal. volumes 168 (1997)：Page 194；And United States Patent (USP) case US 5143879).
Titanium-containing silicon oxide material is prepared using template, is to import titanium in the earth silicon material with high surface area,
The catalytic activity of the material can be made to have more diversity.But since titanium is temperature sensitive, titaniferous oxidation is prepared with template
While silicon materials and process calcining manners removal organic formwork, the catalytic activity of the material can also declined and (please refers to periodical
Nature volumes 368 (1994)：Page 321；J.Catal. volume 235 (2004)：Page 423；J.Catal. volume 254 (2008)：
Page 64；And J.Catal. volumes 236 (2009)：Page 75).In order to avoid titanium is substantially to the sensibility of heat, prepared with template
The mode of extraction must be utilized to remove organic formwork during titanium-containing silicon oxide material, can just make this material that there is excellent catalytic activity
(please referring to United States Patent (USP) case US 7018950, US 6887823, US 6512128).
However, compared to extraction mode, organic formwork is removed in the presence of having many advantages using calcining manners, including organic matter
Residual quantity is less, material mechanical strength in itself and hydrothermal stability is higher and required equipment and operating method are simpler etc..
To solve the above-mentioned problems, applicant of the present invention, which is particularly developed a kind of prepared using template, has high heat stability
The method of the titanium-containing silicon oxide material of property and application, organic formwork is removed using the mode of calcining, and allows titanium-containing silicon oxide material
Excellent catalytic activity is showed, epoxidation reaction is carried out for catalyzed alkene class compound, to help the life of epoxides
Production.
Invention content
It is a primary object of the present invention to provide a kind of preparation method of the titanium-containing silicon oxide material with high thermal stability
And application, the preparation method are prepared water-soluble using titanium source, silicon source, alkali source, template molecule, solvent and peroxide
Liquid is after being mutually mixed reaction, using filter, dry and calcining, you can obtain the titanium-containing silicon oxide material with high thermal stability
Material.This titanium-containing silicon oxide material has high-specific surface area and high catalytic activity, can further be used as catalyst catalyzed alkene class chemical combination
Object carries out epoxidation reaction, to produce epoxides.
In order to achieve the above object, the present invention provides a kind of preparation method of the titanium-containing silicon oxide material with high thermal stability,
It comprises the steps of：
(1) titanium source, silicon source, alkali source, template molecule, solvent and peroxide are hybridly prepared into aqueous solution；
(2) after making the reactant aqueous solution, separation of solid and liquid and drying are carried out；
(3) calcination processing is carried out to the solid of gained after separation of solid and liquid and drying, obtains the titanium-containing silicon oxide material, this contains
Silicon oxide material has chemical formula (I) under anhydrous conditions：
xTiO2(1-x)SiO2 (Ⅰ)
Wherein, x 0.00001-0.5.
Titanium source used in the present invention, including, but be not limited to：Titanate esters, inorganic ti sources or combination.Specifically,
Titanate esters can be tetramethoxy titanate ester, tetraethyl titanate, n- metatitanic acid orthocarbonate, tetraisopropyl titanate, n- butyl titanate, titanium
Sour four secondary butyl esters, iso- butyl titanate, four tert-butyl ester of metatitanic acid, four (2-Ethylhexyl Alcohol) titanate esters, four (octadecyl) positive metatitanic acids
Salt or combination；Inorganic ti sources can be halogenated titanium, include titanium trichloride, titanium tetrachloride, titanium tribromide, titanium tetrabromide, triiodo
Change titanium, titanium tetra iodide, titanium sulfate, titanium dioxide or combination.More than titanium source all can be used alone or mix a variety of titanium sources
It uses.
Silicon source used in the present invention, including, but be not limited to：Silica, the alkoxy of amorphous phase (amorphous)
Silane (alkoxysilane), silicate or combination.Specifically, the general formula of the silica of amorphous phase is SiO2, including,
But it is not limited to：Silicon-dioxide powderies or the bulks such as smoked silicon, white cigarette, silica dioxide gel, silicon dioxide gel；Alkoxy silane
Can be the silane containing four alkoxies, including tetramethoxy-silicane (tetramethylorthosilicate), tetraethoxy
Silane (tetraethylorthosilicate) and tetrapropoxysilane (tetrapropylorthosilicate) and similar
Substance.It illustrates further, the alkoxy silane containing different organic functional bases can also be used as silicon source, such as monoalkyl three
Alkoxy silane (alkyltrialkoxysilanes), dialkyl dialkoxy silicane (dialkyldialkoxysilanes),
Trialkylmonoalkoxysilanes (trialkylmonoalkoxysilanes) and the like；Silicate can be waterglass,
Silicic acid sylvite, britesorb, calsil and the like.More than silicon source all can be used alone or mix a variety of silicon sources
It uses.
Alkali source used in the present invention, including, but be not limited to：Organic base, inorganic base, relative ion (counter
It ion) can be simultaneously as the organic molecule of template or any substance that pH value can be made to increase for hydroxy anion；It is specific and
Speech, organic base can be the substance containing nitrogen-atoms, such as ammonium hydroxide, pyridine, imidazoles, benzimidazole, histidine and similar
Substance；Inorganic base can be the hydroxide containing metal ion, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, hydroxide
Magnesium, calcium hydroxide, strontium hydroxide, barium hydroxide and the like；Relative ion can be used as mould simultaneously for hydroxy anion
The organic molecule of plate can be trimethyl ammonium hydroxide (Dodecyl trimethyl ammonium
Hydroxide), myristyl benzyl dimethyl ammonium hydroxide (Tetradecyl dimethyl benzyl ammonium
Hydroxide), cetyltrimethylammonium hydroxide (Cetyltrimethylammonium hydroxide), cetyl
Tributyl ammonium hydroxide (hexadecyl tributyl ammonium hydroxide), benzyltrimethylammonium hydroxide
(Benzyltrimethylammonium hydroxide), double dodecyl dimethyl ammonium hydroxide
(Dimethyldidodecylammonium hydroxide), cetyl pyridinium (Hexadecylpyridinium), ten
Eight alkyltrimethylammonium hydroxides (Trimethyloctadecylammonium hydroxide) and the like.More than alkali
Source can be used alone or be used in mixed way a variety of alkali sources.
Template molecule used in the present invention, including, but be not limited to：Cationic surface active agent, anionic table
Face activating agent, nonionic surface active agent and amphoteric ionic surfactant；Specifically, cationic surfactant
Agent can be alkylammonium (alkyl ammoniums), dialkyl ammonium (dialkyl ammoniums), trialkyl ammonium (trialkyl
Ammoniums), hexadecyldimethyl benzyl ammonium (benzyl ammoniums), alkyl pyridine (alkylpiridinium) and the like；
Anionic surfactant can be alkylsulfonate ion (alkylsulfate ion), alkyl phosphoric acid ion
(alkylphosphate ion) and the like；Nonionic surface active agent can be polyalkylene oxide
(polyalkylene oxide), block copolymer (block copolymer), alkylamine (alkylamines) and similar
Substance；Amphoteric ionic surfactant can be 3- sulfopropyl dodecyldimethylamine base ammoniums (3- (N, N-
DiMethylMyristylaMMonio) propanesulfonate) or the Long carbon chain molecule containing ammonium and carboxyl simultaneously；On
It states in template molecule for the molecule containing nitrogen and with following molecule formula (II) or molecule containing quaternary ammonium salt ion and with such as
Lower molecule formula (III) is more applicable in.
R1NR2R3 (II)
Wherein, R1The functional group of straight-chain or branched, R are made of the hydrocarbon molecules of 2 to 36 carbon2With R3Be by
Hydrogen atom or the alkyl or phenyl being made of 1 to 8 carbon atoms.
[NR1R4R5R6]+ (III)
Wherein, R1The functional group of straight-chain or branched, R are made of the hydrocarbon molecules of 2 to 36 carbon4To R6It is by 1
The alkyl or phenyl formed to 8 carbon atoms.
R in above-mentioned molecule formula (II)1The function of straight-chain or branched is made of the hydrocarbon molecules of 2 to 36 carbon
Base, more appropriate carbon composition number is 10 to 18.R2With R3By hydrogen atom or the alkyl or benzene that are made of 1 to 8 carbon atoms
Base, more appropriate composed atom are hydrogen atom.Specifically, nitrogenous functional group's molecule as template molecule, such as molecular formula
(II), comprising dodecyl amine (Dodecylamine), tetradecylamine (n-tetradecylamine), cetylamine
(Hexadecylamine), octadecylamine (Octadecylamine), tetradecyldimethylamine (tetradecyl dimethyl
Amine), cetyl methyl amine (Hexadecylmethylamine), hexadecyldimethyl benzyl ammonium amine
(Hexadecyldimethylamine) and the like.
R in above-mentioned molecule formula (III)1The official of straight-chain or branched is made of the hydrocarbon molecules of 2 to 36 carbon
Energy base, more appropriate carbon composition number is 10 to 18.R4To R6The alkyl or phenyl being made of 1 to 8 carbon atoms, more suitably
Alkyl be methyl.Specifically, the nitrogenous functional group cation as template molecule, such as molecule formula (III), includes dodecane
Base trimethyl ammonium (Dodecyl trimethyl ammonium), myristyl benzyl dimethyl ammonium (Tetradecyl
Dimethyl benzyl ammonium), cetyltrimethyl ammonium (Cetyltrimethylammonium), cetyl three
It is butyl ammonium (hexadecyl tributyl ammonium), benzyltrimethylammon.um (Benzyltrimethylammonium), double
Dodecyl dimethyl ammonium (Dimethyldidodecylammonium), cetyl pyridinium
(Hexadecylpyridinium), octadecyltrimethylammonium (Trimethyloctadecylammonium) and the like
Matter.Template above molecule can be used alone or use various template molecular mixing.
Solvent used in the present invention, including, but be not limited to：Alcohols solvent；Specifically, alcohols solvent refers to include
Has the alcohols of 1-10 carbon, for example, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, vinyl butanol, acrylic butanol, n-butanol, secondary
The combination that one or more alcohols such as butanol, the tert-butyl alcohol, amylalcohol, cyclohexanol, benzyl alcohol and double alcoholic compounds are mutually mixed.
Peroxide used in the present invention, including, but be not limited to：Hydrogen peroxide or organic peroxide.Peroxidating
The general formula of hydrogen is H-O-O-H；For R-O-O-H, (R represents a kind of acyl group (acyl group) or hydrocarbon to the general formula of organic peroxide
Base), the substituted base or the group (preferable carbon number is 1-10) without substituent group that R bases are made of 1-20 carbon, including, but
It is not limited to：Acyl group, alkyl, cycloalkyl, secondary or tertiary alkyl (tertiary alkyl group), hydroxyl, cycloalkenyl group
(cycloalkenyl group), aromatic alkyl (aralkyl group) or fragrant alkane alkenyl (aralkenyl group).Tool
For body, organic peroxide can be peroxyformic acid (peroxyformic acid), Peracetic acid (peroxyacetic
Acid), Perpropionic Acid (peroxypropionic acid), peroxystearic acid (peroxystearic acid), peroxide Zong Beam-at-the-eaves
Sour (peroxypalmitic acid), peroxide lauric acid (peroxylauric acid), metachloroperbenzoic acid (meta-
Chloroperoxybenzoic acid), ethylbenzene hydroperoxide, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, cyclohexyl mistake
Hydrogen oxide, tetrahydronaphthalene hydrogen peroxide (tetralin hydroperoxide), methylethyl ketone peroxide (methyl ethyl
Ketone peroxide), methylcyclohexene hydrogen peroxide (methylcyclohexene hydroperoxide) and similar
Substance.More than peroxide can be used alone or be used in mixed way a variety of peroxide.
Meanwhile peroxide used in the present invention, can be directly added into the aqueous solution of preparation peroxide or
Person can also add in the object by that can generate peroxide in the presence of suitable catalyst or under the conditions of appropriate reaction in aqueous solution
Matter generates to react, for example, can be reacted by barium monoxide with dilute sulfuric acid, the hydrolysis of dithionate, hydrogen, oxygen are in metal
Catalysis reaction or aldehydes, alkanes or fragrant alkanes on catalyst coordinate appropriate catalyst in air or oxygen or are not necessary to add
Catalysis under conditions of catalyst reacts to generate and provide peroxide.
In addition, the titanium source in aqueous solution is 0.00001-1, preferably 0.00008-0.5 than the molar ratio range of silicon source；Mould
Plate molecular proportion titanium source adds the molar ratio range of the summation of silicon source to be 0.01-2；Alkali source is 0.1- than the molar ratio range of template molecule
6, preferably 1-4；Template molecule is 0.001-1, preferably 0.005-0.5 than the molar ratio range of water；Solvent is than the weight of water
Than ranging from 0-5, preferably 0.01-3；Peroxide adds the molar ratio range of the summation of silicon source to be 0.001-5 than titanium source, preferably
For 0.01-3.
Then, it such as step (2), then is reacted at a temperature of this aqueous solution is placed in -20-200 DEG C, it is lasting to stir, instead
It is 0.5-180 hours between seasonable, later, by appropriate solid-liquid separating method, will be separated in solid autoreaction solution, then
It is dried being placed in baking oven as the solid obtained by separation of solid and liquid, oven temperature control is in 30-120 DEG C, drying time
0.5-6 hours.
Finally, such as step (3), dried solid is subjected to calcination processing.Calcination temperature range is 300-800 DEG C, compared with
Good is 350-650 DEG C；And calcination time ranging from 1-9 hours, preferably 3-6 hours.So far, you can obtain with high-ratio surface
The titanium-containing silicon oxide material of product and high thermal stability；This titanium-containing silicon oxide material with high thermal stability has under anhydrous conditions
There is chemical formula (I)：
xTiO2(1-x)SiO2 (I)
Wherein, x 0.00001-0.5.
Titanium-containing silicon oxide material prepared by the present invention can be used as catalyst, this catalyst, can be with before catalysis reaction is carried out
The mode handled using silanization (silylation), such as step (4), to reduce containing for silanol group in titanium-containing silicon oxide material
Amount to reduce acidity, the surface characteristic of change catalyst of catalyst substantially, and then increases the catalytic activity of catalyst.
The gas phase that gas-phase silylation reagent is reacted with titanium-containing silicon oxide material may be used in the method for carrying out silanization treatment
Method or the liquid phase method reacted using liquid phase silylating reagent with titanium-containing silicon oxide material.Silanization can use a kind of or more
Kind organosilan is carried out according to general fashion.
And it can be halosilanes (general formula R to perform organosilan used in silanization1R2R3SiX), silazane (general formula
For [R4R5R6Si]2NH), silicyl imidazoles (general formula R7R8R9Si[N2C3H3]) or silylamine (general formula be (R10)3SiN
(R11)2), wherein R1、R2And R3It is identical or different, the respectively saturated alkyl or phenyl for 1-6 carbon；R4、R5And R6It is identical
Or it is different, it is respectively 1-6 alkyl, alkylhalide group or phenyl；R7-R11The respectively saturated alkyl for 1-3 carbon.Preferentially
The organosilan selected is hexamethyldisilazane, silylamine, trim,ethylchlorosilane and N- trimethyl silyl miaows
One or more combinations in azoles.It performs the solvent needed for silanization and can use and one or more be made of 6-16 carbon
Aromatic hydrocarbon or the saturated alkane being made of 6-16 carbon, the solvent preferentially selected is toluene, in benzene and hexamethylene isopropylbenzene
One or more combinations.When performing silanization, the weight ratio of organosilan and titanium-containing silicon oxide material is 0.01-1, preferably
0.1-0.8；The weight ratio of solvent and titanium-containing silicon oxide material is 1-200, preferably 1-100.And the reaction temperature of silanization is
25-200 DEG C, preferably 50-150 DEG C；Reaction time is 0.5-3 hours, preferably 1-2 hours.
In addition, also a kind of selectable way, such as step (5), is incorporated to titanium-containing silicon oxide material to carry by transition metal
Rise the catalytic activity of the material.
In titanium-containing silicon oxide material prepared by the present invention, it can optionally use impregnated with method, the precipitation method, blend method or other classes
Other transition metal are incorporated to like method.Wherein, impregnated with method is scattered in transition metal solution after appropriate solvent with containing titanyl
Silicon nitride material mixes, and forms the titanium-containing silicon oxide material for being impregnated with transition metal, and will optionally be impregnated with containing for transition metal
Silicon oxide material makees further dry and calcining.Wherein, the concentration range of transition metal accounts for the total of titanium-containing silicon oxide material
The 0.01-10 weight percent (wt%) of amount, preferably 0.005-5wt%.What is be obtained by this method has been impregnated with transition metal
Titanium-containing silicon oxide material, transition metal are located in the skeleton of titanium-containing silicon oxide material or outside skeleton.
Titanium-containing silicon oxide material prepared by the present invention can be if necessary in before calcination processing, after calcination processing, before silanization
And any stage after silanization etc. carries out the processing of molding granulation.The mode of molding granulation can optionally select compression forming
Method (compression molding process) or extrusion moulding (extrusion molding process) etc. are suitble to
Mode by titanium-containing silicon oxide material be made tool specified particle diameter range particle.
Titanium-containing silicon oxide material prepared by the present invention is because the titanium with high specific surface area and high dispersive degree is lived
Property position, therefore many organic compounds can be used as and aoxidized or the catalyst of selective oxidation reaction.On the other hand,
If third is added in the titanium-containing silicon oxide material prepared by the present invention forms part (for example, aluminium) to promote acid position, can
Catalytic alkylation (alkylation), reforming reaction (reforming) etc..
So far, the present invention also provides a kind of preparation method of epoxides, is using having as obtained by preceding method
The titanium-containing silicon oxide material of high thermal stability makes alkenes compounds be reacted with oxide, forms epoxidation as catalyst
Object.
Titanium-containing silicon oxide material used in above-mentioned epoxidation reaction can be powdered, lumps, microspheroidal, monolithic shape,
Also can be extrusion forming, compression forming or other any forms.Alkenes compounds used in epoxidation reaction, including, but
It is not limited to：Aliphatic, ring-type include monocyclic, bicyclic or polycyclic compound；Can also be monoene hydro carbons (mono-olefin),
Diene hydro carbons (di-olefin) or Polyene Hydrocarbons (poly-olefin) compound.When the number of double bonds of alkenes compounds are more than
When 2, the type of double bond can be conjugated double bond or unconjugated double bond.Wherein, monoene hydrocarbon compound, including, but be not limited to：
The alkenes compounds being made of 2-60 carbon, alkenes compounds can have there are one substituent group, and the substituent group with
Metastable substituent group is preferable.Wherein, monoene hydrocarbon compound, including, but be not limited to：Ethylene, propylene, 1- butylene,
Isobutene, 1- hexenes, 2- hexenes, 3- hexenes, 1- octenes, 1- decene, styrene or cyclohexene.Diene hydrocarbon compound, including,
But it is not limited to：Butadiene or isoprene.
In addition, oxide used in epoxidation reaction can be organic peroxide, for R-O-O-H, (R represents one to general formula
Kind alkyl)；The group (preferable carbon number is 3-10) that alkyl is made of 3-20 carbon, including, but be not limited to：Secondary or tertiary alkane
Base (tertiary alkyl group) or aromatic alkyl (aralkyl group), for example, tertiary butyl, tertiary pentyl, pentamethylene base
Or 2- phenyl -2- propyl.These organic peroxides, including, but be not limited to：Ethylbenzene hydroperoxide, isopropyl benzene hydroperoxide,
Tert-butyl hydroperoxide or cyclohexyl hydroperoxide；When using isopropyl benzene hydroperoxide as organic peroxide, after reaction
Product is α-isopropylbenzene alcohol (alpha-Cumyl alcohol).α-isopropylbenzene alcohol can be transformed into α-methylstyrene by dehydration
(alpha-methyl styrene), this compound using hydrogenation in addition to there are many other than, can industrially be transformed into different
Propyl benzene and as isopropyl benzene hydroperoxide predecessor；The organic peroxide of other types also has similar characteristic.
Oxide used in epoxidation reaction is alternatively hydrogen peroxide, general formula H-O-O-H.Hydrogen peroxide can be with water
The form of solution obtains, and epoxides and water can be generated after being reacted with alkenes compounds.
Oxide as reactant can be pure or impure substance that is concentrated or diluting.
Can add a kind of solvent or diluent when carrying out epoxidation reaction production epoxides makes reaction in the liquid state
It carries out.Solvent and diluent are in a liquid state and each reactant and product are all showed lazy under conditions of epoxidation reaction progress
Property.These solvents, including, but be not limited to：Methanol, acetone, ethylbenzene, isopropylbenzene, iso-butane or hexamethylene etc. are a kind of or mix
Composition.And solvent can be a kind of substance being present in oxide solution to be used, for example, when selected with isopropylbenzene peroxide
When changing the raw material isopropyl benzene aquatic solution of hydrogen and oxide as oxide, isopropylbenzene can be used as solvent without specially adding one kind
Solvent.
In preceding method, there is no stringent limitations for the usage amount of catalyst, only need to can make epoxidation within the shortest time
The reaction was complete carries out.And it is between 1 to react the molar ratio of used alkenes compounds and oxide when carrying out:100-
100:Between 1, preferably then between 1:10-10:Between 1.There is no particular restriction for reaction temperature, usually 0-200 DEG C, preferably
25-150℃.Reaction pressure be make enough all reactants be in a liquid state more than pressure, preferably then between 1-100 air
Between pressure.It is to obtain the shortest time of epoxides maximum output to react the residence time, generally -48 hours 1 minute, preferably
It is then -8 hours 5 minutes.This program is suitable for any reactor or instrument, for example, fixed bed, conveying bed, liquid bed, slurry
Stirring or continuous flow stirred reactor are carried out in a manner of batch, continous way or semi continuous.
In general, method of the invention, not only program is simple, of low cost, and obtained catalyst is because with outstanding
Thermal stability and the advantages that show excellent catalytic activity, actual gains is in the application in industry.
Below by specific embodiment elaborate, to be easier to understand the goal of the invention of the present invention, technology contents, skill
Art feature and its it is reached the effect of.
Description of the drawings
Fig. 1 is a kind of flow of the preparation method of the titanium-containing silicon oxide material with high thermal stability provided by the present invention
Figure；
Fig. 2 is a kind of flow chart of the preparation method of epoxides provided by the present invention.
Specific implementation method
Fig. 1 shows a kind of streams of the preparation method of the titanium-containing silicon oxide material with high thermal stability provided by the present invention
Cheng Tu.Show five step (1)-(5) in figure.Step (1)-(3) represent a kind of titanium-containing silicon oxide material with high thermal stability
The preparation method of material.Step (4) and (5) represent that the mistake for preparing the titanium-containing silicon oxide material with high thermal stability can be added to
Two possible steps in journey, to obtain the titanium-containing silicon oxide material with high catalytic activity.In fact, step (4) can be used
(5) wherein one or more steps are in single manufacturing process, but for brevity, and are in together by these steps
Existing (representing that these are characterized as what can be selected with dotted line frame), is placed in single flow chart.
Fig. 2 represents that obtained titanium-containing silicon oxide material is applied to the flow of the preparation method of epoxides by the present invention
Figure.Show three step (A)-(C) in figure.Step (C) represents a kind of preparation method of epoxides.Step (A) and (B) are represented
The two possible steps prepared during epoxides can be added to, to improve the high catalytic activity of catalyst.It in fact, can
Using step (A) and wherein one or more steps of (B) in single manufacturing process, but for brevity, and by this
A little steps present (represent that these are characterized as what can be selected with dotted line frame) together, are placed in single flow chart.
Below by several specific embodiments, further illustrate the present invention and how effectively to prepare containing with high thermal stability
Silicon oxide material, and it is anti-to generate epoxidation with oxide by the use of this material as catalyst catalyzed alkene class compound
Should, and produce epoxides.
Embodiment one
Prepare titanium-containing silicon oxide material：It will be by tetraisopropyl titanate (tetraisopropyl orthotitanate) 0.58
Kilogram, 15.6 kilograms of tetraethoxysilane (tetraethylorthosilicate), the ammonium hydroxide of 28 weight percent (wt%) it is molten
4.56 kilograms of liquid, 7.81 kilograms of cetyltrimethylammonium hydroxide (Cetyltrimethylammonium hydroxide),
24.6 kilograms of 2.42 kilograms of 35wt% hydrogen peroxide, 3 kilograms of isopropanol and water reaction solutions being configured to are placed in and stir 3 at room temperature
After hour, it is filtered.After solution removes, powder is placed in 70 DEG C of dryings.Dried powder is calcined, calcination temperature
Be 550 DEG C, heating rate be 5 DEG C per minute, hold temperature 6 hours after Temperature fall.
Prepare propylene oxide：Using 7.5 grams of titanium-containing silicon oxide material obtained by embodiment one as catalyst, with 225 grams
The cumyl hydroperoxide solution (solvent is isopropylbenzene) of 25wt% and 125 grams of propylene are in 1 liter of closed reaction under high pressure
It is uniformly mixed in device (autoclave), and calorifies 85 DEG C and reacted, the reaction time is less than 1.5 hours.Reaction result such as table
Shown in one.
Embodiment two
Prepare titanium-containing silicon oxide material：Preparation method is identical with embodiment one, but by obtained titanium-containing silicon oxide material
Take 16.5 grams of progress silanizations.Specially by this titanium-containing silicon oxide material and 165 grams of toluene and 11.2 grams of two silicon nitrogen of hexamethyl
Alkane (hexamethyldisilazane) is uniformly mixed, and filtration drying after being stirred 1 hour at 120 DEG C.
Prepare propylene oxide：Preparation method is identical with embodiment one, but used catalyst is changed to obtained by embodiment two
Titanium-containing silicon oxide material.Reaction result is as shown in Table 1.
Embodiment three
Prepare titanium-containing silicon oxide material：Preparation method is identical with embodiment two, but by obtained titanium-containing silicon oxide material
Particle of the grain size between 1-2 millimeters (mm) is made into using compression forming methods.
Prepare propylene oxide：Preparation method is identical with embodiment one, but used catalyst is changed to obtained by embodiment three
Titanium-containing silicon oxide material.Reaction result is as shown in Table 1.
Example IV
Prepare titanium-containing silicon oxide material：Preparation method is identical with embodiment three.
Prepare propylene oxide：Titanium-containing silicon oxide material obtained by Example four inserts internal diameter as 2 English as catalyst
Very little, length is 75 centimeters of fixed bed reactors.The cumyl hydroperoxide solution (solvent is isopropylbenzene) and propylene of 25wt%
Continue to be rubbed by the lower endfeed of fixed bed (Fix bed) reactor, propylene/cumyl hydroperoxide after static mixer
You are controlled than the feed rate of the cumyl hydroperoxide solution for 8,25wt% in WHSV=10h-1, system temperature maintains 85
DEG C, system pressure, which maintains 30bar, makes propylene ring oxidation reaction continue to occur in catalyst layer.Reaction solution from upper end discharge after by
Gas-liquid separation slot after excessive propylene separation, carries out the analysis of product.The propylene ring oxidation reaction is carried out continuously more than 300
The reaction result of hour is as shown in Table 1.
Comparative example one
Prepare titanium-containing silicon oxide material：According to document J.Catal. volumes 254 (2008)：It is prepared by the mode disclosed in page 64
After going out titanium-containing silicon oxide material, 16.5 grams of progress silanizations are taken.By this titanium-containing silicon oxide material and 165 grams of toluene and 11.2 grams
Hexamethyldisilazane (hexamethyldisilazane) is uniformly mixed, and filtration drying after being stirred 1 hour at 120 DEG C.
Prepare propylene oxide：Preparation method is identical with embodiment one, but used catalyst is changed to obtained by comparative example one
Titanium-containing silicon oxide material.Reaction result is as shown in Table 1.
Comparative example two
Prepare titanium-containing silicon oxide material：It will be by 0.72 kilogram of tetraisopropyl titanate, 20.3 kilograms of tetraethoxysilane, 28 weights
0.05 kilogram of 2.7 kilograms of ammonia spirit, potassium hydroxide, the cetyltrimethylammonium hydroxide 7.81 for measuring percentage (wt%) are public
After 38.3 kilograms of jin, 3.9 kilograms of isopropanol and water reaction solutions being configured to are placed in stirring at room temperature 3 hours, it is filtered.
After solution removes, powder is placed in 70 DEG C of dryings.Dried powder is calcined, calcination temperature is 550 DEG C, heating rate
Be 5 DEG C per minute, hold temperature 6 hours after Temperature fall.
Obtained titanium-containing silicon oxide material is taken into 16.5 grams of progress silanizations.By this titanium-containing silicon oxide material and 165 grams
Toluene and 11.2 grams of hexamethyldisilazane are uniformly mixed, and filtration drying after being stirred 1 hour at 120 DEG C.
Prepare propylene oxide：Preparation method is identical with embodiment one, but used catalyst is changed to obtained by comparative example two
Titanium-containing silicon oxide material.Reaction result is as shown in Table 1.
Table one
Note1Cumyl hydroperoxide conversion ratio=cumyl hydroperoxide consumption/cumyl hydroperoxide additive amount ×
100%.
Note2Propylene oxide selection rate=propylene oxide production quantity/cumyl hydroperoxide consumption × 100%.
As table one as it can be seen that the titanium-containing silicon oxide material prepared by the reaction result display present invention of embodiment one is by calcining
Afterwards, there is outstanding catalytic activity for the epoxidation reaction of catalyzed alkene class compound；The reaction result of embodiment two is shown
Titanium-containing silicon oxide material prepared by the present invention can be substantially improved it and carry out ring to catalyzed alkene class compound after silanization
The catalytic activity of oxidation reaction；Titanium-containing silicon oxide material prepared by the reaction result display present invention of embodiment three is by forming
After granulation, to the catalytic activity of itself, there is no significant impacts；Prepared by the reaction result display present invention of example IV
Titanium-containing silicon oxide material by long-time carry out continous way alkenes compounds epoxidation reaction test after, still maintain outstanding
Catalytic activity；Comparative example one is with the titanium-containing silicon oxide material prepared by the reaction result display present invention of comparative example two for alkene
The catalytic activity of the epoxidation reaction of hydrocarbon compound, hence it is evident that the titanium-containing silicon oxide material obtained by Billy's prior art is high.
Generally speaking, the preparation method and application of the titanium-containing silicon oxide material according to the present invention with high thermal stability,
It only needs that using general easy template the titanium-containing silicon oxide material with superior heat-stability can be prepared, and it is obtained
Titanium-containing silicon oxide material there is high catalytic activity, catalyst can be further used as, the epoxy of success catalyzed alkene class compound
Change reaction, and either all show catalytic activity that is outstanding and stablizing using batch reactor or flow reactor.
Above-described embodiment is only exemplary, does not form any restrictions to the scope of the present invention.Therefore without departing from this hair
Can the details and form of technical solution of the present invention be modified or be replaced under bright spirit and scope, but these are changed and replace
It changes and each falls in protection scope of the present invention.
Claims (21)
1. a kind of preparation method of the titanium-containing silicon oxide material with high thermal stability, which is characterized in that comprise the steps of：
(1) titanium source, silicon source, alkali source, template molecule, solvent and peroxide are hybridly prepared into aqueous solution；
(2) after making the reactant aqueous solution, separation of solid and liquid and drying are carried out；
(3) calcination processing is carried out to the solid of gained after separation of solid and liquid and drying, obtains the titanium-containing silicon oxide material, this contains titanyl
Silicon nitride material has chemical formula (I) under anhydrous conditions：
xTiO2(1-x)SiO2 (Ⅰ)
Wherein, x 0.00001-0.5.
2. the preparation method of the titanium-containing silicon oxide material with high thermal stability as described in claim 1, which is characterized in that institute
Titanium source is stated as titanate esters, inorganic ti sources or combination；The silicon source is silica, the alkoxy of amorphous phase (amorphous)
Silane (alkoxysilane), silicate or combination；The alkali source is organic base, inorganic base, relative ion (counter
It ion) can be simultaneously as the organic molecule or combination of template for hydroxy anion；The template molecule is cationic
Activating agent, anionic surfactant, nonionic surface active agent, amphoteric ionic surfactant or combination；Institute
State solvent be selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol, vinyl butanol, acrylic butanol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol,
Amylalcohol, cyclohexanol, benzyl alcohol, double alcoholic compounds and combinations thereof；The peroxide is hydrogen peroxide or organic peroxide.
3. the preparation method of the titanium-containing silicon oxide material with high thermal stability as claimed in claim 2, which is characterized in that institute
It states titanate esters and is selected from tetramethoxy titanate ester, tetraethyl titanate, n- metatitanic acid orthocarbonate, tetraisopropyl titanate, n- butyl titanate, titanium
Sour four secondary butyl esters, iso- butyl titanate, four tert-butyl ester of metatitanic acid, four (2-Ethylhexyl Alcohol) titanate esters, four (octadecyl) positive metatitanic acids
Salt and combinations thereof；The inorganic ti sources are selected from titanium trichloride, titanium tetrachloride, titanium tribromide, titanium tetrabromide, titanium triiodide, the tetraiodo
Change titanium, titanium sulfate, titanium dioxide and combinations thereof.
4. the preparation method of the titanium-containing silicon oxide material with high thermal stability as claimed in claim 2, which is characterized in that institute
The silica for stating amorphous phase is selected from smoked silicon, white cigarette, silica dioxide gel, silicon dioxide gel and combinations thereof；The alkoxy
Silane is selected from tetramethoxy-silicane (tetramethylorthosilicate), tetraethoxysilane
(tetraethylorthosilicate), tetrapropoxysilane (tetrapropylorthosilicate), three alcoxyl of monoalkyl
Base silane (alkyltrialkoxysilanes), dialkyl dialkoxy silicane (dialkyldialkoxysilanes), three alkane
Base monoalkoxysilane (trialkylmonoalkoxysilanes) and combinations thereof；The silicate is selected from waterglass, potassium silicate
Salt, britesorb, calsil and combinations thereof.
5. the preparation method of the titanium-containing silicon oxide material with high thermal stability as claimed in claim 2, which is characterized in that institute
It states organic base and is selected from ammonium hydroxide, pyridine, imidazoles, benzimidazole, histidine and combinations thereof；The inorganic base is selected from hydroxide
Lithium, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide and combinations thereof；The relative ion
For hydroxy anion trimethyl ammonium hydroxide (Dodecyl can be selected from as the organic molecule of template simultaneously
Trimethyl ammonium hydroxide), myristyl benzyl dimethyl ammonium hydroxide (Tetradecyl dimethyl
Benzyl ammonium hydroxide), cetyltrimethylammonium hydroxide (Cetyltrimethylammonium
Hydroxide), cetyltributylphosphonium ammonium hydroxide (hexadecyl tributyl ammonium hydroxide), benzyl
Trimethylammonium hydroxide (Benzyltrimethylammonium hydroxide), double dodecyl dimethyl ammonium hydroxide
(Dimethyldidodecylammonium hydroxide), cetyl pyridinium (Hexadecylpyridinium), ten
Eight alkyltrimethylammonium hydroxides (Trimethyloctadecylammonium hydroxide) and combinations thereof.
6. the preparation method of the titanium-containing silicon oxide material with high thermal stability as claimed in claim 2, which is characterized in that institute
It is R to state template molecule and be selected from molecular formula1NR2R3Nitrogen-containing molecules, molecular formula be [NR1R4R5R6]+Containing quaternary ammonium salt ion point
Son and combinations thereof, wherein, R1The functional group of straight-chain or branched, R are made of the hydrocarbon molecules of 2 to 36 carbon2With R3It is
By hydrogen atom or the alkyl or phenyl being made of 1 to 8 carbon atoms, R4To R6The alkyl being made of 1 to 8 carbon atoms
Or phenyl.
7. the preparation method of the titanium-containing silicon oxide material with high thermal stability as claimed in claim 6, which is characterized in that institute
It states template molecule and is selected from dodecyl amine (Dodecylamine), tetradecylamine (n-tetradecylamine), cetylamine
(Hexadecylamine), octadecylamine (Octadecylamine), tetradecyldimethylamine (tetradecyl dimethyl
Amine), cetyl methyl amine (Hexadecylmethylamine), hexadecyldimethyl benzyl ammonium amine
(Hexadecyldimethylamine), dodecyl trimethyl ammonium (Dodecyl trimethyl ammonium), the tetradecane
Base dimethyl benzyl ammonium (Tetradecyl dimethyl benzyl ammonium), cetyltrimethyl ammonium
(Cetyltrimethylammonium), cetyltributylphosphonium ammonium (hexadecyl tributyl ammonium), benzyl three
Methyl ammonium (Benzyltrimethylammonium), double dodecyl dimethyl ammoniums
(Dimethyldidodecylammonium), cetyl pyridinium (Hexadecylpyridinium), octadecyl front three
Base ammonium (Trimethyloctadecylammonium) and combinations thereof.
8. the preparation method of the titanium-containing silicon oxide material with high thermal stability as claimed in claim 2, which is characterized in that institute
It states organic peroxide and is selected from peroxyformic acid (peroxyformic acid), Peracetic acid (peroxyacetic acid), mistake
Oxygen propionic acid (peroxypropionic acid), peroxystearic acid (peroxystearic acid), peroxide Zong Beam-at-the-eaves acid
(peroxypalmitic acid), peroxide lauric acid (peroxylauric acid), metachloroperbenzoic acid (meta-
Chloroperoxybenzoic acid), ethylbenzene hydroperoxide, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, cyclohexyl mistake
Hydrogen oxide, tetrahydronaphthalene hydrogen peroxide (tetralin hydroperoxide), methylethyl ketone peroxide (methylethyl ketone
Peroxide), methylcyclohexene hydrogen peroxide (methylcyclohexene hydroperoxide) and combinations thereof.
9. the preparation method of the titanium-containing silicon oxide material with high thermal stability as described in claim 1, which is characterized in that institute
State peroxide and can be reacted in the aqueous solution by barium monoxide with dilute sulfuric acid, the hydrolysis of dithionate, hydrogen with
Catalysis of the oxygen on metal solvent is reacted or aldehydes, alkanes or fragrant alkanes are used or do not used in air or oxygen
Produced by the catalysis reaction of catalyst.
10. the preparation method of the titanium-containing silicon oxide material with high thermal stability as described in claim 1, which is characterized in that
Titanium in the aqueous solution is 0.00001-1 than the molar ratio range of silicon, and the template molecule is than titanium and mole of the summation of silicon
Than ranging from 0.01-2, the solvent is than the weight ratio ranging from 0-5 of water, and the peroxide is than titanium and mole of the summation of silicon
Than ranging from 0.001-5, the template molecule is 0.001-1 than the molar ratio range of water, and the alkali source is than the template molecule
Molar ratio range be 0.1-6.
11. the preparation method of the titanium-containing silicon oxide material with high thermal stability as claimed in claim 10, which is characterized in that
Titanium in the aqueous solution is 0.00008-0.5 than the molar ratio range of silicon, and the solvent is than the weight ratio ranging from 0.01- of water
3, the peroxide is 0.01-3 than the molar ratio range of titanium and the summation of silicon, and the template molecule is than the molar ratio range of water
For 0.005-0.5, the alkali source is 1-4 than the molar ratio range of the template molecule.
12. the preparation method of the titanium-containing silicon oxide material with high thermal stability as described in claim 1, which is characterized in that
Reaction is reacted 0.5-180 hours at -20-200 DEG C described in step (2), and the drying is persistently done at 30-120 DEG C
It is 0.5-6 hours dry.
13. the preparation method of the titanium-containing silicon oxide material with high thermal stability as described in claim 1, which is characterized in that
The calcination temperature of calcination processing described in step (3) is 300-800 DEG C, and calcination time is 1-9 hours.
14. the preparation method of the titanium-containing silicon oxide material with high thermal stability as claimed in claim 13, which is characterized in that
The calcination temperature of the calcination processing is 350-650 DEG C, and calcination time is 3-6 hours.
15. the preparation method of the titanium-containing silicon oxide material with high thermal stability as described in claim 1, which is characterized in that
After step (3), at least one of the following steps are added in：
(4) silanization treatment is carried out to the titanium-containing silicon oxide material, reaction temperature is 25-200 DEG C, and the reaction time is small for 0.5-3
When；
(5) transition metal is incorporated in the titanium-containing silicon oxide material, the concentration range of the transition metal accounts for the titaniferous oxidation
The 0.01-10 weight percent of silicon materials total amount.
16. the preparation method of the titanium-containing silicon oxide material with high thermal stability as claimed in claim 15, which is characterized in that
The concentration range of the transition metal accounts for the 0.005-5 weight percent of the total amount of the titanium-containing silicon oxide material.
17. a kind of preparation method of epoxides, which is characterized in that using the tool obtained by the method as described in claim 1
There is the titanium-containing silicon oxide material of high thermal stability as catalyst, alkenes compounds is made to be reacted with oxide, form epoxy
Compound.
18. the preparation method of epoxides as claimed in claim 17, which is characterized in that the alkenes compounds are monoene
Hydro carbons, diene hydro carbons or Polyene Hydrocarbons compound；The oxide is organic peroxide or hydroperoxides.
19. the preparation method of epoxides as claimed in claim 18, which is characterized in that the monoene hydrocarbon compound is selected from
Ethylene, propylene, 1- butylene, isobutene, 1- hexenes, 2- hexenes, 3- hexenes, 1- octenes, 1- decene, styrene and cyclohexene and its
Combination；The diene hydrocarbon compound is butadiene or isoprene；The organic peroxide is ethylbenzene hydroperoxide, isopropyl
Benzene hydrogen peroxide, tert-butyl hydroperoxide or cyclohexyl hydroperoxide.
20. the preparation method of epoxides as claimed in claim 17, which is characterized in that the alkenes compounds with it is described
The molar ratio of oxide is between 1:100-100:Between 1, the reaction temperature of the reaction is 0-200 DEG C, and reaction pressure is enough
Make pressure that all reactants are in a liquid state and more than, the reaction time is -48 hours 1 minute.
21. the preparation method of epoxides as claimed in claim 20, which is characterized in that the alkenes compounds with it is described
The molar ratio of oxide is between 1:10-10:Between 1, the reaction temperature of the reaction is 25-150 DEG C, reaction pressure 1-100
Atmospheric pressure, reaction time are -8 hours 5 minutes.
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