CN106946670B - 制备4-甲基-3-癸烯-5-酮的方法 - Google Patents
制备4-甲基-3-癸烯-5-酮的方法 Download PDFInfo
- Publication number
- CN106946670B CN106946670B CN201611142757.XA CN201611142757A CN106946670B CN 106946670 B CN106946670 B CN 106946670B CN 201611142757 A CN201611142757 A CN 201611142757A CN 106946670 B CN106946670 B CN 106946670B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- decen
- methyl
- oxygen
- metal catalyst
- 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.)
- Expired - Fee Related
Links
- VPGZKDXGOZRHSB-UHFFFAOYSA-N 4-methyldec-3-en-5-one Chemical compound CCCCCC(=O)C(C)=CCC VPGZKDXGOZRHSB-UHFFFAOYSA-N 0.000 title claims description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 123
- 229910052751 metal Inorganic materials 0.000 claims abstract description 85
- 239000002184 metal Substances 0.000 claims abstract description 85
- WSTQLNQRVZNEDV-CSKARUKUSA-N (e)-4-methyldec-3-en-5-ol Chemical compound CCCCCC(O)C(\C)=C\CC WSTQLNQRVZNEDV-CSKARUKUSA-N 0.000 claims abstract description 48
- 239000002105 nanoparticle Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000010931 gold Substances 0.000 claims description 67
- 229910052737 gold Inorganic materials 0.000 claims description 33
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000011734 sodium Substances 0.000 claims description 15
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 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 claims description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000003849 aromatic solvent Substances 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 24
- 238000007254 oxidation reaction Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 238000003786 synthesis reaction Methods 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910004042 HAuCl4 Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910018885 Pt—Au Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000004808 allyl alcohols Chemical class 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 238000006036 Oppenauer oxidation reaction Methods 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- -1 alkali metals (e.g. Chemical class 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000010724 circulating oil Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 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
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012285 osmium tetroxide Substances 0.000 description 1
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000000075 primary alcohol group Chemical group 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 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 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明提供一种制备4‑甲基‑3‑癸烯‑5‑酮的方法。所述方法包括在(i)氧和(ii)金属催化剂的存在下氧化4‑甲基‑3‑癸烯‑5‑醇的步骤,其中所述金属催化剂包含沉积在纳米颗粒载体上的催化金属。
Description
技术领域
本发明涉及通过在金属催化剂的存在下氧化4-甲基-3-癸烯-5-醇(式II)制备4-甲基-3-癸烯-5-酮(式I)。4-甲基-3-癸烯-5-酮是香味成分,其用于香料、花露水、古龙水、个人产品等。
背景技术
4-甲基-3-癸烯-5-酮的制备在美国专利申请号2006/0178291A1中描述,基于起始材料4-甲基-3-癸烯-5-醇,使用45mol%的异丙醇铝和3当量的丙酮经由Oppenauer氧化反应进行。由于在工业生产期间使用异丙醇铝,该反应产生大量的固体废料。固体铝废料对环境有害,并且处理需要昂贵成本。
Villa等人报道了使用在碳纳米管上支持的Au-Pd催化剂氧化烯丙醇如肉桂醇。参见Villa,等人,Catalysis Today 157,89(2010)。Abad等人研究了使用沉积在纳米晶体氧化铈上的金纳米颗粒将仲烯丙醇氧化为其相应酮。参见Abad等人,Angewandte ChemieInternational Edition 44,4066(2005)和Chemical Communications 2006,3179。用于氧化烯丙醇的其他催化剂包括二氧化锰、四氧化锇、Pt/Bi/石墨和铬酸。参见Gritter等人,J.Org.Chem.24(8),1051–56(1959);Cha等人,Tetrahedron 40(12),2247-55(1984);Lee等人,Green Chemistry 2,279-82(2000);Harding等人,J.Org.Chem.40,1664-65(1975)。这些氧化反应都没有用于制备4-甲基-3-癸烯-5-酮。
存在开发大规模制备4-甲基-3-癸烯-5-酮的有效的和环境友好的方法的需要。
发明内容
本发明基于这样的发现:4-甲基-3-癸烯-5-酮可以以绿色方法高产率制备,即使用金属催化剂选择性氧化4-甲基-3-癸烯-5-醇。
因此,本发明的一个方面涉及通过在(i)氧和(ii)金属催化剂的存在下氧化4-甲基-3-癸烯-5-醇制备4-甲基-3-癸烯-5-酮的方法,其中所述金属催化剂含有沉积在纳米颗粒载体上的催化金属。
催化金属通常是加氢金属。催化金属的非限制性实例是Pd、Au、Pt、Ru、Rh、或其任意组合。Au是优选的催化金属。以金属催化剂的重量计,催化金属(例如,Au)以0.1至10%的量存在。
纳米颗粒载体通常是选自碱土金属、镧系元素、和p-区元素的氧化物的有机或无机载体。示例性纳米颗粒载体包括氧化铁、氧化钛、氧化铈、氧化锆、氧化铝、炭、羟基磷灰石、或其任意组合。这些载体是具有0.05至200纳米(例如,0.05至100nm,0.1至50nm,和0.1至25nm)的粒径的纳米颗粒的形式。
在一些实施方案中,金属催化剂还含有一种以上掺杂金属,如碱金属(例如,Li、Na、K、Rb和Cs),碱土金属(例如,Be、Mg、Ca、Sr和Ba),和其任意组合。掺杂金属还可以是Fe、Mn、或其组合。以金属催化剂的重量计,这些掺杂金属(例如,Na、Fe和Mn)通常以0至50,000ppm(例如,10至40,000ppm,10至10,000ppm,20至5,000ppm,50至3,000ppm,和100至2,000ppm)的量存在。
在任一上述方法中,氧可以以氧气、空气、经洗涤的空气(stripped air)、富集的空气、或其任意组合的形式提供。氧化反应优选在20至240℃(例如,40至140℃)的温度和在0.1至20巴(例如,1至15巴)的压力下进行。
上述任意方法,氧化反应可以在存在或不存在溶剂的情况下进行。溶剂的实例包括水、卤化的或非卤化的烷基和/或芳族溶剂、羧酸溶剂、和其任意组合。
在一些实施方案中,氧化反应在间歇反应器中进行。金属催化剂以4-甲基-3-癸烯-5-醇的重量计至少1%(例如,至少3%,至少6%,至少6.5%,至少7%,1至50%,6至50%,3至40%,6.5至40%,5至20%,和7至20%)的量存在。催化金属(例如,Au)以4-甲基-3-癸烯-5-醇的至少0.05摩尔%(例如,至少0.3摩尔%,0.01至10摩尔%,0.3至5摩尔%,和0.3至2摩尔%)的量存在。
在其他实施方案中,氧化反应在半连续或连续反应器中进行。连续反应器可以是单个连续搅拌槽反应器(CSTR)、串联的多个CSTR、或微型反应器。
CSTR是开放系统,具有恒定体积的槽、进料管、和出口管。进料管和出口管二者分开连接于所述槽。将起始材料(4-甲基-3-癸烯-5-醇)经由进料管连续引入槽,并且将产物(4-甲基-3-癸烯-5-酮)经由出口管连续从所述槽移出。反应在槽内发生。对于使用CSTR的示例性化学反应,参见美国专利申请号20150133694。
微型反应器是含有一个或多个反应通道的装置,所述通道各自具有0.1至200mm(例如,0.2至150mm,0.2至100mm,0.3至100mm,0.3至50nm,和0.4至50mm,和0.5至20mm)的内径(ID)。
CSTR和微型反应器二者可以是填充床反应器,其中反应器填充有材料如金属催化剂、玻璃珠(具有10至100μm的粒径)。如本文使用的,术语"填充的"和“填充”意为用一种以上允许有效生产4-甲基-3-癸烯-5-酮的材料填充反应器。在一个实施方案中,CSTR或微型反应器填充有所述反应器的20至90体积%的金属催化剂。
本发明的一个以上实施方案的详述在下文陈述。根据说明书、附图和权利要求,本发明的其他特征、目的和优势将显而易见。
附图说明
图1显示五次反应中4-甲基-3-癸烯-5-酮的产率相对于反应时间,每次反应使用不同量的Au/CeO2催化剂。
具体实施方式
4-甲基-3-癸烯-5-酮可以通过异源催化反应以高产率制备,即,使用含有沉积在纳米颗粒载体上的催化金属的金属催化剂,利用含氧气体选择性氧化反应4-甲基-3-癸烯-5-醇。
含氧气体的实例包括空气、纯氧气、富氧空气、在惰性气体如氮、氦或氩中稀释的纯氧。
本文中使用的金属催化剂是指含有催化金属、纳米颗粒载体,和任选地,促进剂金属的催化剂,其中所述催化金属沉积在纳米颗粒载体上。
金属催化剂中含有的催化金属通常是加氢金属,催化加氢或氧化反应的金属。其可以选自由以下各项组成的组:贵金属和过渡金属,如金(Au)、铂(Pt)、钯(Pd)、钌(Ru)、铑(Rh)、铱(Ir)、铁(Fe)、镍(Ni)、和锰(Mn)、或其组合。以金属催化剂的重量计,催化金属的重量百分数在0.05至20%,优选0.1至20%,并且更优选0.5至10%的范围内。
金属催化剂中含有的促进剂金属本身不催化加氢或氧化反应。然而,当与催化金属组合时,其将增加催化金属的催化效应(例如,增加反应速度、选择性、和/或产率)。促进剂金属的实例是碱金属或碱土金属如Li、Na、K、Rb、Cs、Be、Mg、Ca、Sr、Ba、和其组合。
促进剂金属的量优选以金属催化剂重量计在1至40,000ppm之间(例如,10至50,000ppm之间,10至20,000ppm之间,100至20000ppm之间,100至10,000ppm之间,200至5000ppm之间,400至4000ppm之间)。
纳米颗粒载体是金属氧化物的纳米颗粒,所述金属氧化物选自由以下各项组成的组:碱土金属氧化物、过渡金属氧化物、镧系元素和p区元素氧化物,如二氧化硅(SiO2),氧化镁(MgO),氧化铝(Al2O3),二氧化钛(TiO2),二氧化铈(CeO2),二氧化锆(ZrO2),或其混合物。在本发明中,炭有时也用作纳米颗粒载体。
在一个实施方案中,金属催化剂是金催化剂,其含有沉积在纳米颗粒载体(例如,二氧化铈纳米颗粒载体)上的金。以金催化剂的重量计,金含量是0.1至20%(例如,0.2至15%和0.5至10%),并且氧化铈纳米颗粒载体含量是80至99.9%(例如,85至99.8%和90至99.5%)。
在另一实施方案中,金属催化剂是钠掺杂的金催化剂,其含有沉积在二氧化铈纳米颗粒载体上的金和钠。以金属催化剂的重量计,钠含量是1至100,000ppm(例如,1至40,000,10至40,000ppm,100至20,000ppm,200至10,000ppm,400至5,000ppm)。通过将促进剂金属钠加入至金催化剂,所需产物的选择性和产率出人意料地得到改善。还改善的是对所需产物(4-甲基-3-癸烯-5-酮)的选择性。此外,碱金属的存在增加金属催化剂的稳定性和再利用性。
金属催化剂可以按照已知方法制备,如用通过将催化金属卤酸或盐溶于水中获得的催化金属盐水溶液浸渍纳米颗粒载体。作为说明,将纳米颗粒载体(例如,CeO2纳米颗粒)浸没在HAuCl4溶液,从而金纳米颗粒吸附在纳米颗粒载体上。另一制备方法包括将催化金属(例如,不溶金属氢氧化物)沉淀在纳米颗粒载体上。
在将其用于反应之前,可以将金属催化剂进一步处理,如在氧化剂或还原气体(例如,空气和氢气),或惰性气体(氮)的存在下,在静态或流动条件下,在25至800℃的温度(例如,50至600℃,50至400℃,50至250℃,和50至220℃)煅烧(热处理)。
金属催化剂的另一合成后处理是在伯醇或仲醇如苯基乙醇溶液中在预定的温度(例如,40至240℃),在氮流下还原催化金属化合物5分钟至24小时的时期。作为说明,在氮流下,将醇苯基乙醇加入至二氧化铈纳米颗粒(Au/CeO2)上支持的金催化剂。Au/CeO2和苯基乙醇之间的重量比是1:100至1:2。然后将得到的悬浮液加热至预定温度(例如,40至120℃)达10分钟至5小时(例如,15分钟至3小时)的时期。随后,将悬浮液过滤并将还原的金属催化剂用有机质子溶剂洗涤数次(例如,1-10次和2-5次),所述质子溶剂如丙酮、乙醇、甲醇、和异丙醇。然后在温度50至100℃将还原的金属催化剂(例如,还原的Au/CeO2)干燥数小时(例如,1至10小时和1至5小时)。
可以进行这些合成后处理的组合。此外,金属催化剂可以如制备的使用,不进行任何合成后处理。
4-甲基-3-癸烯-5-醇的氧化在一种上述金属催化剂的存在下进行。金属催化剂的量通常在就4-甲基-3-癸烯-5-醇的重量而言,0.01至50%(例如,0.1至50%,1至50%,6至50%,1至40%,6至40%,3至40%,6.5至40%,3至30%,7至30%,4至15%,和7.5至20%)的范围内。通过说明,当氧化1克4-甲基-3-癸烯-5-醇时,优选使用0.03至0.4克(例如,0.06至0.4克)的金属催化剂,即,就4-甲基-3-癸烯-5-醇的重量而言3至40%(例如,6至40%)。在每种这些金属催化剂中,以金属催化剂的重量计,催化金属通常以0.01至50%(例如,0.1至40%,0.5至30%和1至20%)的水平存在。4-甲基-3-癸烯-5-醇与催化金属的摩尔比可以在15:1至150000:1之间(例如,20:1至20000:1,20:1至1000:3,50:1至5000:1,和50:1至1000:3)之间。关于摩尔百分数,催化金属以就4-甲基-3-癸烯-5-醇的摩尔而言0.0007至6.7摩尔%(例如,0.005至5摩尔%,0.3至5摩尔%,0.02至2摩尔%,和0.3至2摩尔%)的量存在。
4-甲基-3-癸烯-5-醇向4-甲基-3-癸烯-5-酮的氧化可以在填充有含氧气体的反应器,在静止状态(即,在常规静态反应器中)或在含氧气体流中(即,在流动反应器中)进行。在每个条件中,反应器中的含氧气体优选具有0.1至30巴的压力,更优选1至15巴。在流动反应器中,对于每克4-甲基-3-癸烯-5-醇,含氧气体具有0.2至100mL/min(优选,0.5至30mL/min)的流速。
在一些实施方案中,反应温度在20至240℃的范围内。优选,其在60至140℃的范围内。更优选,其在75至110℃的范围内。
氧化反应可以在存在或不存在溶剂的情况下进行。示例性溶剂包括腈(例如,乙腈和苄腈),含卤素的或不含卤素的烷基和/或芳族溶剂(例如,苯、甲苯和三氟甲苯),羧酸溶剂(例如,乙酸和丙酸)。
在本发明中,4-甲基-3-癸烯-5-醇的氧化反应产生水和所需产物4-甲基-3-癸烯-5-酮。当氧化反应获得其平衡时,4-甲基-3-癸烯-5-醇、4-甲基-3-癸烯-5-酮、和水之间的比例保持不变。为了改变平衡,使用任何蒸馏技术,或通过使用干燥剂如分子筛吸附将水从反应混合物中去除。
氧化反应可以通过碱加速。任选地,氧化4-甲基-3-癸烯-5-醇在无机碱、有机碱或其组合的存在下进行。优选,无机碱选自由以下各项组成的组:碱金属和/或碱土金属氧化物、碳酸盐、磷酸盐和其组合。有机碱可以选自由以下各项组成的组:碱性醇化物、磷腈、胺、季铵氢氧化物和其组合。
氧化反应在间歇反应器、半连续反应器或连续反应器中发生。
间歇反应器是指常规静态反应器,其中4-甲基-3-癸烯-5-醇、金属催化剂、和含氧气体固定在反应器中以允许氧化反应发生。
半连续或连续反应器是指包括单个连续搅拌槽反应器(CSTR),串联的多个CSTR,或微型反应器的流动反应器。
在一些实施方案中,将液体4-甲基-3-癸烯-5-醇与含氧气体一起泵入流动反应器。在其他实施方案中,将4-甲基-3-癸烯-5-醇溶解在溶剂中或使用静态混合器在管线中混合,之后进入反应器。在其他实施方案中,反应器可以包括催化剂保持器以防止金属催化剂从反应器移开。在一些实施方案中,使用加热循环油浴或电加热器加热反应器系统。从所述反应器系统,在产物接收器中收集反应混合物。使用仪器如气相色谱(GC)对反应混合物分析反应完成。
本文和权利要求中涉及的所有部分、百分数和比例全部以重量计,除非另有说明。
本文中公开的值和尺寸不应该理解为限制到所述的准确数值。而是(除非另有说明)每个该值意在表示该所述的值和该值周围的功能上相当的范围。例如,公开为"50%"的值意在表示"约50%"。
如本文中使用的,L理解为升,mL理解为微升,M理解为摩尔/升,m理解为米,mm理解为毫米,μm理解为微米,nm理解为纳米,mol理解为摩尔,psig理解为磅/平方英寸(表压),g理解为克,kg理解为千克,并且min理解为分钟。
通过以下非限制性实例更详细描述本发明。没有进一步详述,据信本领域技术人员基于本文中的说明书,可以利用本发明到其最充分的程度。
本文中引用的所有出版物通过参考以其整体并入。
实施例1
使用金属催化剂Au/CeO2纳米颗粒制备4-甲基-3-癸烯-5-酮。
催化剂I:Au/CeO2的合成
将氧化铈(CeO2)纳米颗粒制备为用于金属催化剂的纳米颗粒载体。在磁力搅拌下在室温(即,20℃)将Ce(NO3)4的水溶液(375mL,0.8M)用氨水溶液(1.12L,0.8M)处理,形成CeO2纳米颗粒。随后,在密闭的PET容器中将CeO2纳米颗粒的分散液加热至100℃达24小时。将得到的黄色沉淀过滤并在真空下干燥过夜。由此制备的CeO2纳米颗粒显示小的粒径(直径≤10nm)和高表面积(180m2/g)。
然后如下将金纳米颗粒沉积在CeO2纳米颗粒上。将HAuCl4·3H2O(100mg)溶解在水(100mL)中并将pH调节至10以获得金溶液,然后将其加入至CeO2(1g)纳米颗粒在水(50mL)中的悬浮液中。将得到的浆液的pH调节至10。将浆液在室温剧烈搅拌18小时,获得催化剂I,Au/CeO2,为固体沉淀,通过过滤收集并用水洗涤。
将催化剂I在真空下在室温干燥1小时。如通过化学分析确定的,Au含量以催化剂I的重量计为4.5wt%。
使用催化剂I合成4-甲基-3-癸烯-5-酮
在装有Dean Stark装置和冷凝器的三颈烧瓶中,将1g 4-甲基-3-癸烯-5-醇加入至75mg的催化剂I(以4-甲基-3-癸烯-5-醇的重量计7.5%的金属催化剂和以4-甲基-3-癸烯-5-醇的摩尔计0.34mol%Au)。在100℃的温度搅拌下在大气压下将空气流(10mL/min)通过得到的混合物。4-甲基-3-癸烯-5-醇的氧化通过GC或GC-MS分析在不同反应时间采集的样品来监测。在GC分析中,十二烷用作外部标准。7小时后,以76%的产率,96.5%的选择性获得产物4-甲基-3-癸烯-5-酮。
如下计算产率:获自反应的4-甲基-3-癸烯-5-酮的实际量(g)/4-甲基-3-癸烯-5-酮的理论量(g)x100%。理论产率是指当所有4-甲基-3-癸烯-5-醇被转变,没有产生任何副产物时,4-甲基-3-癸烯-5-酮的量。
选择性是指转变为4-甲基-3-癸烯-5-酮的反应的4-甲基-3-癸烯-5-醇的摩尔百分数。
实施例2
催化剂II:Na(1000ppm)-掺杂的Au/CeO2的合成
按照以下步骤,使用苯基乙醇还原催化剂I并用1000ppm钠掺杂,获得催化剂II。
在装有冷凝器的双颈圆烧瓶中,在氮流(5ml/min)下加入12mL苯基乙醇,接着加入1g催化剂I(Au/CeO2)。将得到的含有固体催化剂的混合物加热至80℃并在搅拌下在此温度保持2小时。随后,通过过滤收集固体催化剂,用丙酮(500mL)彻底洗涤,并在100℃干燥3小时。然后将固体催化剂悬浮在0.5mL乙酸钠水溶液(0.52M)中。
在100℃干燥悬浮液,得到催化剂II,即,Na(1000ppm)-掺杂的Au/CeO2。
使用催化剂II合成4-甲基-3-癸烯-5-酮
按照与实施例1中所述相同的步骤制备4-甲基-3-癸烯-5-酮,除了使用催化剂II替代催化剂I。4-甲基-3-癸烯-5-酮的产率和选择性分别是83.5和98.5%。
下表1总结了实施例1和2中获得的结果。
表1
实施例3
催化剂II,Na(1000ppm)-掺杂的Au/CeO2的再利用
收集实施例2中所述的反应中使用的催化剂II并按照上述实施例2中的相同步骤再利用以制备4-甲基-3-癸烯-5-酮。7小时的反应时间后,4-甲基-3-癸烯-5-酮的产率和选择性分别是88和96.5。
实施例4
催化剂IV:Au/HPA的合成
按照如下所述制备催化剂IV,即,羟基磷灰石纳米颗粒上支撑的金(Au/HPA)。制备两个溶液:Ca(NO3)2·4H2O(15.74g,0.066mol)在水(150mL)中的第一溶液和(NH4)2HPO4(5.28g,0.04mol)在水(120mL)中的第二溶液。将两种溶液的pH用浓氨水溶液(NH4OH)调至pH=11。经30分钟的时期在搅拌下向第一溶液中逐滴加入第二溶液,产生乳白色混合物,然后将其在90℃搅拌2小时。形成HPA纳米颗粒,通过过滤收集,用水洗涤,在120℃干燥16小时。
然后将Au纳米颗粒沉积在由此制备的HPA纳米颗粒上。更具体地,将脲溶液(600mg于30mL水中)加入至1g的HPA纳米颗粒中,接着加入HAuCl4·3H2O溶液(35mg于5mL水中)。将得到的混合物在90℃剧烈搅拌4小时,获得Au/HPA固体,将其通过过滤收集,用水和丙酮洗涤并通过空气干燥。然后在室温将Au/HPA固体通过NaBH4(0.07M,15mL于水中)还原30分钟,获得催化剂IV。
过滤,水洗涤,和在100℃干燥过夜,得到约1g的催化剂IV:Au/HPA。如通过化学分析确定的,发现Au含量为2wt%。
使用催化剂IV合成4-甲基-3-癸烯-5-酮
在高压釜中,将1.48g的4-甲基-3-癸烯-5-醇加入至250mg的催化剂IV(以4-甲基-3-癸烯-5-醇重量计17%金属催化剂和以4-甲基-3-癸烯-5-醇的摩尔计0.34mol%Au)中。在大气压下,在搅拌下在100℃的温度将空气流(20mL/min)通过得到的混合物。通过GC或GC-MS分析监测4-甲基-3-癸烯-5-醇的氧化。
4.5小时后,获得4-甲基-3-癸烯-5-酮,产率和选择性分别为89和92%。
实施例5
催化剂V:Pt-Au/CeO2的合成
催化剂V,即,掺杂有200ppm的铂的Au/CeO2,如下制备。制备12.7mg六水合氯铂酸在10mL水中的溶液。然后将0.5mL该溶液加入至1g实施例1中所述催化剂I中。将得到的浆液在100℃干燥12小时,获得Pt-Au/CeO2固体。随后,在氮流(5ml/min)下将固体加入至12mL苯基乙醇中,加热至80℃,并维持在该温度2小时,获得催化剂V,将其通过过滤收集,用丙酮洗涤,并在100℃干燥3小时。
使用催化剂V合成4-甲基-3-癸烯-5-酮
在高压釜中,将1g 4-甲基-3-癸烯-5-醇加入至75mg催化剂V(以4-甲基-3-癸烯-5-醇重量计7.5%的金属催化剂和以4-甲基-3-癸烯-5-醇的摩尔计0.34mol%的Au)中。在搅拌下,在100℃的温度在4.5巴压力下将空气流(10mL/min)通过得到的混合物。通过GC监测4-甲基-3-癸烯-5-醇的氧化。1小时后,获得4-甲基-3-癸烯-5-酮,产率53%并且选择性88%。
实施例6
催化剂VI:Mn-Au/CeO2的合成
催化剂VI,即,掺杂有200ppm锰的Au/CeO2,按照以下步骤制备。通过将18mg四水合氯化锰(II)溶解在100mL水中制备MnCl2溶液。将5mL该溶液加入至1g上述催化剂I中。将得到的悬浮液在室温搅拌2小时。将悬浮液中的Mn-Au/CeO2固体过滤并在100℃干燥12小时。
随后,在80℃使用12mL的苯基乙醇将干燥的Mn-Au/CeO2还原2小时,获得催化剂V,将其通过过滤收集,用丙酮洗涤,并在100℃干燥3小时。
使用催化剂VI合成4-甲基-3-癸烯-5-酮
根据与实施例5中所述相同的步骤制备4-甲基-3-癸烯-5-酮,除了(i)使用催化剂VI替代催化剂V和(ii)反应时间是3小时,而不是1小时。其产率和选择性分别是68%和88%。
实施例7
催化剂VII:Fe-Au/CeO2的合成
催化剂VII,即,掺杂有200ppm铁的Au/CeO2,如下制备。FeCl2溶液通过将12.5mg乙酸铁(II)溶解在100mL水中来制备。将5mL该溶液加入至1g催化剂I中。将得到的悬浮液在室温搅拌2小时。将悬浮液中的Fe-Au/CeO2固体过滤并在100℃干燥12小时。
随后,在80℃使用12mL苯基乙醇还原干燥的Fe-Au/CeO2历时2小时,得到催化剂VII,将其通过过滤收集,用丙酮洗涤,并在100℃干燥3小时。
使用催化剂VII合成4-甲基-3-癸烯-5-酮
按照与实施例5中所述相同的步骤制备4-甲基-3-癸烯-5-酮,除了使用催化剂VII替代催化剂V。其产率和选择性分别是52%和88%。
实施例8
催化剂VIII:Au/C的合成
催化剂VIII,即,在碳纳米颗粒上支撑的金(2wt%),按照以下步骤制备。
第一溶液,即,溶液A,通过将75mg HAuCl4·3H2O溶解在500mL水中制备。
第二溶液,即,溶液B,通过将75mg聚(乙烯醇)溶解在3.75mL水中制备。
合并两种溶液,接着逐滴加入NaBH4(72.5mg NaBH4于19mL水中)。将得到的混合物的pH调节至2,获得还原的金溶液。随后,将250mL的该还原的金溶液加入至0.626g的碳纳米颗粒中并在室温搅拌2小时,获得催化剂VIII,将其通过过滤收集,用水洗涤,并在60℃干燥过夜。催化剂VIII,即,Au/C,含有2wt%金。
使用催化剂VIII:Au/C合成4-甲基-3-癸烯-5-酮
按照与实施例5中所述相同的步骤制备4-甲基-3-癸烯-5-酮,除了(i)使用150mg的催化剂VIII替代75mg催化剂V,和(ii)反应时间是5小时,而不是1小时。其产率和选择性分别是49%和57%。
实施例9-13
实施例9:使用2wt%催化剂II合成4-甲基-3-癸烯-5-酮
在高压釜中,将1g的4-甲基-3-癸烯-5-醇加入至20mg的催化剂II(以4-甲基-3-癸烯-5-醇的重量计2%Au/CeO2和以4-甲基-3-癸烯-5-醇的摩尔计0.09mol%Au)。在4.5巴压力下,在100℃温度搅拌下将氧流(10mL/min)通过得到的混合物。通过GC监测4-甲基-3-癸烯-5-醇的氧化。在不同反应时间点收集样品并分析4-甲基-3-癸烯-5-酮的产率和选择性。结果显示在图1和下表2中。
实施例10:使用5wt%催化剂II合成4-甲基-3-癸烯-5-酮
按照上述相同步骤,使用以4-甲基-3-癸烯-5-醇的重量计5wt%催化剂II(0.23mol%Au)进行另一反应,除了使用不同量的金属催化剂。结果显示在图1和下表2中。
实施例11:使用7.5wt%催化剂II合成4-甲基-3-癸烯-5-酮
按照上述相同步骤,使用以4-甲基-3-癸烯-5-醇的重量计7.5wt%催化剂II(0.34mol%Au),进行第三反应,除了使用不同量的金属催化剂。结果显示在图1和下表2中。
实施例12:使用10wt%催化剂II合成4-甲基-3-癸烯-5-酮
按照上述相同步骤,使用以4-甲基-3-癸烯-5-醇的重量计10wt%催化剂II(0.46mol%Au),进行第四反应,除了使用不同量的金属催化剂。结果显示在图1和下表2中。
实施例13:使用20wt%催化剂II合成4-甲基-3-癸烯-5-酮
按照上述相同步骤,使用以4-甲基-3-癸烯-5-醇的重量计20wt%催化剂II(0.92mol%Au)进行第五反应,除了使用不同量的金属催化剂。结果显示在图1和下表2中。
表2
其他实施方案
本说明书中公开的所有特征可以以任意组合合并。本说明书中公开的每个特征可以用用于相同、相当或类似目的的备选特征替代。因此,除非另外明确说明,公开的每个特征仅是一个通用的系列的相当或类似特征的实例。
实际上,为了实现高产率和选择性制备4-甲基-3-癸烯-5-酮的目的,本领域技术人员可以选择不同催化金属、纳米颗粒载体、掺杂金属、反应温度、氧源、压力、和/或反应时间。此外,4-甲基-3-癸烯-5-醇、金属催化剂、催化金属和掺杂金属之间的比例还可以由技术人员通过本领域已知测定确定。
根据以上说明书,技术人员可以容易地确定本发明的本质特征,并且在不偏离其精神和范围的情况下,可以进行本发明的多种改变和变化,以使其适于各种用途和条件。因此,其他实施方案也在权利要求内。
Claims (16)
1.一种制备4-甲基-3-癸烯-5-酮的方法,所述方法包括在(i)含氧气体和(ii)金属催化剂的存在下氧化4-甲基-3-癸烯-5-醇,其中所述金属催化剂是含有沉积在纳米颗粒载体上的金(Au)和钠(Na)的钠掺杂的金催化剂,其中所述钠的含量为以所述金属催化剂的重量计200至10,000ppm。
2.权利要求1所述的方法,其中所述纳米颗粒载体是氧化铁、氧化钛、氧化铈、氧化锆、氧化铝、炭、羟基磷灰石、或其任意组合。
3.权利要求2所述的方法,其中所述纳米颗粒载体是氧化铈。
4.权利要求1所述的方法,其中Au以所述金属催化剂的0.2至10重量%的量存在。
5.权利要求1所述的方法,其中所述含氧气体以氧气、空气或其任意组合的形式提供。
6.权利要求1所述的方法,其中所述含氧气体以氧气、经洗涤的空气、富集的空气或其任意组合的形式提供。
7.权利要求1所述的方法,其中所述反应在20至240℃的温度,并且在0.1至20巴的压力下进行。
8.权利要求1所述的方法,其中所述反应在存在溶剂或没有溶剂的情况下进行,当使用溶剂时,溶剂选自由以下各项组成的组:腈、含卤素的或不含卤素的烷基和/或芳族溶剂、羧酸溶剂、和其任意组合。
9.权利要求1所述的方法,其中所述反应在间歇反应器或连续反应器中进行。
10.权利要求9所述的方法,其中所述连续反应器是单个CSTR、串联的多个CSTR、或微型反应器。
11.权利要求9所述的方法,其中所述连续反应器是填充有玻璃珠、金属催化剂、或其组合的填充床反应器。
12.权利要求11所述的方法,其中所述催化剂在反应器中具有在从20至90%的范围内的体积。
13.权利要求10所述的方法,其中所述连续反应器是含有通道的微型反应器,所述通道各自具有在从0.1至200mm的范围内的内径。
14.权利要求1所述的方法,其中所述含氧气体以氧气的形式提供,并且所述反应在没有溶剂的情况下在60至140℃的温度并且在1至15巴的压力下进行。
15.权利要求1所述的方法,其中所述催化剂以4-甲基-3-癸烯-5-醇的重量计6至50%的量存在。
16.权利要求15所述的方法,其中所述金属催化剂是含有沉积在二氧化铈纳米颗粒载体上的金和钠的钠掺杂金催化剂。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES201531801 | 2015-12-14 | ||
ESP201531801 | 2015-12-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106946670A CN106946670A (zh) | 2017-07-14 |
CN106946670B true CN106946670B (zh) | 2020-03-13 |
Family
ID=57629259
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611142757.XA Expired - Fee Related CN106946670B (zh) | 2015-12-14 | 2016-12-12 | 制备4-甲基-3-癸烯-5-酮的方法 |
Country Status (3)
Country | Link |
---|---|
US (1) | US9815758B2 (zh) |
EP (1) | EP3181543B1 (zh) |
CN (1) | CN106946670B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BR112017016223A2 (pt) * | 2015-01-29 | 2018-03-27 | Basf Corp | ?material catalítico, compósito de catalisador, sistema de tratamento de um fluxo de escape do motor de combustão interna, e, métodos para tratar gases de escape e para fabricação de um material catalítico? |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1865212A (zh) * | 2005-02-10 | 2006-11-22 | 国际香味香料公司 | 取代的3-癸烯-5-酮/醇衍生物 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9216935B2 (en) | 2013-05-21 | 2015-12-22 | International Flavors & Fragrances Inc. | Green process for producing 3-methyl-3-pentene-2-one |
-
2016
- 2016-12-12 US US15/375,252 patent/US9815758B2/en active Active
- 2016-12-12 CN CN201611142757.XA patent/CN106946670B/zh not_active Expired - Fee Related
- 2016-12-13 EP EP16203777.4A patent/EP3181543B1/en not_active Not-in-force
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1865212A (zh) * | 2005-02-10 | 2006-11-22 | 国际香味香料公司 | 取代的3-癸烯-5-酮/醇衍生物 |
Non-Patent Citations (2)
Title |
---|
A Collaborative Effect between Gold and a Support Induces the Selective Oxidation of Alcohols;Alberto Abad et al.;《Angew.Chem.Int.Ed.》;20050525;第44卷;4066-4069 * |
Nitrogen functionalized carbon nanostructures supported Pd and Au–Pd NPs as catalyst for alcohols oxidation;Alberto Villa et al.;《Catalysis Today》;20100221;第157卷;89-93 * |
Also Published As
Publication number | Publication date |
---|---|
US20170166504A1 (en) | 2017-06-15 |
EP3181543B1 (en) | 2019-02-20 |
EP3181543A1 (en) | 2017-06-21 |
CN106946670A (zh) | 2017-07-14 |
US9815758B2 (en) | 2017-11-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Corma et al. | Supported gold nanoparticles as catalysts for organic reactions | |
Ali et al. | Heterogeneous metal catalysts for oxidation reactions | |
Zhan et al. | Liquid phase oxidation of benzyl alcohol to benzaldehyde with novel uncalcined bioreduction Au catalysts: high activity and durability | |
JP5073133B2 (ja) | 過酸化水素を直接合成するための触媒および方法 | |
CN102513104B (zh) | 一种苯甲醛类化合物的制备方法及其用新型介孔碳担载的双金属催化剂 | |
CN106573231B (zh) | 氢化触媒及其制造方法 | |
US7973184B2 (en) | Method for producing propylene oxide | |
Deshmukh et al. | Catalytic activity of metal nanoparticles supported on nitrogen-doped carbon spheres | |
CN101238063A (zh) | 催化剂的改进 | |
JP7368813B2 (ja) | アミド化合物の水素化に用いる水素添加反応用触媒およびこれを用いたアミン化合物の製造方法 | |
JP2002532483A (ja) | オレフィンからのエポキシドの連続的製造法 | |
Lu et al. | Direct and efficient synthesis of clean H2O2 from CO-assisted aqueous O2 reduction | |
Shin et al. | The effects of impregnation of precious metals on the catalytic activity of titanium silicate (TS-1) in epoxidation of propene using hydrogen peroxide | |
Prieto et al. | Propylene epoxidation with in situ generated H2O2 in supercritical conditions | |
Choi et al. | Nanoscale palladium cluster immobilized on a TiO2 surface as an efficient catalyst for liquid-phase Wacker oxidation of higher terminal olefins | |
CN106946670B (zh) | 制备4-甲基-3-癸烯-5-酮的方法 | |
JP2015533344A (ja) | 過酸化水素の直接合成 | |
Yan et al. | Selective propylene epoxidation in liquid phase using highly dispersed Nb catalysts incorporated in mesoporous silicates | |
CN110903265A (zh) | 一种在钯膜反应器中进行气相丙烯环氧化反应的方法 | |
JPWO2020175309A1 (ja) | アミド化合物の水素化に用いる水素添加反応用触媒およびこれを用いたアミン化合物の製造方法 | |
WO2008041654A1 (fr) | Procédé de fabrication d'un composé époxy | |
JP5530074B2 (ja) | 複合体およびその製造方法 | |
TW513326B (en) | A method of regenerating support catalysts coated with gold particles for the oxidation of unsaturated hydrocarbons | |
WO2012171892A1 (en) | Process for the manufacture of hydrogen peroxide | |
WO2023073592A1 (en) | Selective aerobic oxidation of methane |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200313 |