CN101307039A - Method for producing epoxide - Google Patents
Method for producing epoxide Download PDFInfo
- Publication number
- CN101307039A CN101307039A CNA2007100407003A CN200710040700A CN101307039A CN 101307039 A CN101307039 A CN 101307039A CN A2007100407003 A CNA2007100407003 A CN A2007100407003A CN 200710040700 A CN200710040700 A CN 200710040700A CN 101307039 A CN101307039 A CN 101307039A
- Authority
- CN
- China
- Prior art keywords
- epoxide
- hour
- titanium
- acid
- alkene
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 150000002118 epoxides Chemical class 0.000 title claims abstract 15
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 238000002444 silanisation Methods 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 27
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 150000001336 alkenes Chemical class 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical group C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 14
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 239000012018 catalyst precursor Substances 0.000 claims description 10
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 8
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 claims description 8
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 8
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 8
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 8
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 8
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- -1 silicon ester Chemical class 0.000 claims description 8
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- GQNOPVSQPBUJKQ-UHFFFAOYSA-N 1-hydroperoxyethylbenzene Chemical group OOC(C)C1=CC=CC=C1 GQNOPVSQPBUJKQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 5
- VIDOPANCAUPXNH-UHFFFAOYSA-N 1,2,3-triethylbenzene Chemical compound CCC1=CC=CC(CC)=C1CC VIDOPANCAUPXNH-UHFFFAOYSA-N 0.000 claims description 4
- DCSOPUDOZMRWRP-UHFFFAOYSA-N Cc1cc(C)cc([SiH2]Cl)c1 Chemical compound Cc1cc(C)cc([SiH2]Cl)c1 DCSOPUDOZMRWRP-UHFFFAOYSA-N 0.000 claims description 4
- YKFRUJSEPGHZFJ-UHFFFAOYSA-N N-trimethylsilylimidazole Chemical group C[Si](C)(C)N1C=CN=C1 YKFRUJSEPGHZFJ-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 claims description 4
- AVDUEHWPPXIAEB-UHFFFAOYSA-N chloro-ethyl-dimethylsilane Chemical compound CC[Si](C)(C)Cl AVDUEHWPPXIAEB-UHFFFAOYSA-N 0.000 claims description 4
- YGHUUVGIRWMJGE-UHFFFAOYSA-N chlorodimethylsilane Chemical compound C[SiH](C)Cl YGHUUVGIRWMJGE-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 150000003609 titanium compounds Chemical class 0.000 claims description 4
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 2
- XJOVUXIJZZFRIH-UHFFFAOYSA-N N-(chloromethylsilyl)-N-trimethylsilylmethanamine Chemical compound ClC[SiH2]N([Si](C)(C)C)C XJOVUXIJZZFRIH-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- VJOJBPHQBSIICD-UHFFFAOYSA-N NC[SiH](Cl)C1=CC=CC=C1 Chemical compound NC[SiH](Cl)C1=CC=CC=C1 VJOJBPHQBSIICD-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- GWFIFNPYMZJOMD-UHFFFAOYSA-N [SiH4].CCC(C)(C)Cl Chemical compound [SiH4].CCC(C)(C)Cl GWFIFNPYMZJOMD-UHFFFAOYSA-N 0.000 claims description 2
- WYUIWUCVZCRTRH-UHFFFAOYSA-N [[[ethenyl(dimethyl)silyl]amino]-dimethylsilyl]ethene Chemical compound C=C[Si](C)(C)N[Si](C)(C)C=C WYUIWUCVZCRTRH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- ACTAPAGNZPZLEF-UHFFFAOYSA-N chloro(tripropyl)silane Chemical compound CCC[Si](Cl)(CCC)CCC ACTAPAGNZPZLEF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001925 cycloalkenes Chemical class 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- VUENSYJCBOSTCS-UHFFFAOYSA-N tert-butyl-imidazol-1-yl-dimethylsilane Chemical class CC(C)(C)[Si](C)(C)N1C=CN=C1 VUENSYJCBOSTCS-UHFFFAOYSA-N 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-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
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 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
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-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
- JSQJUDVTRRCSRU-UHFFFAOYSA-N tributyl(chloro)silane Chemical compound CCCC[Si](Cl)(CCCC)CCCC JSQJUDVTRRCSRU-UHFFFAOYSA-N 0.000 claims description 2
- HUYLAMJIPCOVOM-UHFFFAOYSA-K triiodotitanium Chemical compound [Ti+3].[I-].[I-].[I-] HUYLAMJIPCOVOM-UHFFFAOYSA-K 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 10
- 238000006735 epoxidation reaction Methods 0.000 abstract description 7
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- 229920002521 macromolecule Polymers 0.000 description 1
- OCKPCBLVNKHBMX-UHFFFAOYSA-N n-butyl-benzene Natural products CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 1
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- 238000010189 synthetic method Methods 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 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 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention relates to a method for producing epoxide, which mainly solves a problem that the prior art is low in the activity of catalyst for producing epoxide, poor in mass transfer effect and high in production cost. By adopting a technical proposal of using organic amine as template agent, grafting inorganic titanium to a silicon dioxide framework with a hexagonal meso-porous structure to form an active titanium species with a four-coordination structure, and preparing epoxidation catalyst via silanization treatment, the method solves the problem well and can be used in the industrial production of epoxide.
Description
Technical field
The present invention relates to produce the method for epoxide.
Background technology
Epoxide is the important organic chemical industry's intermediate of a class, and the method for industrial production epoxide mainly contains chlorohydrination and conjugated oxidation at present.Chlorohydrination is owing to produce a large amount of chlorine-contained wastewaters in process of production, and environmental pollution and equipment corrosion are serious; Conjugated oxidation has overcome shortcomings such as the pollution of chlorohydrination and corrosion, but long flow path, investment is big, co-product is many, and joint product market has influenced the production of propylene oxide to a certain extent.
As everyone knows, titaniferous porous silica material has good catalytic activity to the selective oxidation of hydro carbons, can be used as the catalyzer that the alkene selective oxidation prepares epoxide.
Patent US4410501 discloses the synthetic method of TS-1 molecular sieve first.At first, the aqueous solution, organic titanate and the organosilicon acid esters with TPAOH is the titaniferous colloidal silica solution of feedstock production.Then, directly synthetic again by hydrothermal crystallizing.The invention of this new catalytic material is laid a good foundation for the friendly technology with development environment of the hydrocarbon oxidization of research highly selective, but because TS-1 is the micro-pore zeolite with MFI structure, its aperture has only 0.55 nanometer, the oxidizing reaction that can not catalysis organic macromolecule (as tetrahydrobenzene and vinylbenzene etc.) participates in, when being oxygenant with the organo-peroxide in addition, TS-1 does not almost have catalytic activity.
It is catalyzer that patent US3923843 and US4367342 disclose with titaniferous amorphous silica, and ethylbenzene hydroperoxide (EBHP) can be a propylene oxide with Selective Oxidation of Propylene.But because its specific surface area of amorphous silica carrier and the pore volume that are adopted are little, the charge capacity of titanium is difficult to improve, activity of such catalysts is low, the internal diffusion performance of catalyzer is also poor simultaneously, therefore, to be difficult to competent be the catalysis epoxidation system of oxygenant with other superoxide (as isopropyl benzene hydroperoxide) to such catalyzer.
It is oxygenant that patent CN1500004A and CN 1248579A disclose with isopropyl benzene hydroperoxide (CHP) or ethylbenzene hydroperoxide (EBHP), and the Ti-MCM41 catalyzer can become propylene oxide with Selective Oxidation of Propylene.But because the Ti-MCM41 catalyzer adopts expensive quaternary ammonium salt to make template in building-up process, need long crystallization process simultaneously, the production efficiency of catalyzer is low, thereby causes the manufacturing cost height of catalyzer, and the industrial economy of propylene oxide is subjected to remarkably influenced.
It is the novel titanium-containing molecular sieve catalyst (Ti-HMS) with mesoporous feature of oxygenant selective oxidation 2,6 di t butyl phenol and benzene with the hydrogen peroxide that Nature magazine (1994,368,321) has been introduced a kind of.The Ti-HMS catalyzer is that the mixing solutions with water, ethanol and Virahol is a solvent, with isopropyl titanate and tetraethoxy be raw material, to adopt positive amino dodecane be template, synthetic at ambient temperature.Compare with Ti-MCM41, Ti-HMS has better Technological Economy.But the document be not to do any research aspect the oxidizer catalytic olefin oxide with the organo-peroxide to the Ti-HMS catalyzer.
Summary of the invention
Technical problem to be solved by this invention be produce in the prior art that the catalyst activity of epoxide is low, mass transfer effect difference and the high problem of production cost, a kind of method of new production epoxide is provided.This method has catalyst activity and selectivity height, and mass transfer effect reaches the low characteristics of production cost well.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of producing epoxide, with alkene and organo-peroxide is raw material, reaction system is the inert non-polar compound is solvent, in temperature of reaction is 25～200 ℃, the reaction absolute pressure is 0.1～10MPa, the mol ratio of alkene and organo-peroxide is 1～20: 1, the mol ratio of solvent and alkene is 0.01～60: 1, catalyst levels be reacted under 0.1～10% condition of weight of solvent 0.5～24 hour epoxide, wherein used catalyzer is Ti-HMS, and its preparation may further comprise the steps:
A) with the silicon ester be the silicon source, general formula is RNH
2Organic amine be template, organic alcohol and water is a solvent, wherein R is the chain alkylene that contains 7～36 carbon atoms, with molar ratio computing RNH
2/ Si=0.01～1.0: 1, water/pure volume ratio is 0.01～5: 1, and above-mentioned reaction mixture was at room temperature stirred crystallization 0.5～48 hour, and crystallized product is through separation, washing, drying, and 300～1000 ℃ of roastings obtained HMS in 0.5～48 hour;
B) above-mentioned HMS being reacted 0.5～100 hour with the inorganic titanium compound that is dissolved in the organic solvent at 25～300 ℃, obtain Ti-HMS, is 5～200 with molar ratio computing Si/Ti wherein;
C) above-mentioned Ti-HMS is activated 0.5～48 hour at 300～1000 ℃, obtain catalyst Precursors;
D) the above-mentioned catalyst Precursors that obtains was handled 0.5～100 hour with the organic silicon solution that is dissolved in the organic solvent at 25～400 ℃, obtained the Ti-HMS catalyzer through the silanization processing, wherein organosilyl consumption is 10～70% of a catalyst Precursors weight.
In the technique scheme, described alkene preferred version is alkene, cycloolefin or fragrant alkene; Described organo-peroxide preferred version is ethylbenzene hydroperoxide, isopropyl benzene hydroperoxide, tertbutyl peroxide or cyclohexyl hydroperoxide; It is described that reaction system is inert non-polar compound preferred version is ethylbenzene, isopropyl benzene, Trimethylmethane or hexanaphthene.The temperature of reaction preferable range is 40～130 ℃, reaction absolute pressure preferable range is 0.1～5.0MPa, the mol ratio preferable range of alkene and organo-peroxide is 2～15: 1, the mol ratio preferable range of solvent and alkene is 0.1～20: 1, and the catalyst consumption preferable range is 0.5～5% of a weight of solvent.A) preferred version of silicon ester described in the step is methyl silicate, tetraethoxy, positive silicic acid n-propyl, positive isopropyl silicate or butyl silicate; Described pure preferred version is at least a in methyl alcohol, ethanol, n-propyl alcohol, Virahol, vinyl alcohol, allyl alcohol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, amylalcohol, hexalin, ethylene glycol or the propylene glycol; The R preferred version is the chain alkylene that contains 10～20 carbon atoms; With molar ratio computing RNH
2/ Si preferable range is 0.1～5: 1, and water/pure volume ratio preferable range is 0.1～2: 1, and crystallization time preferable range is 1～24 hour.B) preferred version of inorganic titanium compound described in step preferred version is titanium tetrachloride, titanous chloride, titanium tetrabromide, titanium tribromide, titanium tetra iodide or titanium triiodide, is 10～100 with molar ratio computing Si/Ti preferable range wherein; Described organic solvent preferred version is to be selected from least a in benzene,toluene,xylene, trimethylbenzene, ethylbenzene, diethylbenzene, triethyl-benzene, isopropyl benzene, hexane, hexanaphthene, heptane, octane, nonane, decane, undecane or the dodecane; Carrying titanium temperature preferable range is 50～250 ℃, and carrying titanium time preferable range is 1～48 hour.C) the activation temperature preferable range is 400～800 ℃ in the step, and the soak time preferable range is 1～24 hour.D) in the step organosilicon preferred version for being selected from halosilanes, at least a in silazane or the silylamine, wherein the halosilanes preferred version is for being selected from trimethylchlorosilane, chlorotriethyl silane, the tripropyl chlorosilane, the tributyl chlorosilane, chlorodimethyl silane, dimethyldichlorosilane(DMCS), the 3,5-dimethylphenyl chlorosilane, the dimethyl ethyl chlorosilane, dimethyl n propyl chloride silane, dimethyl isopropyl chloride silane, normal-butyl dimethylchlorosilane or aminomethyl phenyl chlorosilane, more preferably scheme is for being selected from trimethylchlorosilane, chlorotriethyl silane, chlorodimethyl silane, dimethyldichlorosilane(DMCS), 3,5-dimethylphenyl chlorosilane or dimethyl ethyl chlorosilane; The silazane preferred version is for being selected from hexamethyldisilazane, 1,1,3,3-tetramethyl-disilazane, 1,3-two (chloromethyl) tetramethyl-disilazane, 1,3-divinyl-1,1,3,3-tetramethyl-disilazane or 1,3-phenylbenzene tetramethyl-disilazane, more preferably scheme is for being selected from hexamethyldisilazane or 1,1,3, the 3-tetramethyl-disilazane; The silylamine preferred version is for being selected from N-trimethyl-silyl-imidazole, N-t-butyldimethylsilyl imidazoles, N-dimethylethylsilyl imidazoles, N-dimethyl n propyl group silyl imidazoles, N-dimethyl sec.-propyl silyl imidazoles, N-trimethyl silyl dimethyl amine or N-trimethyl silyl diethylamide, and more preferably scheme is for being selected from N-trimethyl-silyl-imidazole, N-dimethylethylsilyl imidazoles, N-trimethyl silyl dimethyl amine or N-trimethyl silyl diethylamide; Described organic solvent preferred version is to be selected from least a in benzene,toluene,xylene, trimethylbenzene, ethylbenzene, diethylbenzene, triethyl-benzene, isopropyl benzene, hexane, hexanaphthene, heptane, octane, nonane, decane, undecane or the dodecane; Silanization temperature preferable range is 50～350 ℃, and silanization time preferable range is 1～48 hour.
In support of the catalyst HMS building-up process, preferably in reaction mixture, add acid or alkali, the mol ratio of acid or alkali and silicon ester is 0.001～10: 1.Wherein acid is selected from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetate or propionic acid, and alkali is selected from sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood or ammoniacal liquor.
Catalyzer among the present invention is at 960 ± 10cm of infrared absorpting light spectra
-1All have charateristic avsorption band with 210 ± 10nm place at uv-visible absorption spectra figure, this indicate titanium grafting in silicon dioxide skeleton and formed active titanium species with four-coordination structure.
Epoxidation reaction of the present invention can be carried out in slurry bed or fixed bed.Because the catalyzer for preparing among the present invention is a kind of typical heterogeneous catalyst, so, in adopting the epoxide reaction liquid that this method produced, not containing catalyzer substantially, product is not subjected to catalyst contamination.
Synthetic Ti-HMS among the present invention, owing to adopt cheap organic amine to make template, crystallization time is short simultaneously, thus the production efficiency height of catalyzer, manufacturing cost significantly reduces.In addition, the catalyst Precursors of handling without silanization among the present invention is because abundant silicon hydroxyl and titanium hydroxyl are contained in its surface, so possess hydrophilic property and acidity, yield and the selectivity of catalyzer to epoxide in this remarkably influenced.In order to improve the epoxidation performance of catalyzer, catalyst Precursors is carried out silanization handle, the hydroxyl that its surface is existed is converted into the alkyl siloxy, strengthens hydrophobic nature, reduces acid.The raising of catalyzer hydrophobic nature can reduce the absorption of polarity oxidation products at catalyst surface, also can avoid the loss of active constituent titanium on the catalyzer.Synthetic specific surface area of catalyst and pore volume are big among the present invention, and the charge capacity of titanium can be guaranteed, so the activity of such catalysts height, the internal diffusion performance of catalyzer might as well simultaneously.When therefore the synthetic catalyzer is used to prepare epoxide among the present invention, the catalyst activity height, the selectivity of product height has been obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
In room temperature with under stirring, 10 gram cetylamines, 5 gram amino dodecanes are joined 80 milliliters of H
2In the mixing solutions of O, 60 milliliters of ethanol and 5 milliliters of (1M) hydrochloric acid, be stirred to solution and be a phase.To be dissolved in 65.0 in 30 milliliters of ethanol grams tetraethoxy and join in the above-mentioned mixing solutions, stir after 30 minutes crystallization 24 hours.Filter resulting decorating film, wash with water to remove remaining Cl
-Solid after the washing after 12 hours, 600 ℃ of roastings 4 hours, is promptly got the HMS with hexagonal mesoporous structure in 110 ℃ of oven dry.
In 100 milliliters there-necked flask, add and contain 1.2 gram TiCl
450 milliliters of octane solution, the powdered samples of the above-mentioned preparation of 10.0 grams are joined in the flask, under stirring and refluxing, elevated temperature to 120 ℃, and reaction 4 hours under this temperature.Under this temperature, after the solvent evaporated in vacuo, got catalyst Precursors in 4 hours in the following 600 ℃ of calcination activations of nitrogen atmosphere.
The catalyst Precursors of above-mentioned preparation is put into 100 milliliters there-necked flask, and add 50 milliliters of cumene solutions containing 4.0 gram hexamethyldisilazanes, under stirring and refluxing, elevated temperature to 150 ℃, and reaction 4 hours under this temperature.Under this temperature, the hexamethyldisilazane of evaporated in vacuo remnants and isopropyl benzene solvent promptly make the Ti-HMS catalyzer of handling through silanization then, and its specific surface area is 890 meters
2/ gram, pore volume is 0.9 centimetre
3/ gram, mean pore size is
[embodiment 2]
Except TiCl
4Amount be 1.5 the gram outside, all the other conditions are identical with [embodiment 1].The specific surface area of the Ti-HMS catalyzer that makes is 850 meters
2/ gram, pore volume is 0.8 centimetre
3/ gram, mean pore size is
[embodiment 3]
Except TiCl
4Amount be 0.8 the gram outside, all the other conditions are identical with [embodiment 1].The specific surface area of the Ti-HMS catalyzer that makes is 930 meters
2/ gram, pore volume is 1.0 centimetres
3/ gram, mean pore size is
[embodiment 4]
Except template was 16.0 gram cetylamines, all the other conditions were identical with [embodiment 1].The specific surface area of the Ti-HMS catalyzer that makes is 870 meters
2/ gram, pore volume is 0.95 centimetre
3/ gram, mean pore size is
[embodiment 5]
Except template was 12.5 gram amino dodecanes, all the other conditions were identical with [embodiment 1].The specific surface area of the Ti-HMS catalyzer that makes is 940 meters
2/ gram, pore volume is 1.0 centimetres
3/ gram, mean pore size is
[comparative example 1]
In room temperature with under stirring, 4.3 gram tetrabutyl titanates are joined the ethanolic soln that forms tetrabutyl titanate in 20 milliliters of ethanol, restrain commercially available silica gel (80-120 order, 340 meters of the specific surface areas that drying treatment are crossed with 20.0
2/ gram, 0.71 centimetre of pore volume
3/ gram, mean pore size
) join in 60 milliliters of ethanol.Under nitrogen atmosphere, the ethanolic soln of tetrabutyl titanate is added drop-wise in the ethanol that contains commercially available silica gel, at room temperature stir 2 hours after-filtration of this mixture, with washing with alcohol filtrate three times.Solid in air atmosphere after 110 ℃ of above-mentioned filtrations of oven dry 12 hours 600 ℃ of roastings 4 hours, promptly gets titaniferous SiO 2 catalyst.In one 100 milliliters there-necked flask, add 50 milliliters of cumene solutions that contain 4.0 gram hexamethyldisilazanes, the titaniferous silica sample of the above-mentioned preparation of 10.0 grams is joined in the flask, under stirring and refluxing, elevated temperature to 150 ℃, and reaction 4 hours under this temperature.Under this temperature, the hexamethyldisilazane of evaporated in vacuo remnants and isopropyl benzene solvent promptly make the TiO that handles through silanization then
2/ SiO
2Catalyzer.Its specific surface area of the catalyzer that so makes is 270 meters
2/ gram, pore volume is 0.61 centimetre
3/ gram, mean pore size is
[comparative example 2]
Take by weighing commercially available silica gel (80-120 order, 340 meters of specific surface areas that 20.0 gram dryings were handled
2/ gram, 0.71 centimetre of pore volume
3/ gram, mean pore size
) be immersed in 60 milliliters of octane solvents.Under stirring and nitrogen atmosphere, will be dissolved with 2.4 gram TiCl
420 milliliters of octane mixtures be added drop-wise in the above-mentioned paste mixture, be warming up to 100 ℃ after constant temperature stirring and refluxing 2 hours, elevated temperature to 150 ℃ solvent evaporated under vacuum condition then.The solid of above-mentioned acquisition is put in the quartz tube reactor, in nitrogen atmosphere, elevated temperature to 700 ℃, and this roasting temperature 2 hours, reduce the temperature to 300 ℃ after, feed saturated steam 3.0 grams, nitrogen purging 2 hours.Further reduce temperature to 220 ℃, the nitrogen that will contain 6.0 gram hexamethyldisilazane saturation steams under this temperature were used nitrogen purging 2 hours then by beds, promptly made the TiO that handles through silanization
2/ SiO
2Catalyzer.Its specific surface area of the catalyzer that so makes is 280 meters
2/ gram, pore volume is 0.65 centimetre
3/ gram, mean pore size is
[embodiment 6～10]
Preparing epoxypropane by epoxidation of propene (PO)
In 300 milliliters of stainless steel autoclaves, add catalyzer 2.0 grams of [embodiment 1～5], the cumene solution of 46.0 gram 35.0 (weight) % isopropyl benzene hydroperoxides (CHP), behind the elevated temperature to 90 ℃, add 43.0 gram propylene, system pressure is 1.5MPa, stirring reaction 2 hours.Reaction result sees Table 1.
[comparative example 3～4]
The catalyzer of [comparative example 1～2] is checked and rated according to [embodiment 6～10], and reaction result sees Table 1.
Table 1
[embodiment 11～15]
Preparing epoxypropane by epoxidation of propene (PO)
In 300 milliliters of stainless steel autoclaves, add catalyzer 2.0 grams of [embodiment 1～5], the ethylbenzene solution of 71.0 gram 20 (weight) % ethylbenzene hydroperoxides (EBHP), behind the elevated temperature to 80 ℃, add 35.0 gram propylene, system pressure is 1.3MPa, stirring reaction 2 hours.Reaction result sees Table 2.
[comparative example 5～6]
The catalyzer of [comparative example 1～2] is checked and rated according to [embodiment 11～15], and reaction result sees Table 2.
Table 2
[embodiment 16～20]
The cyclohexene ring oxidation prepares epoxy cyclohexane (CHO)
In 100 milliliters of Florence flasks, add catalyzer 1.0 grams of [embodiment 1～5], the cumene solution of 23.0 gram 35.0 (weight) % isopropyl benzene hydroperoxides (CHP), behind the elevated temperature to 60 ℃, add 8.5 gram tetrahydrobenzene, system pressure is 0.1MPa, under agitation reacts 1 hour.Reaction result sees Table 3.
[comparative example 7～8]
The catalyzer of [comparative example 1～2] is checked and rated according to [embodiment 16～20], and reaction result sees Table 3.
Table 3
[embodiment 21～25]
Epoxidation of styrene prepares Styryl oxide (SMO)
In 100 milliliters of Florence flasks, add catalyzer 1.0 grams of [embodiment 1～5], the cumene solution of 23.0 gram 35.0 (weight) % isopropyl benzene hydroperoxides (CHP), behind the elevated temperature to 80 ℃, add 11.0 gram vinylbenzene, system pressure is 0.1MPa, stirring reaction 2 hours.Reaction result sees Table 4.
[comparative example 9～10]
The catalyzer of [comparative example 1～2] is checked and rated according to [embodiment 21～25], and reaction result sees Table 4.
Table 4
Claims (10)
1, a kind of method of producing epoxide, with alkene and organo-peroxide is raw material, reaction system is the inert non-polar compound is solvent, in temperature of reaction is 25～200 ℃, the reaction absolute pressure is 0.1～10MPa, the mol ratio of alkene and organo-peroxide is 1～20: 1, the mol ratio of solvent and alkene is 0.01～60: 1, catalyst levels be reacted under 0.1～10% condition of weight of solvent 0.5～24 hour epoxide, wherein used catalyzer is Ti-HMS, and its preparation may further comprise the steps:
A) with the silicon ester be the silicon source, general formula is RNH
2Organic amine be template, organic alcohol and water is a solvent, wherein R is the chain alkylene that contains 7～36 carbon atoms, with molar ratio computing RNH
2/ Si=0.01～1.0: 1, water/pure volume ratio is 0.01～5: 1, and above-mentioned reaction mixture was at room temperature stirred crystallization 0.5～48 hour, and crystallized product is through separation, washing, drying, and 300～1000 ℃ of roastings obtained HMS in 0.5～48 hour;
B) above-mentioned HMS being reacted 0.5～100 hour with the inorganic titanium compound that is dissolved in the organic solvent at 25～300 ℃, obtain Ti-HMS, is 5～200 with molar ratio computing Si/Ti wherein;
C) above-mentioned Ti-HMS is activated 0.5～48 hour at 300～1000 ℃, obtain catalyst Precursors;
D) the above-mentioned catalyst Precursors that obtains was handled 0.5～100 hour with the organic silicon solution that is dissolved in the organic solvent at 25～400 ℃, obtained the Ti-HMS catalyzer through the silanization processing, wherein organosilyl consumption is 10～70% of a catalyst Precursors weight.
2,, it is characterized in that described alkene is alkene, cycloolefin or fragrant alkene according to the method for the described production epoxide of claim 1; Described organo-peroxide is ethylbenzene hydroperoxide, isopropyl benzene hydroperoxide, tertbutyl peroxide or cyclohexyl hydroperoxide; It is described that reaction system is the inert non-polar compound is ethylbenzene, isopropyl benzene, Trimethylmethane or hexanaphthene.
3, according to the method for the described production epoxide of claim 1, it is characterized in that temperature of reaction is 40～130 ℃, the reaction absolute pressure is 0.1～5.0MPa, the mol ratio of alkene and organo-peroxide is 2～15: 1, the mol ratio of solvent and alkene is 0.1～20: 1, and catalyst consumption is 0.5～5% of a weight of solvent.
4,, it is characterized in that a) silicon ester described in the step is methyl silicate, tetraethoxy, positive silicic acid n-propyl, positive isopropyl silicate or butyl silicate according to the method for the described production epoxide of claim 1; Described alcohol is at least a in methyl alcohol, ethanol, n-propyl alcohol, Virahol, vinyl alcohol, allyl alcohol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, amylalcohol, hexalin, ethylene glycol or the propylene glycol; R is the chain alkylene that contains 10～20 carbon atoms; With molar ratio computing RNH
2/ Si=0.1～5: 1, water/pure volume ratio is 0.1～2: 1, the crystallization time is 1～24 hour.
5, according to the method for the described production epoxide of claim 1, it is characterized in that b) inorganic titanium compound described in the step is titanium tetrachloride, titanous chloride, titanium tetrabromide, titanium tribromide, titanium tetra iodide or titanium triiodide, is 10～100 with molar ratio computing Si/Ti wherein; Described organic solvent is selected from least a in benzene,toluene,xylene, trimethylbenzene, ethylbenzene, diethylbenzene, triethyl-benzene, isopropyl benzene, hexane, hexanaphthene, heptane, octane, nonane, decane, undecane or the dodecane; Carrying the titanium temperature is 50～250 ℃, and carrying the titanium time is 1～48 hour.
6, according to the method for the described production epoxide of claim 1, it is characterized in that c) activation temperature is 400～800 ℃ in the step, soak time is 1～24 hour.
7, according to the method for the described production epoxide of claim 1, it is characterized in that d) organosilicon is selected from least a in halosilanes, silazane or the silylamine in the step; Described organic solvent is selected from least a in benzene,toluene,xylene, trimethylbenzene, ethylbenzene, diethylbenzene, triethyl-benzene, isopropyl benzene, hexane, hexanaphthene, heptane, octane, nonane, decane, undecane or the dodecane; The silanization temperature is 50～350 ℃, and the silanization time is 1～48 hour.
8,, it is characterized in that halosilanes is selected from trimethylchlorosilane, chlorotriethyl silane, tripropyl chlorosilane, tributyl chlorosilane, chlorodimethyl silane, dimethyldichlorosilane(DMCS), 3,5-dimethylphenyl chlorosilane, dimethyl ethyl chlorosilane, dimethyl n propyl chloride silane, dimethyl isopropyl chloride silane, normal-butyl dimethylchlorosilane or aminomethyl phenyl chlorosilane according to the method for the described production epoxide of claim 7; Silazane is selected from hexamethyldisilazane, 1,1,3,3-tetramethyl-disilazane, 1,3-two (chloromethyl) tetramethyl-disilazane, 1,3-divinyl-1,1,3,3-tetramethyl-disilazane or 1,3-phenylbenzene tetramethyl-disilazane; Silylamine is selected from N-trimethyl-silyl-imidazole, N-t-butyldimethylsilyl imidazoles, N-dimethylethylsilyl imidazoles, N-dimethyl n propyl group silyl imidazoles, N-dimethyl sec.-propyl silyl imidazoles, N-trimethyl silyl dimethyl amine or N-trimethyl silyl diethylamide.
9, the method for described according to Claim 8 production epoxide is characterized in that halosilanes is selected from trimethylchlorosilane, chlorotriethyl silane, chlorodimethyl silane, dimethyldichlorosilane(DMCS), 3,5-dimethylphenyl chlorosilane or dimethyl ethyl chlorosilane; Silazane is selected from hexamethyldisilazane or 1,1,3, the 3-tetramethyl-disilazane; Silylamine is selected from N-trimethyl-silyl-imidazole, N-dimethylethylsilyl imidazoles, N-trimethyl silyl dimethyl amine or N-trimethyl silyl diethylamide.
10, according to the described method for preparing epoxide of claim 1, it is characterized in that a) also containing acid or alkali in the step reaction mixture, the mol ratio of acid or alkali and silicon ester is 0.001～10: 1, wherein acid is selected from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetate or propionic acid, and alkali is selected from sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood or ammoniacal liquor.
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| CN102295533A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Preparation method of alpha, alpha-dimethyl benzyl alcohol |
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| WO2021192592A1 (en) | 2020-03-27 | 2021-09-30 | 住友化学株式会社 | Propylene oxide production apparatus and propylene oxide production method |
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| JP4889865B2 (en) * | 2001-01-31 | 2012-03-07 | 住友化学株式会社 | Method for producing titanium-containing silicon oxide catalyst |
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| CN102295533A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Preparation method of alpha, alpha-dimethyl benzyl alcohol |
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| WO2018021271A1 (en) | 2016-07-29 | 2018-02-01 | 住友化学株式会社 | Method for producing propylene oxide |
| CN108262030A (en) * | 2017-01-04 | 2018-07-10 | 东联化学股份有限公司 | Preparation method and application of titanium-containing silicon oxide material with high thermal stability |
| WO2021060263A1 (en) | 2019-09-25 | 2021-04-01 | 住友化学株式会社 | Method for producing propylene oxide |
| WO2021192592A1 (en) | 2020-03-27 | 2021-09-30 | 住友化学株式会社 | Propylene oxide production apparatus and propylene oxide production method |
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