WO2007116112A1 - Procédé de préparation d'oxymes au moyen de catalyseurs d'or - Google Patents
Procédé de préparation d'oxymes au moyen de catalyseurs d'or Download PDFInfo
- Publication number
- WO2007116112A1 WO2007116112A1 PCT/ES2007/070065 ES2007070065W WO2007116112A1 WO 2007116112 A1 WO2007116112 A1 WO 2007116112A1 ES 2007070065 W ES2007070065 W ES 2007070065W WO 2007116112 A1 WO2007116112 A1 WO 2007116112A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gold
- combinations
- process according
- solvent
- carried out
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 69
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 39
- 239000010931 gold Substances 0.000 title claims abstract description 39
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 150000002828 nitro derivatives Chemical class 0.000 claims abstract description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 4
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical group ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 150000002923 oximes Chemical class 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- DJBRXNRKYAWTBL-UHFFFAOYSA-N 1-nitrocyclohexene Chemical compound [O-][N+](=O)C1=CCCCC1 DJBRXNRKYAWTBL-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical class ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000000852 hydrogen donor Substances 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 claims description 2
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000003 Lead carbonate Inorganic materials 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 229930188620 butyrolactone Natural products 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000006184 cosolvent Substances 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910000464 lead oxide Inorganic materials 0.000 claims description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000012454 non-polar solvent Substances 0.000 claims description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims 1
- -1 decaborane Chemical compound 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- SYZVQXIUVGKCBJ-UHFFFAOYSA-N 1-ethenyl-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(C=C)=C1 SYZVQXIUVGKCBJ-UHFFFAOYSA-N 0.000 description 2
- IFSSSYDVRQSDSG-UHFFFAOYSA-N 3-ethenylaniline Chemical compound NC1=CC=CC(C=C)=C1 IFSSSYDVRQSDSG-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002343 gold Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229940078552 o-xylene Drugs 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GNKTZDSRQHMHLZ-UHFFFAOYSA-N [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] Chemical compound [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] GNKTZDSRQHMHLZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000035899 viability Effects 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
- 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
- B01J23/66—Silver or gold
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/10—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes from nitro compounds or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C251/44—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
Definitions
- the present invention deals with a new process for the production of oximes by selective hydrogenation of the corresponding nitro ⁇ , ⁇ -unsaturated compound using gold catalysts.
- the oximes specifically, the cyclohexanone oxime is a key product as an intermediate in the production of epsilon-caprolactam, a precursor to nylon-6.
- commercial processes for the production of cyclohexanone oxime include the reaction of cyclohexanone with hydroxylamine sulfate and ammonia. This process is far from ideal, considering the large number of steps required and the generation of sulfates as a byproduct.
- Various processes have been proposed in order to improve the production process of cyclohexanone oxime. In most cases, the direct use of hydroxylamine or its generation in situ in the reaction medium is considered, assuming a relatively high degree of danger due to the high explosive index of the product.
- cyclohexanone oxime Some variants of the above processes for producing cyclohexanone oxime disclose different forms for the production of hydrogen peroxide in situ, prior to its reaction with ammonia.
- the CN- 1,472, 197 patent relates to a process of producing cyclohexanone oxime by ammoximation of cyclohexanone with ammonia and H 2 O 2 produced by the method of the anthraquinone.
- US Patent 5,599,987 the production of cyclohexanone oxime is disclosed by a process similar, but in which hydrogen peroxide is obtained by oxidation of isopropanol with O 2 .
- JP-2001-213,854 an alternative route for the production of cyclohexanone oxime is proposed in which benzene is used as the starting product to form cyclohexene by partial dehydrogenation with a catalyst.
- 1-nitro-1-cyclohexene is obtained by a nitration reaction and as a last step a catalyst B is used to produce the cyclohexanone oxime through the partial hydrogenation of the nitro ⁇ - ⁇ -unsaturated compound.
- the present invention relates to a process for the preparation of oximes characterized in that it comprises a catalytic hydrogenation of the corresponding nitro ⁇ , ⁇ -unsaturated compound using a gold catalyst.
- the oxime is cyclohexanone oxime and the nitro compound is 1-nitro-1-cyclohexene.
- it is a process for the preparation of the cyclohexanone oxime characterized in that it comprises a catalytic hydrogenation of 1-nitro-1-cyclohexene using gold catalysts.
- the gold catalysts of the present invention catalyze the selective hydrogenation of nitro ⁇ , ⁇ -unsaturated groups to the corresponding oxime, avoiding the direct hydrogenation of the double bond to form the saturated nitro compound.
- gold can be supported on an inorganic support.
- Gold, or modified gold, as explained later in this report, can be supported in order to increase its dispersion and decrease the particle size on supports of inorganic or carbonaceous nature, as is known in the field. of metal catalysts.
- the percentage by weight of gold with respect to the solid support on which it is supported is preferably between 0.1 and 15% gold and more preferably between 0.5 and 5% gold.
- gold can be applied in metallic or ionic form on the support.
- said support is selected from active carbon, iron oxide, titanium oxide, cerium oxide, magnesium oxide, zirconium oxide, silica gel, silicic acid, lanthanum oxide, alumina, zinc oxide, calcium carbonate, calcium phosphate, calcium sulfate, barium sulfate, lead oxide, lead sulfate, lead carbonate and combinations thereof.
- said support is selected from iron oxide, titanium oxide, cerium oxide, silica and combinations thereof.
- the molar ratio between gold and the nitro compound is preferably between 0.01 and 10%, more preferably between 0.05 and 3%.
- the gold may be doped with a second metal.
- a metal other than gold as a modifier or dopant is introduced into the catalyst of the process.
- This metal modifier can improve the catalytic properties of the material.
- this doped or modified gold may also be supported, as explained above.
- the modifying metal is selected from palladium, platinum, rhodium, nickel, copper, ruthenium, lead, mercury, bismuth, germanium, cadmium, arsenic, antimony, silver, iron, manganese, cobalt, ruthenium and combinations thereof .
- the weight ratio of gold to said modifying metal is preferably 1: 0.001 and more preferably 1: 0.5.
- the process of the present invention further comprises a source of hydrogen that can be any hydrogen donor molecule.
- the hydrogen source is selected from ammonium formate, formic acid, decaborane, cyclohexene, cyclohexadiene, phosphoric acid and combinations thereof.
- the process is preferably carried out at atmospheric pressure and at a temperature between 25 0 C and
- the source of hydrogen is molecular hydrogen. This process is preferably carried out at a pressure between 1 and 100 bar and at a temperature between 2O 0 C and 25O 0 C, and more preferably at a pressure between 5 and 50 bar and at a temperature between 100 0 C and 15O 0 C.
- the hydrogenation reaction can be carried out with or without solvent.
- a particularly interesting advantage of the use of gold, according to the present invention is that the choice of the reaction solvent is not critical. It is possible to use solvents that are not normally inert in the presence of palladium and platinum catalysts.
- solvent it is preferably selected from water, alcohols preferably selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, isomeric butane, cyclohexanol and combinations thereof; ethers preferably selected from diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane and combinations thereof; esters preferably selected from ethyl acetate, butyl acetate and combinations thereof; ketones preferably selected from butyrolactone, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and combinations thereof; carboxylic acids preferably selected from acetic acid, propionic acid and combinations thereof; aprotic dipole solvents preferably selected from dimethylformamide, N-methylpyrrolidine, dimethylacetamide, sulfo
- Said solvent serves as a means of dissolution or to facilitate separation processes.
- said solvent is selected from toluene, xylene, tetrahydrofuran, dioxane, methyl ethyl ketone, methanol, ethanol and combinations thereof.
- the process of the present invention can also be carried out in the presence of one or more co-solvents.
- Said co-solvent is preferably selected from ethanol, acetone, acetonitrile and combinations thereof.
- the process is carried out in the absence of solvent.
- the reagents that are hydrogenated during the process are preferably in the liquid, gas or coexistence phase of both.
- the process of the present invention can be carried out in the gas-solid phase (catalyst) or in a gas-liquid-solid system (catalyst).
- said process can be carried out in a reactor in discontinuous or continuous mode, and catalyst recovery can be enhanced by recirculation or regeneration.
- the use of gold as a catalyst can be complemented with any promoter additive.
- Example-1 Preparation of catalyst 1.5% A11 / TIO2
- the gold catalyst supported on titanium oxide was prepared by deposition-precipitation technique. Deposition-precipitation of gold was carried out by adding the support to an aqueous solution of HAuCU (0.01M), previously adjusted to pH 7 with NaOH. To prepare 1 g of catalyst, 75 mg of HAuCU should be used. The mixture was kept stirring at 343 K under vigorous stirring for 2 hours, controlling the pH to a value of 7. The sample was then filtered, washed with deionized water until the chlorides were removed, dried under vacuum at 353 K and calcined at 673 K in air.
- Example-2 Preparation of cyclohexanone oxime with H 2 using 1.5% Au / TiO 2 catalyst
- Example-3 Preparation of cyclohexanone oxime with ammonium formate using catalyst 1.5% Au / Ti ⁇ 2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
L'invention se rapporte à un procédé de préparation d'oxymes qui comprend l'hydrogénation catalytique du composé nitro α, β-insaturé correspondant au moyen d'un catalyseur d'or.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ESP200601117 | 2006-04-12 | ||
ES200601117A ES2289925B2 (es) | 2006-04-12 | 2006-04-12 | Procedimiento para la preparacion de oximas utilizando catalizadores de oro. |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007116112A1 true WO2007116112A1 (fr) | 2007-10-18 |
Family
ID=38580727
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/ES2007/070065 WO2007116112A1 (fr) | 2006-04-12 | 2007-03-28 | Procédé de préparation d'oxymes au moyen de catalyseurs d'or |
Country Status (2)
Country | Link |
---|---|
ES (1) | ES2289925B2 (fr) |
WO (1) | WO2007116112A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2337004A1 (es) * | 2008-10-16 | 2010-04-19 | Universidad Politecnica De Valencia | Procedimiento de hidrogeneracion selectiva de nitrocicloalcanos para obtener oximas ciclicas. |
WO2014191589A1 (fr) * | 2013-05-27 | 2014-12-04 | Consejo Superior De Investigaciones Científicas (Csic) | Procédé d'obtention directe d'oxime de cyclohexanone à partir de nitrodérivés |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0346674A1 (fr) * | 1988-06-13 | 1989-12-20 | Mitsubishi Kasei Corporation | Procédé pour la synthèse d'oximes |
JP2001213854A (ja) * | 2000-02-02 | 2001-08-07 | Asahi Kasei Corp | シクロヘキサノンオキシムの製造方法 |
-
2006
- 2006-04-12 ES ES200601117A patent/ES2289925B2/es not_active Expired - Fee Related
-
2007
- 2007-03-28 WO PCT/ES2007/070065 patent/WO2007116112A1/fr active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0346674A1 (fr) * | 1988-06-13 | 1989-12-20 | Mitsubishi Kasei Corporation | Procédé pour la synthèse d'oximes |
JP2001213854A (ja) * | 2000-02-02 | 2001-08-07 | Asahi Kasei Corp | シクロヘキサノンオキシムの製造方法 |
Non-Patent Citations (3)
Title |
---|
DATABASE WPI Week 200175, Derwent World Patents Index; AN 2001-650716 * |
KABALKA ET AL.: "The palladium assisted transfer reduction of a,b-unsaturated nitroalkenes to oximes using ammonium formate", SYNTHETIC COMMUNICATIONS, vol. 20, no. 16, 1990, pages 2453 - 2458 * |
SEUNG HWANG LEE ET AL.: "Catalytic transfer hydrogenation of conjugated nitroalkenes using decarborane: synthesis of oximes", ORGANIC AND BIOMOLECULAR CHEMISTRY, vol. 1, no. 7, 2003, pages 1099 - 1100 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2337004A1 (es) * | 2008-10-16 | 2010-04-19 | Universidad Politecnica De Valencia | Procedimiento de hidrogeneracion selectiva de nitrocicloalcanos para obtener oximas ciclicas. |
WO2010043738A1 (fr) * | 2008-10-16 | 2010-04-22 | Universidad Politécnica De Valencia (Upv) | Procédé d'hydrogénation sélective de nitrocycloalcanes pour obtenir des oximes cycliques |
WO2014191589A1 (fr) * | 2013-05-27 | 2014-12-04 | Consejo Superior De Investigaciones Científicas (Csic) | Procédé d'obtention directe d'oxime de cyclohexanone à partir de nitrodérivés |
Also Published As
Publication number | Publication date |
---|---|
ES2289925B2 (es) | 2008-08-16 |
ES2289925A1 (es) | 2008-02-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
ES2285934B1 (es) | Procedimiento para preparar compuestos amino utilizando catalizadores de oro. | |
CN109499566B (zh) | 一种贵金属载体催化剂及其制备方法和应用 | |
ES2295980T3 (es) | Coamoximacion de cetonas. | |
JPS61183237A (ja) | 酢酸の水素添加方法 | |
ES2228736T3 (es) | Rocedimiento cocatalizado para la preparacion de oximas mediante sales de amonio o sales de amonio sustituidas. | |
CN101314577B (zh) | 一种催化环己酮氨肟化的方法 | |
WO2009071727A1 (fr) | Procédé d'hydrogénation sélective de composés nitroaromatiques substitués | |
CN106904633B (zh) | 贵金属改性介孔钛硅分子筛及其合成方法和应用以及一种氧化环酮的方法 | |
CN114849694B (zh) | 一种基于金属负载氧化钨氢化硝基芳烃的催化剂及其制备方法和应用 | |
EP3907000A1 (fr) | Catalyseur composite de métal de transition-métal précieux à base de carbone et son procédé de préparation | |
ES2289925B2 (es) | Procedimiento para la preparacion de oximas utilizando catalizadores de oro. | |
ES2337004B1 (es) | Procedimiento de hidrogenacion selectiva de nitrocicloalcanos para obtener oximas ciclicas. | |
CN101397235B (zh) | 一种催化氧化环己烷的方法 | |
JP2019526588A (ja) | 1,3−シクロヘキサンジメタノールの製造方法 | |
WO2019061358A1 (fr) | Procédé de production directe d'acétate de méthyle et/ou d'acide acétique à partir de gaz de synthèse | |
CN106946668A (zh) | 一种苯酚加氢制备环己酮的方法 | |
CN103537301A (zh) | 用于甲醇氧化联产甲缩醛和甲酸甲酯的催化剂及其制法和应用 | |
WO2000051725A1 (fr) | Catalyseur pour produire de l'acide acetique, procede de preparation de ce catalyseur, et procede de production d'acide acetique au moyen de ce catalyseur | |
Ni et al. | Novel functional TiPO/SiO2 catalyst enriched surface hydroxyl groups for highly selective catalytic oxidation of cyclohexylamine to cyclohexanone oxime | |
CN101544582B (zh) | 一种丁酮肟的合成方法 | |
CN108525670B (zh) | 氧化硅限域镍基催化剂及其制备方法与应用 | |
CN107721804B (zh) | 一种经3-硝基邻二甲苯制备邻二甲苯的方法 | |
CN102892741B (zh) | 制备二羧酸的方法 | |
CN107954835B (zh) | 一种制备二氯丙醇的方法 | |
CN105597741A (zh) | 用于co合成草酸二甲酯的催化剂及其制备方法及用途 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07730505 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 07730505 Country of ref document: EP Kind code of ref document: A1 |