CN1925911A - 使用混合催化剂体系的环氧化方法 - Google Patents
使用混合催化剂体系的环氧化方法 Download PDFInfo
- Publication number
- CN1925911A CN1925911A CNA2005800030858A CN200580003085A CN1925911A CN 1925911 A CN1925911 A CN 1925911A CN A2005800030858 A CNA2005800030858 A CN A2005800030858A CN 200580003085 A CN200580003085 A CN 200580003085A CN 1925911 A CN1925911 A CN 1925911A
- Authority
- CN
- China
- Prior art keywords
- palladium
- zeolite
- titanium zeolite
- catalyst
- titanium
- 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
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims description 64
- 238000006735 epoxidation reaction Methods 0.000 title abstract description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 187
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 91
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000010457 zeolite Substances 0.000 claims abstract description 79
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 77
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 72
- 239000010936 titanium Substances 0.000 claims abstract description 71
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 65
- 150000001336 alkenes Chemical class 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 12
- 229910004339 Ti-Si Inorganic materials 0.000 claims description 11
- 229910010978 Ti—Si Inorganic materials 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052737 gold Inorganic materials 0.000 claims description 10
- 239000010931 gold Substances 0.000 claims description 10
- 229910000510 noble metal Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 150000002118 epoxides Chemical class 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000001294 propane Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000012159 carrier gas Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 150000002924 oxiranes Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- -1 vacuum Chemical compound 0.000 description 4
- 239000004254 Ammonium phosphate Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 3
- 235000019289 ammonium phosphates Nutrition 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GQNOPVSQPBUJKQ-UHFFFAOYSA-N 1-hydroperoxyethylbenzene Chemical compound OOC(C)C1=CC=CC=C1 GQNOPVSQPBUJKQ-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
本发明为一种在含有含钯的钛沸石和不含钯的钛沸石存在下烯烃与氢和氧环氧化的方法。所述的方法对烯烃用氢和氧的环氧化有良好的生产率和选择性。令人吃惊的是,除了含钯的钛沸石外,不含钯的钛沸石在方法中的存在提高了方法的钯生产率。
Description
发明领域
本发明涉及一种使用混合催化剂体系由氢、氧和烯烃生产环氧化物的环氧化方法。所述的混合催化剂体系包括含钯的钛沸石和不含钯的钛沸石。令人吃惊的是,除了含钯的钛沸石外,不含钯的钛沸石的存在使单位钯量的生产率提高。
发明背景
已开发了许多不同的生产环氧化物的方法。通常,环氧化物通过烯烃与氧化剂在催化剂存在下反应来制备。由丙烯和有机氢过氧化物氧化剂例如乙基苯氢过氧化物或叔丁基氢过氧化物生产环氧丙烷是商业上实施的技术。这一方法在溶解的钼催化剂(参见US 3351635)或非均相氧化钛/氧化硅催化剂(参见US 4367342)存在下进行。过氧化氢为另一种适用于生产环氧化物的氧化剂。在US 4833260中说明了使用过氧化氢和钛硅沸石的烯烃环氧化。这两种方法的一个缺点是在与烯烃反应以前需要预先制备氧化剂。
另一种商业上实施的技术是通过与氧在银催化剂上的反应使乙烯直接环氧化生成环氧乙烷。遗憾的是,银催化剂不适用于更高碳烯烃的商业环氧化。所以,更新的研究集中在更高碳烯烃与氧和氢在催化剂存在下的直接环氧化。在这一方法中,据认为氧和氢就地反应生成氧化剂。因此,一种有效方法(和催化剂)的开发希望一种比采用预先制备氧化剂的商业技术有更低费用的技术。
为了用于更高碳烯烃的直接环氧化,已提出许多不同的催化剂。例如,JP 4-352771和US 5859265、6008388和6281369公开了使用结合贵金属例如钯的钛沸石催化剂来生产环氧丙烷。此外,公开的其它催化剂还包括负载在氧化钛上的金(例如参见US 5623090)以及负载在钛硅沸石上的金(例如参见WO 98/00413)。
还公开了用于烯烃用氢和氧环氧化的混合催化剂体系。例如,JP4-352771在实施例13中公开了钛硅沸石和Pd/C的混合物用于丙烯的环氧化。US 6498259公开了一种钛沸石和负载钯配合物的催化剂混合物,其中钯负载在炭、氧化硅、氧化硅-氧化铝、氧化钛、氧化锆和氧化铌上。此外,US 6441204公开了一种钛沸石和钯/含铌载体的混合物。此外,US 6307073公开了一种适用于烯烃环氧化的混合催化剂体系,所述的混合催化剂体系包含钛沸石和含金的负载催化剂,其中金负载在载体上,例如氧化锆、氧化钛和氧化钛-氧化硅。
所公开的直接环氧化催化剂的一个缺点是,它们都比最佳选择性或生产率低。正如任何一种化学方法的情况一样,仍然希望进一步改进直接环氧化方法和催化剂。
我们已发现一种适用于烯烃用氧和氢直接环氧化的有效方便的环氧化催化剂混合物。
发明概述
本发明为一种烯烃环氧化方法,所述的方法包含烯烃、氧和氢在包括含钯的钛沸石和不含钯的钛沸石的催化剂混合物存在下反应。与仅使用含钯的钛沸石相比,所述的方法令人吃惊地提高了钯的环氧化生产率。
发明详述
本发明的方法使用一种包括含钯的钛沸石和不含钯的钛沸石的催化剂混合物。在本专业中含钯的钛沸石催化剂是大家熟悉的,例如在JP 4-352771和US 5859265、6008388和6281369中公开。这样的催化剂包括钯和钛沸石。含钯的钛沸石还可含有其它贵金属,优选铂、金、银、铱、铼、钌或锇,而最优选铂或金。
含钯的钛沸石和不含钯的钛沸石都含有钛沸石。钛沸石为这样一类沸石物质,其中钛原子取代分子筛晶格骨架中部分硅原子。这样的场质在本专业中是大家熟悉的。特别优选的钛沸石包括这样一类通常称为钛硅沸石的催化剂,特别是“TS-1”(有类似于ZSM-5硅铝酸盐沸石的MFI拓扑)、“TS-2”(有类似于ZSM-11硅铝酸盐沸石的MEL拓扑)和“TS-3”(正如在比利时专利1001038中公开的)。具有与β沸石、丝光沸石、ZSM-48、ZSM-12和MCM-41同晶的骨架结构的含钛催化剂也是适用的。钛沸石的晶格骨架中优选不含除钛、硅和氧以外的元素,虽然少量的硼、铁、铝、钠、钾、铜等也可能存在。
在含钯的钛沸石中存在的钯的典型数量为约0.01-20wt%、优选0.01-10wt%、特别是0.03-5wt%。钯结合到催化剂中的方式不是特别重要的。例如,可通过浸渍等将钯负载在沸石上。另一方面,可通过离子交换例如四胺合氯化钯离子交换将钯结合到沸石中。
对用作钯源的钯化合物的选择没有特别的限制。例如,适合的化合物包括钯的硝酸盐、硫酸盐、卤化物(例如氯化物、溴化物)、羧酸盐(例如乙酸盐)和胺配合物。钯可处于0至+4的氧化态或这样的氧化态组合。为了达到所希望的氧化态或其组合,钯化合物可在加到催化剂中以后完全或部分预还原。但是,满意的催化性能可在没有任何预还原的条件下达到。为了达到钯的活性状态,可将含钯的钛沸石进行预处理,例如在氮、真空、氢或空气中热处理。
如果含钯的钛沸石含有其它的贵金属例如铂、金、银、铱、铼、钌或锇,那么贵金属的数量通常为约0.001-10wt%、优选0.01-5wt%。将其它贵金属结合到催化剂中的方式不特别重要。可使用用于加入钯的相同技术将其它贵金属加到钛沸石中。可在钯加入以前、加入过程中或加入以后将其它贵金属加入。
本发明的方法还使用一种不含钯的钛沸石。所谓“不含钯的”是指钛沸石不含加入的钯。不含钯的钛沸石可与构成本发明的含钯的钛沸石为相同沸石或不同沸石。
所述的含钯的钛沸石和不含钯的钛沸石可作为粉末混合物或小球混合物用于所述的环氧化法。此外,还可在用于环氧化以前将所述的含钯的钛沸石和不含钯的钛沸石一起造粒或挤条。如果在一起造粒或挤条,那么催化剂混合物另外还可含有粘合剂等,以及可在用于环氧化以前模化、喷雾干燥、成型或挤条成任何希望的形状。含钯的钛沸石与不含钯的钛沸石的重量比并不特别重要。但是,含钯的钛沸石与不含钯的钛沸石的重量比为0.01-100(g含钯的钛沸石/g不含钯的钛沸石)是优选的,特别优选0.1-10。
含钯的钛沸石和不含钯的钛沸石的混合物适用于催化烯烃用氧和氢的环氧化。这一环氧化方法包括烯烃、氧和氢在催化剂混合物存在下接触。适合的烯烃包括有至少一个碳-碳双键的任何烯烃,通常有2-60个碳原子。优选的是,烯烃为2-30个碳原子的无环链烯烃;本发明的方法特别适用于C2-C6烯烃环氧化。可存在一个以上双键,例如在二烯烃或三烯烃中。所述的烯烃可为烃类(也就是仅含有碳原子和氢原子)或可含有官能基团,例如卤基、羧基、羟基、醚基、羰基、氰基或硝基等。本发明的方法特别适用于将丙烯转化成环氧丙烷。
对于环氧化法来说,氧和氢也是需要的。虽然任何氧源和氢源都是适合的,但分子氧和分子氢是优选的。
本发明的环氧化在有效进行所需烯烃环氧化的温度下进行、优选0-250℃、更优选20-100℃。氢与氧的摩尔比通常可为H2∶O2=1∶10至5∶1、特别优选1∶5至2∶1。氧与烯烃的摩尔比通常为2∶1至1∶20、优选1∶1至1∶10。对于某些烯烃来说,相对高的氧/烯烃摩尔比(例如1∶1至1∶3)可能是有利的。载气也可用于环氧化法。作为载气,任何希望的惰性气体都可使用。烯烃与载气的摩尔比通常为100∶1至1∶10、特别是20∶1至1∶10。
作为惰性载气,除氮和二氧化碳外,稀有气体例如氦、氖和氩也是适用的。1-8个碳原子、特别是1-6个碳原子、优选1-4个碳原子的饱和烃类例如甲烷、乙烷、丙烷和正丁烷也是适用的。氮和饱和C1-C4烃类是优选的惰性载气。也可使用所列惰性载气的混合物。
具体地说,在丙烯的环氧化中,可以这样的方式提供丙烷,以致在适当过量的载气存在下,安全地避开丙烯、丙烷、氢和氧混合物的爆炸极限,因此可在反应器中或进料管线和排料管线中不生成爆炸混合物。
含钯的钛沸石和不含钯的钛沸石的用量可随包括含钯的钛沸石中钯的数量在内的许多因素变化。可在钛(含钯的钛沸石和不含钯的钛沸石所含的)与单位时间送入的烯烃的摩尔比的基础上决定催化剂混合物的总量。通常,足够的催化剂混合物存在以提供0.0001-0.1h的钛/烯烃进料比。可在气时空速的基础上也就是在单位时间单位催化剂体积的烯烃、氢、氧和载气的总体积(简称GHSV)的基础上决定环氧化所需的时间。通常GHSV为10-10000h-1是满意的。
视要反应的烯烃而定,本发明的环氧化可在液相、气相或超临界相中进行。当使用液体反应介质时,催化剂优选呈悬浮液或固定床形式。所述的方法可用连续流、半间歇或间歇操作方式进行。
如果环氧化在液相(或超临界相)中进行,在1-100bar和一种或多种溶剂存在下进行是有利的。适合的溶剂包括但不限于醇类、水、超临界CO2或其混合物。适合的醇包括C1-C4醇,例如甲醇、乙醇、异丙醇和叔丁醇及其混合物。也可使用氟化的醇。使用上述醇与水的混合物是优选的。
如果环氧化在液相(或超临界相)中进行,使用缓冲剂是有利的。
通常将缓冲剂加到溶剂中,以便生成缓冲剂溶液。在反应中使用缓冲剂溶液,以便抑制在环氧化过程中生成二元醇。在本专业中缓冲剂是大家熟悉的。
适用于本发明的缓冲剂包括任何适合的含氧酸盐,在混合物中它们的性质和比例是这样的,以致溶液的pH值可为3-10、优选4-9、更优选5-8。适合的含氧酸盐含有阴离子和阳离子。盐的阴离子部分可包括这样的阴离子,例如磷酸根、碳酸根、碳酸氢根、羧酸根(例如乙酸根、邻苯二甲酸根等)、柠檬酸根、硼酸根、氢氧根、硅酸根、硅铝酸根等。盐的阳离子部分可包括这样的阳离子,例如铵、烷基铵(例如四烷基铵、吡啶阳离子等)、碱金属、碱土金属等。阳离子的例子包括NH4、NBu4、NMe4、Li、Na、K、Cs、Mg和Ca阳离子。更优选的缓冲剂包含碱金属磷酸盐和磷酸铵缓冲剂。缓冲剂可优选含有一种以上适合盐的组合物。通常,缓冲剂在溶剂中的浓度为约0.0001至约1M、优选约0.001至约0.3M。适用于本发明的缓冲剂还可包括加到反应体系中的氨气。
用本发明的方法生产环氧化物产品。
以下实施例仅用来说明本发明。熟悉本专业的技术人员将会认识到许多在本发明的精神实质和权利要求书范围内的改变。
实施例1:催化剂的制备
催化剂1A:将放在圆底烧瓶中的经喷雾干燥的TS-1(112g,80%TS-1、20%氧化硅;1.7wt%Ti)在空气中在550℃下焙烧,然后浆化在去离子水(250mL)中。将Pd(NH3)4Cl2水溶液(1.3g在90g去离子水中)加到浆液中,混合30分钟以上。将浆液在30℃水浴中在30rpm旋转蒸发器上再混合2h。用过滤法分离固体,通过再浆化在去离子水(140mL)中来洗涤滤饼,然后再次过滤。进行4次洗涤。将固体空气干燥过夜,然后在真空炉中在50℃下干燥8h。进行元素分析,干燥材料含有0.34wt%Pd和1.67wt%Ti;残留氯化物小于20ppm。
干燥的固体通过在炉中加热到110℃(以10℃/min的速率)并在110℃下保持4h,然后加热到150℃(以2℃/min)的速率并在150℃下保持4h来进行空气焙烧。将焙烧过的固体转移到石英管中,并用氢(5%在氮中;100mL/min)在50℃下处理4h,随后在冷却到室温以前仅用氮处理1h,分离出催化剂1A。
催化剂1B:催化剂1B按催化剂1A相同的步骤制备,不同的是Pd(NH3)4Cl2水溶液在30g去离子水中仅含有0.45g Pd(NH3)4Cl2。催化剂1B含有0.11wt%Pd和1.7wt%Ti;残留的氯化物小于20ppm。
催化剂1C:将TS-1粉末(2.2wt%Ti,在550℃下在空气中焙烧)浆化在去离子水(100g)中。在氮气下,将乙酸钯溶液(0.5g在50mL丙酮中)在5min内加到浆液中,然后在氮气下将混合物在23℃下在旋转蒸发器(30rpm)上处理30min,再在50℃下处理4h。在真空下除去大约一半液体,然后用过滤法分离固体,用50g去离子水洗涤两次,然后在110℃下干燥4h。进行元素分析,干燥材料含有0.4wt%Pd和2.17wt%Ti。
将固体转移到石英管中,并用氢(5%在氮中;100mL/min)在60℃下处理2h,随后在冷却到室温以前仅用氮处理1h,分离出催化剂1C。
实施例2:缓冲剂的制备
缓冲剂2A-0.1mol pH值6的磷酸铵缓冲剂:将磷酸二氢铵(NH4H2PO4,11.5g)溶于去离子水(900g)中。然后将氢氧化铵水溶液(30%NH4OH)加到上述溶液中,一直到pH计的pH值读数为6。通过加入去离子水将溶液的体积提高到1000mL。
缓冲剂2B-0.2mol pH值7的磷酸铵缓冲剂:将磷酸二氢铵(23g)溶于去离子水(900g)中。然后将氢氧化铵水溶液(30%NH4OH)加到上述溶液中,一直到pH计的pH值读数为7。通过加入去离子水将溶液的体积提高到1000mL。
实施例3:丙烯在甲醇/水中的环氧化
实施例3A:将催化剂1A(0.2g)、喷雾干燥的TS-1(0.5g,80%TS-1、20%二氧化硅;1.7wt%Ti)、缓冲剂2A(13g)和甲醇(100g)装入300mL不锈钢反应器。然后用含有2v%H2、4v%O2、5v%丙烯、0.5v%甲烷和其余为氮的进料将反应器加压到300psig。通过背压调节器将反应器的压力保持在300psig,进料气体以1600mL/min的速率连续通过反应器(在21℃和1大气压下测量的)。为了在操作过程中将反应器中的溶剂液面保持不变,氧、氮和丙烯进料在通过反应器以前首先通过一个装有1.5L甲醇的2L不锈钢容器(饱和器)。将反应器在1500rpm下搅拌,并将混合物加热到60℃。用在线GC每小时分析一次气体流出物,而用离线GC在操作18h结束时分析液体产物。结果列入表1。
对比例3B:对比例3B按实施例3A的步骤进行,不同的是0.7g催化剂1B用作唯一的催化剂。结果列入表1。
实施例4:丙烯在水中环氧化
实施例4A:将催化剂1C(12g)、TS-1粉末(12g,2.2wt%Ti,在550℃下空气中焙烧)和缓冲剂2B(376g)装入1L不锈钢反应器。然后用含有4v%H2、4v%O2、27v%丙烯、0.5v%甲烷和其余为氮的进料将反应器加压到500psig。通过背压调节器将反应器的压力保持在500psig,进料气体以405L/h的速率连续通过反应器(在21℃和1大气压下测量的)。将反应器在500rpm下搅拌,并将混合物加热到60℃。用在线GC每小时分析一次气体流出物,而用离线GC在操作18h结束时分析液体产物。结果列入表1。
对比例4B:对比例4B按实施例4A的步骤进行,不同的是仅将催化剂1C(12g)和缓冲剂2B(388g)加入反应器。结果列入表1。
结果表明,与仅使用Pd/TS-1相比,使用催化剂混合物(Pd/TS-1+TS-1)有一个意想不到的优点。与仅Pd/TS-1中的钯相比,催化剂混合物中的钯得到更多的环氧化物。例如,实施例3的甲醇操作表明钯的生产率高17%,而实施例4的水操作表明钯的生产率高36%。除了更高的钯生产率外,在催化剂合成方面还有经济性上的优点。正如实施例3中说明的,仅一部分TS-1需要加入钯(虽然需要更高数量的钯),而不含钯的TS-1的加入仍可得到稍高的生产率。这一观测结果可通过在加钯时需要加工较少的TS-1而节省费用。此外,当使用催化剂混合物时,PO/POE选择性不受影响或稍有提高。“POE”指包括环氧丙烷(PO)、丙二醇(PG)、二丙二醇(DPG)、1-甲氧基-2-丙醇(PM-1)、2-甲氧基-1-丙醇(PM-2)和丙酮醇的PO当量。
表1:催化剂活性的比较
实施例 | 催化剂 | 催化剂总重(g) | 催化剂中钯的重量(mg) | PO/POE选择性(%)1 | 催化剂总生产率2 | 钯生产率3 |
3A | 1A+TS-1 | 0.7 | 0.68 | 93 | 0.33 | 340 |
3B* | 1B | 0.7 | 0.77 | 93 | 0.32 | 290 |
4A | 1C+TS-1 | 24 | 48 | 81 | 0.051 | 26 |
4B* | 1C | 12 | 48 | 76 | 0.076 | 19 |
*对比例
1PO/POE选择性=摩尔PO/(摩尔PO+摩尔丙二醇)×100
2催化剂总生产率=生产的POE克数/克催化剂/小时
3钯生产率=生产的POE克数/克钯/小时
Claims (20)
1.一种生产环氧化物的方法,所述的方法包括烯烃、氧和氢在包括含钯的钛沸石和不含钯的钛沸石的催化剂混合物存在下反应。
2.根据权利要求1的方法,其中含钯的钛沸石包括钯和钛硅沸石。
3.根据权利要求2的方法,其中钛硅沸石为TS-1。
4.根据权利要求1的方法,其中含钯的钛沸石包括钯、钛沸石和选自铂、金、银、铱、铼、钌、锇及其混合物的贵金属。
5.根据权利要求4的方法,其中贵金属选自铂、金及其混合物。
6.根据权利要求1的方法,其中含钯的钛沸石含有约0.01至约10wt%的钯。
7.根据权利要求1的方法,其中不含钯的钛沸石为钛硅沸石。
8.根据权利要求1的方法,其中不含钯的钛沸石为TS-1。
9.根据权利要求1的方法,其中烯烃为C2-C6烯烃。
10.根据权利要求1的方法,其中烯烃为丙烯。
11.根据权利要求1的方法,其中烯烃、氢和氧的反应在溶剂中进行。
12.根据权利要求11的方法,其中溶剂选自水、C1-C4醇、超临界CO2及其混合物。
13.根据权利要求11的方法,其中溶剂含有缓冲剂。
14.一种包含丙烯、氢和氧在溶剂中在包括含钯的钛硅沸石和不含钯的TS-1的催化剂混合物存在下反应的方法,其中含钯的钛硅沸石包括钯和钛硅沸石。
15.根据权利要求14的方法,其中钛硅沸石为TS-1。
16.根据权利要求14的方法,其中含钯的钛沸石还含有选自铂、金、银、铱、铼、钌、锇及其混合物的贵金属。
17.根据权利要求14的方法,其中溶剂选自水、C1-C4醇、超临界CO2及其混合物。
18.根据权利要求14的方法,其中溶剂含有缓冲剂。
19.一种用权利要求1的方法生产的产品。
20.一种用权利要求14的方法生产的产品。
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US3351635A (en) * | 1966-03-14 | 1967-11-07 | Halcon International Inc | Epoxidation process |
US4367342A (en) * | 1969-04-02 | 1983-01-04 | Shell Oil Company | Olefin epoxidation |
IN142430B (zh) * | 1975-04-21 | 1977-07-09 | Standard Oil Co | |
IT1152299B (it) * | 1982-07-28 | 1986-12-31 | Anic Spa | Procedimento per l'espossidazione di composti olefinici |
IT1216500B (it) | 1988-03-23 | 1990-03-08 | Eniricerche S P A Milano Enich | Procedimento per la preparazione di materiali sintetici cristallini porosi costituiti da ossidi di silicio e titanio. |
JP3044836B2 (ja) | 1991-05-28 | 2000-05-22 | 東ソー株式会社 | プロピレンオキシドの製法 |
DE4425672A1 (de) * | 1994-07-20 | 1996-01-25 | Basf Ag | Oxidationskatalysator, Verfahren zu seiner Herstellung und Oxidationsverfahren unter Verwendung des Oxidationskatalysators |
JP2615432B2 (ja) * | 1994-10-28 | 1997-05-28 | 工業技術院長 | 金−酸化チタン含有触媒による炭化水素の部分酸化方法 |
ES2156391T3 (es) | 1996-07-01 | 2001-06-16 | Dow Chemical Co | Proceso para la oxidacion directa de olefinas a oxidos de olefinas. |
US6008388A (en) * | 1998-04-16 | 1999-12-28 | Arco Chemical Technology, L.P. | Epoxidation process |
US6063942A (en) * | 1999-09-27 | 2000-05-16 | Arco Chemical Technology, L.P. | Catalyst preparation and epoxidation process |
US6194591B1 (en) * | 2000-04-27 | 2001-02-27 | Arco Chemical Technology, L.P. | Aqueous epoxidation process using modified titanium zeolite |
US6307073B1 (en) * | 2000-07-25 | 2001-10-23 | Arco Chemical Technology, L.P. | Direct epoxidation process using a mixed catalyst system |
US6281369B1 (en) * | 2000-12-07 | 2001-08-28 | Arco Chemical Technology, L.P. | Epoxidation catalyst and process |
US6498259B1 (en) * | 2001-10-19 | 2002-12-24 | Arco Chemical Technology L.P. | Direct epoxidation process using a mixed catalyst system |
US6441204B1 (en) * | 2001-10-19 | 2002-08-27 | Arco Chemical Technology, L.P. | Direct epoxidation process using a mixed catalyst system |
US6403815B1 (en) | 2001-11-29 | 2002-06-11 | Arco Chemical Technology, L.P. | Direct epoxidation process using a mixed catalyst system |
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