TWI432262B - Method for making epoxides - Google Patents
Method for making epoxides Download PDFInfo
- Publication number
- TWI432262B TWI432262B TW101128916A TW101128916A TWI432262B TW I432262 B TWI432262 B TW I432262B TW 101128916 A TW101128916 A TW 101128916A TW 101128916 A TW101128916 A TW 101128916A TW I432262 B TWI432262 B TW I432262B
- Authority
- TW
- Taiwan
- Prior art keywords
- titanium
- molecular sieve
- present
- reaction
- compound
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 54
- 150000002118 epoxides Chemical class 0.000 title claims 3
- 239000002808 molecular sieve Substances 0.000 claims description 44
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 44
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 37
- ZPPUVHMHXRANPA-UHFFFAOYSA-N germanium titanium Chemical compound [Ti].[Ge] ZPPUVHMHXRANPA-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- -1 olefin compound Chemical class 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 1
- 150000002924 oxiranes Chemical class 0.000 description 20
- 230000008569 process Effects 0.000 description 16
- 239000000126 substance Substances 0.000 description 12
- 238000006735 epoxidation reaction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- RGZQGGVFIISIHZ-UHFFFAOYSA-N strontium titanium Chemical compound [Ti].[Sr] RGZQGGVFIISIHZ-UHFFFAOYSA-N 0.000 description 10
- 229910052723 transition metal Inorganic materials 0.000 description 10
- 150000003624 transition metals Chemical class 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 8
- 229910000420 cerium oxide Inorganic materials 0.000 description 7
- 239000000084 colloidal system Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 7
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 229940091250 magnesium supplement Drugs 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- DPGAAOUOSQHIJH-UHFFFAOYSA-N ruthenium titanium Chemical compound [Ti].[Ru] DPGAAOUOSQHIJH-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 229960003390 magnesium sulfate Drugs 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- MYXPXPFUKKHRQQ-UHFFFAOYSA-N [Ti].[Re] Chemical compound [Ti].[Re] MYXPXPFUKKHRQQ-UHFFFAOYSA-N 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- PFZWDJVEHNQTJI-UHFFFAOYSA-N antimony titanium Chemical compound [Ti].[Sb] PFZWDJVEHNQTJI-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KQQCTWHSWXCZHB-UHFFFAOYSA-N azane;propan-2-ol Chemical compound N.CC(C)O KQQCTWHSWXCZHB-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229960005336 magnesium citrate Drugs 0.000 description 1
- 235000002538 magnesium citrate Nutrition 0.000 description 1
- 239000004337 magnesium citrate Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229960000816 magnesium hydroxide Drugs 0.000 description 1
- 235000012254 magnesium hydroxide Nutrition 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 description 1
- 239000002351 wastewater Substances 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
-
- 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
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- 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
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本發明係關於一種製造環氧化物之方法,更詳而言,係關於一種利用含鎂之鈦-矽分子篩作為催化劑之環氧化物之製法。
製造環氧化物的方法有氯醇法、共氧化法以及直接氧化法等。使用氯醇法製造環氧化物,在反應後會產生大量的含氯廢水對環境造成危害;使用共氧化法製造環氧化物,其製程複雜且具多種聯產品。直接氧化法又可分為氧氣直接氧化法以及過氧化物直接氧化法,利用直接氧化法生產環氧化物係直接通入純氧作為反應物,其製程簡單且無中間產物,但該方法之產物選擇性較低。由於前述缺點,因此利用過氧化物作為氧化劑進行環氧化反應之過氧化物直接氧化法成為目前廣為使用的方法,該方法通常使用鈦-矽分子篩作為催化劑,反應後催化劑與產物易分離。過氧化物直接氧化法不會對環境造成危害且不需耗費大量氧氣,但環氧化物選擇率及產率仍有待提升。
通常結晶性的鈦-矽分子篩係利用水熱法製備,於第5,290,533、5,888,471、5,977,009、6,042,807、6,083,864、6,329,537、6,972,337及7,288,237號美國專利中皆提及,以水熱法製備鈦-矽分子篩時若有鹼金屬離子或鹼土金屬離子的存在會導致非預期的晶相形成,使得鈦-矽分子篩的催化活性下降,因此反應溶液中應盡量避免
該些金屬離子的存在。
惟,開發一種能提高原料轉化率、產物選擇率和產率之環氧化物製法,仍為一迫切待解之課題。
本發明提供一種製造環氧化物之方法,包括:利用如下式(I)之鈦-矽分子篩作為觸媒,使烯烴類化合物及氧化劑進行反應,俾形成環氧化物:(Mgx
Tiy
Si)Oz
式(I)
其中,x為0.001至0.05,y為0.005至0.1,z為x+2y+2。
於一具體實施例中,該鈦-矽分子篩之骨架為MFI、MEL、BEA、ZSM-48、MTW或MCM-41結構。
在前述之方法中,該烯烴類化合物與氧化劑之莫耳比係介於1:100至100:1,較佳係介於1:10至10:1。反應進行的溫度並無特別限制,通常為0至150℃,較佳為25至120℃。反應滯留時間為1分鐘至48小時,較佳為10分鐘至8小時。本發明之方法,可在任何壓力下進行,但較佳為1至100大氣壓,以增加氣體反應物之溶解度。
本發明所揭露之反應程序可使用任何適當的反應容器或儀器,例如固定床、輸送床、流體床、漿態攪拌、或連續流攪拌反應器在單相或兩相系統中以批次式、連續式或半連續式的方式進行。
進行反應時,觸媒的使用量並沒有嚴格的限制,該觸媒用量只需在最短的時間內使環氧化反應能完全進行即
可。於一實施例中,本發明之方法係以批次式進行環氧化反應,通常,1莫耳之烯烴類化合物係使用0.001至10克之鈦-矽分子篩。於另一實施例中,本發明之方法係於固定床反應器中進行,於固定床反應器中進行環氧化反應時,通常,每小時每公斤的觸媒量對應1至100莫耳的烯烴類化合物。在整個環氧化反應混合物中鈦的濃度通常維持在10到10000 ppm。
本發明之方法,不僅製程簡單且具有較高之過氧化氫轉化率及高環氧化物產率等優點,實利於產業上之應用。
以下係藉由特定的具體實施例說明本發明之實施方式,熟習此技藝之人士可由本說明書所揭示之內容輕易地瞭解本發明之優點及功效。本發明亦可藉由其它不同之實施方式加以施行或應用,本說明書中的各項細節亦可基於不同觀點與應用,在不悖離本發明所揭示之精神下賦予不同之修飾與變更。
本發明方法所使用之鈦-矽分子篩在無水狀態的化學式為(Mgx
Tiy
Si)Oz
式(I)
其中,x為0.001至0.05,y為0.005至0.1,z為x+2y+2。
該鈦-矽分子篩可為粉末狀、團塊狀、微球狀、單塊狀、押出成型或其他任何型式。
為得到該鈦-矽分子篩,本發明復揭露鈦-矽分子篩之
製法,係包括:於鹼性環境下將矽源、鈦源、鹼土金屬源及模版劑混合均勻後,再加熱得到混合膠體後;接著將該混合膠體於100至200℃(較佳為140至185℃)下進行水熱反應持續1小時至10天(較佳為6小時至3天);最後於300至800℃升溫條件下煅燒該經水熱反應之含鹼土金屬之混合膠體0.5至24小時,以得到鈦-矽分子篩。此外,本發明之固體觸媒之製法復可包括於形成混合膠體後,在該混合膠體中混入分散液,再對含分散液之混合膠體進行水熱處理,其中,該分散液係包括水和二氧化矽溶膠之分散液。
水熱反應合成得到之鈦-矽分子篩晶體可以藉由任何適當的傳統方法將該晶體自反應溶液中分離出來,該些方法包括過濾、離心、傾析或其他類似的方式。
本發明之鈦-矽分子篩之製法中所使用之矽源,包括,但不限制於:燻矽(二氧化矽)、二氧化矽凝膠、二氧化矽溶膠、四烷基矽酸酯類,例如,四甲基矽酸酯、四乙基矽酸酯、四丙基矽酸酯及四丁基矽酸酯。二氧化矽溶膠的實例如:杜邦公司之Ludox AS-40、Ludox AS-30、Ludox AM-30、Ludox TM-40、Ludox TM-50、Ludox AM-30、Ludox HS-30、Ludox HS-40或日產化學公司之SNOWTEX-40、SNOWTEX-50、SNOWTEX-C、SNOWTEX-N、SNOWTEX-20L、SNOWTEX-ZL、SNOWTEX-UP或其他類似產品。
本發明之鈦-矽分子篩之製法中所使用之鈦源,包括,但不限制於:鈦鹽(如,鈦鹵化物)、四烷基鈦酸酯。於較佳實施例中所使用之鈦源包括,但不限制於:鈦酸四
甲酯、鈦酸四乙酯、正-鈦酸四丙酯、正-鈦酸四丁酯、鈦酸四第二丁酯、異-鈦酸四丁酯、鈦酸四第三丁酯或其組成。
本發明之鈦-矽分子篩之製法中所使用之鹼土金屬源為鎂源例如,鎂烷氧化物或鎂鹽,如:鎂鹵化物、氫氧化鎂、碳酸鎂、磷酸鎂、硫酸鎂、硝酸鎂、醋酸鎂及矽酸鎂。
本發明之鈦-矽分子篩之製法中所使用之模板劑,包括,但不限制於:含氮有機鹼性物質水溶液或醇溶液,其中,該含氮有機鹼性物質之濃度為5至50 wt%,較佳為20至40 wt%。於較佳實施例中,本發明之鈦-矽分子篩之製法中所使用之含氮有機鹼性物質的實例,包括,但不限制於:烷基銨氫氧化物,如:四正丙基氫氧化銨;四正丁基氫氧化銨;烷基銨鹵化物,如:四正丙基溴化銨、四正丁基溴化銨之水溶液或醇溶液;有機胺,如:三乙胺、乙二胺。該醇溶液之醇係指包括具有1至5個碳原子之醇,例如,甲醇、乙醇、異丙醇、正丁醇及第三丁醇,該溶劑可加速鈦-矽分子篩晶體之結晶。
於本發明之鈦-矽分子篩之製法中,該混合膠體中之含氮有機鹼性物質與矽之莫耳比為0.1至0.5,較佳為0.15至0.45,最佳為0.2至0.4。
可藉由改變含氮有機鹼性物質的結構以控制鈦-矽分子篩之構型,例如產生MFI(ZSM-5)、MEL(ZSM-11)、BEA(beta)、ZSM-48、MTW(ZSM-12)、MCM-41或其他預期之構型。舉例而言,四正丙基氫氧化銨可使鈦-矽分子篩為MFI構型。
此外,本發明之鈦-矽分子篩中,復可視需要以含浸法、沉澱法、摻合法或其他類似方法併入其他過渡金屬。含浸法係將過渡金屬溶液分散於適當的溶劑後與分子篩混合形成已含浸過渡金屬的鈦-矽分子篩,並視需要將該已含浸過渡金屬的鈦-矽分子篩作進一步的乾燥以及煅燒,其中,該過渡金屬之濃度範圍為佔本發明之鈦-矽分子篩之總重的0.01至10重量百分比(wt%),較佳為0.05至5 wt%。以此法製得之已含浸過渡金屬的鈦-矽分子篩,該過渡金屬係位於該鈦-矽分子篩之骨架內或骨架外。當利用該已含浸過渡金屬的鈦-矽分子篩作為環氧化反應之催化劑時,全部或部分的過渡金屬會行還原反應。
本發明製備環氧化物之方法中,復可添加額外的溶劑,以溶解鈦-矽分子篩以外之反應物,提供較好的溫度控制,以增加環氧化反應的速率和選擇率,其中,以該環氧化反應混合物之重量計,該溶劑佔該環氧化反應混合物重量之1至99 wt%,且該溶劑於環氧化反應之溫度下為液態。
本發明之環氧化物之製法中,該溶劑包括,但不限於:酮類、醚類、脂肪族、芳香族碳氫化物、鹵化碳氫化合物、醇類、水或過量的烯烴類化合物,且水的存在對於環氧化反應並不會有明顯負面的影響。
此外,於本發明之方法中,可藉由添加有機矽烷化試劑、水溶性鹼性鹽類、非鹼性鹽類、中性鹽類、酸性鹽類、氮原子的有機分子、含氮基鹽類的有機酸或無機酸或羧酸銨鹽水溶液或水-溶劑混合溶液、過氧化氫酸性水溶液以及
氟離子前驅物或含有氟的陰離子物質的過氧化氫水溶液,經由任何已知工藝來活化觸媒,提升環氧化物的選擇率,其可參閱第4,794,198、4,824,976、4,937,216、5,646,314、5,675,026、6,060,610、6,288,004、6,300,506、7,148,381號等全文併入本文參考之美國專利。
本發明之製備環氧化物之方法所使用之烯烴類化合物,包括,但不限制於:至少含有一個乙烯系不飽和官能基(例如C=C)之任何有機物,該有機物之構型為環狀、樹枝狀或直鏈狀,該有機物可包含芳香基。
於一具體實施例中,本發明之製備環氧化物之方法所使用之烯烴類化合物,包括,但不限制於:C2
至C10
之烯烴類化合物。
本發明之製備環氧化物之方法所使用之烯烴類化合物可為單烯烴類化合物,該單烯烴類化合物,包括,但不限制於:乙烯、丙烯、1-丁烯、2-丁烯、1-戊烯或環己烯。
本發明之製備環氧化物之方法所使用之氧化劑為過氧化氫(H2
O2
),包括可以產生或釋放過氧化氫之各種化合物。
當使用含浸過渡金屬的鈦-矽分子篩作為觸媒,則本發明之方法所使用之過氧化氫可為原位生成。舉例而言,將氫氣與氧氣通入含有該含浸過渡金屬(例如鈀、鉑)的鈦-矽分子篩的環氧化反應器中,俾產生過氧化氫。
以下係藉由特定之具體實施例進一步說明本發明之
實施方式,熟習此技藝之人士可由本說明書所揭示之內容瞭解本發明之其他優點與功效。本發明之實施例如下所示,但本發明並不限於這些實施例。
將500毫升(mL)之圓底燒瓶於真空系統中進行氮封,加入60克(g)之四乙基矽酸酯、112 g(20 wt%)之四正丙基氫氧化銨異丙醇溶液,並於5℃持續攪拌,待溫度平衡後加入3.38 g之四正丁基鈦酸酯至圓底燒瓶中,並且持續攪拌1小時。接著,以等壓加料管緩慢添加89.6 g之水,並攪拌1小時,獲得膠體混合物,接著於85℃下除醇1.5小時。在此時同時製備分散液,取21.60 g之二氧化矽溶膠溶液(40%)分散於147 g水中,並將該分散液加入除醇後之膠體混合物中,再攪拌1小時。將此含分散液之經除醇之膠體混合物封入鐵氟龍內襯之不鏽鋼耐壓罐中。並於180℃進行水熱處理120小時,將固體與液體分離後,固體部份以水洗至中性,於100℃乾燥及550℃煅燒8小時,以獲得比較例1之鈦-矽分子篩。
(Mgx
Tiy
Si)Oz
式(I)
將500 mL之圓底燒瓶於真空系統中進行氮封,加入60 g之四乙基矽酸酯、112 g(20 wt%)之四正丙基氫氧化
銨異丙醇溶液,並於5℃持續攪拌,待溫度平衡後加入3.38 g之四正丁基鈦酸酯至圓底燒瓶中,並且持續攪拌1小時。接著,取硫酸鎂0.11 g與89.6 g之水充分混合後,以等壓加料管緩慢添加至圓底燒瓶中,並攪拌1小時,獲得膠體混合物,接著於85℃下除醇1.5小時。在此時同時製備分散液,取21.60 g之二氧化矽溶膠溶液(40%)分散於147 g水中,並將該分散液加入除醇後之膠體混合物中,再攪拌1小時。將此含分散液之經除醇之膠體混合物封入鐵氟龍內襯之不鏽鋼耐壓罐中。並於180℃進行水熱處理120小時,將固體與液體分離後,固體部份以水洗至中性,於100℃乾燥及550℃煅燒8小時,以獲得本發明之鈦-矽分子篩(實施例1),其PXRD光譜分析結果係如第1圖所示,該實施例1具有MFI結構,其於無水狀態的化學式如式(I)所示,其中,x為0.001,y為0.023,z為2.047。
係以與實施例1相同之製法製備,其差異僅在於依下述之硫酸鎂用量在各實施例中添加:0.53 g(實施例2)、1.07 g(實施例3)、2.13 g(實施例4)、3.15 g(實施例5)、4.26 g(實施例6)、5.32 g(實施例7),實施例2至7所製得之本發明之鈦-矽分子篩與不添加額外金屬源的TS-1(比較例1),係如第1圖所示,該實施例2至7與比較例1皆具有MFI結構,其於無水狀態的化學式如表1所示。
分別使用比較例1與實施例1至5製得之鈦-矽分子篩作為觸媒使丙烯與過氧化氫反應產生環氧丙烷,反應步驟如下:於1公升的高壓釜中將3 g之鈦-矽分子篩與500 g之甲醇混合均勻後於密閉條件下,以丙烯氣體建壓至2公斤/平方公分(kg/cm2),反應溫度維持於40℃,接著以每分鐘1.0毫升之進料速率加入16.23 g之過氧化氫(35wt%)至反應系統中,並利用丙烯氣體將壓力維持在2 kg/cm2
。待過氧化氫進料完畢之後直接將反應液取出,利用碘滴定分析過氧化氫之轉化率及以氣相層析法分析各產物之濃度,結果顯示於表2。
XH2O2
=過氧化氫轉化率=過氧化氫消耗莫耳數/過氧化氫總進料莫耳數×100%;SPO
=環氧丙烷選擇率=環氧丙烷生成莫耳數/過氧化氫消耗莫耳數×100%;YPO
=環氧丙烷產率=環氧丙烷生成莫耳數/過氧化氫總進料莫耳數×100%。
請參閱表2,相較於實施例8,含鎂之鈦-矽分子篩中的鎂離子添加量較低(如實施例9及10)時,可在維持相等之環氧丙烷選擇率之情況下,提升過氧化氫的轉化率,且明顯提升環氧丙烷產率。此外,相較於實施例8,本發明之實施例11、12及13,鎂之鈦-矽分子篩中的鎂離子添加量增加時,則可提升環氧丙烷之選擇率。由上述實施例所示,本發明之方法,不僅製程簡單同時又擁有較高之過氧化氫轉化率、環氧化物產率高等優點,實具提升生產效益之功效。
上述實施例僅例示說明本發明之原理及其功效,而非
用於限制本發明。任何熟習此項技藝之人士均可在不違背本發明之精神及範疇下,對上述實施例進行修飾與改變。因此,本發明之權利保護範圍,應如後述之申請專利範圍所列。
第1圖係顯示實施例1至7之鈦-矽分子篩PXRD圖譜。
Claims (12)
- 一種製造環氧化物之方法,包括:利用如下式(I)之鈦-矽分子篩作為觸媒,使烯烴類化合物及氧化劑進行反應,俾形成環氧化物:(Mgx Tiy Si)Oz 式(I)其中,x為0.001至0.05,y為0.005至0.1,z為x+2y+2。
- 如申請專利範圍第1項之方法,其中,該鈦-矽分子篩之骨架為MFI、MEL、BEA、ZSM-48、MTW或MCM-41結構。
- 如申請專利範圍第1項之方法,其中,該烯烴類化合物與氧化劑之莫耳比為1:100至100:1。
- 如申請專利範圍第1項之方法,其中,該烯烴類化合物為C2 至C10 之烯烴類化合物。
- 如申請專利範圍第4項之方法,其中,該烯烴類化合物為單烯烴類化合物。
- 如申請專利範圍第5項之方法,其中,該單烯烴類化合物係乙烯、丙烯、1-丁烯、2-丁烯、1-戊烯或環己烯。
- 如申請專利範圍第6項之方法,其中,該單烯烴類化合物與氧化劑之莫耳比為1:10至10:1。
- 如申請專利範圍第1項之方法,其中,該氧化劑為過氧化氫。
- 如申請專利範圍第1項之方法,復包括溶劑,其中, 該溶劑為水、C1 至C5 之醇或其組合。
- 如申請專利範圍第9項之方法,其中,該溶劑為甲醇。
- 如申請專利範圍第1項之方法,其中,該反應之溫度係為0至150℃。
- 如申請專利範圍第11項之方法,其中,該反應之溫度係為25至120℃。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW101128916A TWI432262B (zh) | 2012-08-10 | 2012-08-10 | Method for making epoxides |
US13/614,684 US8962872B2 (en) | 2012-08-10 | 2012-09-13 | Method for preparing epoxides |
CN201210344544.0A CN103570646B (zh) | 2012-08-10 | 2012-09-14 | 制备环氧化物的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW101128916A TWI432262B (zh) | 2012-08-10 | 2012-08-10 | Method for making epoxides |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201406456A TW201406456A (zh) | 2014-02-16 |
TWI432262B true TWI432262B (zh) | 2014-04-01 |
Family
ID=50043433
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW101128916A TWI432262B (zh) | 2012-08-10 | 2012-08-10 | Method for making epoxides |
Country Status (3)
Country | Link |
---|---|
US (1) | US8962872B2 (zh) |
CN (1) | CN103570646B (zh) |
TW (1) | TWI432262B (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI508935B (zh) * | 2011-08-11 | 2015-11-21 | China Petrochemical Dev Corp Taipei Taiwan | Titanium-silicon molecular sieve and its preparation method and method for producing cyclohexanone oxime using the molecular sieve |
CN110813373A (zh) * | 2019-11-27 | 2020-02-21 | 吉林大学 | 钛硅分子筛催化剂、制备方法及其在烯烃环氧化反应中的应用 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5290533A (en) | 1985-12-19 | 1994-03-01 | Eniricerche S.P.A. | Method for production of a coated substrate with controlled surface characteristics |
DE3780476T2 (de) * | 1986-01-28 | 1992-12-17 | Enichem Sintesi | Verfahren zur epoxydation von olefinischen verbindungen. |
IT1213363B (it) | 1986-10-22 | 1989-12-20 | Eniricerche Spa | Materiale sintetico cristallino poroso contenente ossidi di silicio titanio e gallio. |
US5646314A (en) * | 1994-11-16 | 1997-07-08 | Arco Chemical Technology, L.P. | Process for titanium silicalite-catalyzed epoxidation |
US6042807A (en) | 1997-04-02 | 2000-03-28 | Arco Chemical Technology, L.P. | Tellurium-containing molecular sieves |
US5977009A (en) | 1997-04-02 | 1999-11-02 | Arco Chemical Technology, Lp | Catalyst compositions derived from titanium-containing molecule sieves |
US6252095B1 (en) * | 1998-02-24 | 2001-06-26 | Director-General Of Agency Of Industrial Science And Technology | Catalyst for partially oxidizing unsaturated hydrocarbon |
US6972337B1 (en) | 2004-08-12 | 2005-12-06 | Lyondell Chemical Technology, L.P. | Epoxidation catalyst |
US7288237B2 (en) | 2005-11-17 | 2007-10-30 | Lyondell Chemical Technology, L.P. | Epoxidation catalyst |
EP1970361A1 (en) | 2007-03-13 | 2008-09-17 | Total Petrochemicals Research Feluy | MTO process based on MeAPO molecular sieves combined with an OCP process to make olefins |
EP1970350A1 (en) | 2007-03-13 | 2008-09-17 | Total Petrochemicals Research Feluy | Metalloaluminophosphate molecular sieves with lamellar crystal morphology and their preparation |
CN102441429B (zh) * | 2010-10-11 | 2013-11-27 | 中国石油化工股份有限公司 | 烯烃环氧化催化剂及其制备方法和环氧化烯烃的方法 |
CN102476808B (zh) * | 2010-11-25 | 2013-09-04 | 中国石油化工股份有限公司 | 一种改性钛硅分子筛材料及其制备方法 |
TWI508935B (zh) * | 2011-08-11 | 2015-11-21 | China Petrochemical Dev Corp Taipei Taiwan | Titanium-silicon molecular sieve and its preparation method and method for producing cyclohexanone oxime using the molecular sieve |
-
2012
- 2012-08-10 TW TW101128916A patent/TWI432262B/zh active
- 2012-09-13 US US13/614,684 patent/US8962872B2/en not_active Expired - Fee Related
- 2012-09-14 CN CN201210344544.0A patent/CN103570646B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
US20140046079A1 (en) | 2014-02-13 |
CN103570646B (zh) | 2015-11-25 |
CN103570646A (zh) | 2014-02-12 |
US8962872B2 (en) | 2015-02-24 |
TW201406456A (zh) | 2014-02-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5527520A (en) | Method of making a titanium-containing molecular sieve | |
US5977009A (en) | Catalyst compositions derived from titanium-containing molecule sieves | |
JP5662481B2 (ja) | チタン−mwwゼオライトの製造方法 | |
US5412122A (en) | Epoxidation process | |
TWI466875B (zh) | Method for making epoxides | |
JP2008502571A (ja) | エポキシ化触媒 | |
TWI500607B (zh) | 直接環氧化之方法 | |
JPH08269029A (ja) | プロピレンオキシドの製造方法 | |
TWI432262B (zh) | Method for making epoxides | |
TWI589567B (zh) | Method of making epoxides | |
DE60223708T2 (de) | Direktes epoxidierungsverfahren unter verwendung eines gemischten katalysatorsystems | |
JP3837751B2 (ja) | プロピレンオキシドの製法 | |
TWI480256B (zh) | Method for making ketoxime | |
CN113443635A (zh) | 一种含钛Beta分子筛及其合成方法 | |
WO1998035910A1 (en) | Metal molecular sieve catalysts | |
CN117566751A (zh) | 一种用于液相选择氧化反应的光-热协同催化剂及其一步合成方法 | |
KR20070022093A (ko) | 에폭시화 촉매 |