CN107848937B - 用于使用含氧气体氧化醇的方法 - Google Patents
用于使用含氧气体氧化醇的方法 Download PDFInfo
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- CN107848937B CN107848937B CN201580080099.3A CN201580080099A CN107848937B CN 107848937 B CN107848937 B CN 107848937B CN 201580080099 A CN201580080099 A CN 201580080099A CN 107848937 B CN107848937 B CN 107848937B
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- copper
- gold
- oxide
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 19
- 150000001298 alcohols Chemical class 0.000 title claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000001301 oxygen Substances 0.000 title claims abstract description 18
- 239000007789 gas Substances 0.000 title claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 title claims description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 19
- 239000005749 Copper compound Substances 0.000 claims abstract description 18
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 18
- 150000002344 gold compounds Chemical class 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 8
- 239000010931 gold Substances 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 229910052737 gold Inorganic materials 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 17
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 125000003342 alkenyl group Chemical group 0.000 claims description 11
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- NFFYXVOHHLQALV-UHFFFAOYSA-N copper(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Cu].[Cu] NFFYXVOHHLQALV-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000005750 Copper hydroxide Substances 0.000 claims description 2
- KZNMRPQBBZBTSW-UHFFFAOYSA-N [Au]=O Chemical compound [Au]=O KZNMRPQBBZBTSW-UHFFFAOYSA-N 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
- 150000001768 cations Chemical group 0.000 claims description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 claims description 2
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910001922 gold oxide Inorganic materials 0.000 claims description 2
- OTCKNHQTLOBDDD-UHFFFAOYSA-K gold(3+);triacetate Chemical compound [Au+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OTCKNHQTLOBDDD-UHFFFAOYSA-K 0.000 claims description 2
- ZVUZTTDXWACDHD-UHFFFAOYSA-N gold(3+);trinitrate Chemical compound [Au+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O ZVUZTTDXWACDHD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 claims description 2
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 abstract description 6
- 239000007857 degradation product Substances 0.000 abstract description 3
- 239000010888 waste organic solvent Substances 0.000 abstract description 3
- -1 ether carboxylic acids Chemical class 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229920006395 saturated elastomer Polymers 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000001354 calcination Methods 0.000 description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 125000000623 heterocyclic group Chemical group 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 150000003138 primary alcohols Chemical class 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 238000002296 dynamic light scattering Methods 0.000 description 4
- 125000001072 heteroaryl group Chemical group 0.000 description 4
- 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 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- QZXSMBBFBXPQHI-UHFFFAOYSA-N N-(dodecanoyl)ethanolamine Chemical compound CCCCCCCCCCCC(=O)NCCO QZXSMBBFBXPQHI-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- FZHSPPYCNDYIKD-UHFFFAOYSA-N 5-methoxysalicylaldehyde Chemical compound COC1=CC=C(O)C(C=O)=C1 FZHSPPYCNDYIKD-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 150000001408 amides Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000002837 carbocyclic group Chemical group 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N hydroxymethyl benzene Natural products OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 2
- BVJSUAQZOZWCKN-UHFFFAOYSA-N p-hydroxybenzyl alcohol Chemical compound OCC1=CC=C(O)C=C1 BVJSUAQZOZWCKN-UHFFFAOYSA-N 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
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 1
- 239000001764 (E)-oct-3-en-2-one Substances 0.000 description 1
- BATOPAZDIZEVQF-MQQKCMAXSA-N (E,E)-2,4-hexadienal Chemical compound C\C=C\C=C\C=O BATOPAZDIZEVQF-MQQKCMAXSA-N 0.000 description 1
- 239000005968 1-Decanol Substances 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- BSDNZCQPDVTDET-UHFFFAOYSA-N 2-hydroxy cinnamaldehyde Natural products OC1=CC=CC=C1C=CC=O BSDNZCQPDVTDET-UHFFFAOYSA-N 0.000 description 1
- ZCFOBLITZWHNNC-VOTSOKGWSA-N 3-Octen-2-one Chemical compound CCCC\C=C\C(C)=O ZCFOBLITZWHNNC-VOTSOKGWSA-N 0.000 description 1
- ZCFOBLITZWHNNC-UHFFFAOYSA-N 3-Octen-2-one Natural products CCCCC=CC(C)=O ZCFOBLITZWHNNC-UHFFFAOYSA-N 0.000 description 1
- ZVHAANQOQZVVFD-UHFFFAOYSA-N 5-methylhexan-1-ol Chemical compound CC(C)CCCCO ZVHAANQOQZVVFD-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910002708 Au–Cu Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- OTGQIQQTPXJQRG-UHFFFAOYSA-N N-(octadecanoyl)ethanolamine Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCO OTGQIQQTPXJQRG-UHFFFAOYSA-N 0.000 description 1
- GSILMNFJLONLCJ-UHFFFAOYSA-N N-(octanoyl)ethanolamine Chemical compound CCCCCCCC(=O)NCCO GSILMNFJLONLCJ-UHFFFAOYSA-N 0.000 description 1
- KUGRPPRAQNPSQD-UHFFFAOYSA-N OOOOO Chemical compound OOOOO KUGRPPRAQNPSQD-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
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- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
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- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
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- ZFGJFDFUALJZFF-UHFFFAOYSA-K gold(3+);trichloride;trihydrate Chemical compound O.O.O.Cl[Au](Cl)Cl ZFGJFDFUALJZFF-UHFFFAOYSA-K 0.000 description 1
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- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
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- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
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- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
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- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ZPHGMBGIFODUMF-UHFFFAOYSA-N thiophen-2-ylmethanol Chemical compound OCC1=CC=CS1 ZPHGMBGIFODUMF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
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- 229910052727 yttrium Inorganic materials 0.000 description 1
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Classifications
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- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
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- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/14—Preparation of carboxylic acid amides by formation of carboxamide groups together with reactions not involving the carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
- C07C233/46—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/245—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of keto groups or secondary alcohol groups
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- C—CHEMISTRY; METALLURGY
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- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
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Landscapes
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Abstract
披露了一种氧化醇用于生产其相应的羰基化合物的方法,其中该氧化用氧气或含氧气体在包含至少一种金化合物和铜化合物的催化剂的存在下进行。所述通过气态氧化剂的醇氧化可以实现高的产率和选择性与最小化的降解产物或废弃的有机溶剂。
Description
本发明涉及一种氧化醇用于生产其相应的羰基化合物的方法,其中该氧化用氧气或含氧气体在包含至少一种金化合物和铜化合物的催化剂的存在下进行。所述通过气态氧化剂的醇氧化可以实现高的产率和选择性与最小化的降解产物或废弃的有机溶剂。
现有技术
提供现有技术的以下讨论以便将本发明置于适当的技术背景下并使它的优点得到更充分的理解。然而,应当理解的是在整个说明书中现有技术的任何讨论不应被视为明确的或暗含的承认如此的现有技术是广泛已知的或形成本领域公知常识的一部分。
在一种或多种贵金属催化剂的存在下直接氧化脂肪醇是本领域中已知的并且吸引了相当大的兴趣,因为这种类型的反应具有产生许多具有广泛工业用途(特别是在洗涤剂和化妆品应用中)的脂肪酸最终产物的可能性。
例如,许多公开物描述了醚羧酸和/或其盐可以通过氧化其相应的醚醇,通常在贵金属催化剂的帮助下产生。这些公开物包括JP 50-96516(花王株式会社(KAOCORPORATION))1975/7/31,其披露了一种用于在钯或铂催化剂的存在下通过醚醇的液相脱氢氧化来制备羧酸盐的方法。不利地,该方法需要100℃-270℃的高反应温度,其可容易地降解所希望的产物中的醚键。
为了避免这种高温问题,该方法的许多后来公开的专利选择在贵金属催化剂(在大多数情况下钯或铂)的存在下使用氧气或含氧气体来氧化醚醇,这总体上允许较低的反应温度(例如20℃-95℃)。参见,例如在US 3342858(联合化学公司(ALLIED CHEMICALCORPORATION))1967/9/19、US 4214101 A(花王肥皂有限公司(KAO SOAP CO.,LTD))1980/6/22、DE 3135946 A(拜耳公司(BAYER AG))1983/3/24、EP0304763A(汉高两合股份公司(HENKEL KGAA))1989/3/1、US 5292940 A(汉高两合股份公司)1991/3/7、JP 2903187 B(川研精细化学品有限公司(KAWAKEN FINE CHEMICALS CO.LTD))1992/8/11、US 5463114 A(汉高两合股份公司)1995/10/26、US 8093414 B(科莱恩国际有限公司(CLARIANTINTERNATIONAL LTD))2008/2/21、US 2010056735 A(科莱恩金融英属维尔京群岛有限公司(CLARIANT FINANCE BVI LTD))2008/10/23、US 20110144385A(科莱恩国际有限公司)2010/2/11、CN 101357333 B(中国日用化学工业研究院(CHINA RESEARCH INSTITUTE OFDAILY CHEMICAL INDUSTRY))2009/2/4、US 20120296115 A(花王株式会社(KAO CORP))2011/7/14、JP 2011184379A(花王株式会社)2011/9/22、JP 2011184380 A(花王株式会社)2011/9/22、JP 2012149046 A(花王株式会社)2012/8/9、JP 2012149047 A(花王株式会社)2012/8/9、JP 2013067564 A(花王株式会社)2013/4/18以及JP 2013151469 A(花王株式会社)2013/7/4中的描述。
虽然如此,虽然选择含氧气体作为氧化剂对于放大应用是吸引人的,但是这些现有技术的氧化剂方法不满足用于工业用途的所有效率、经济和环境要求。
因此,本领域中仍存在需要提供一种改进的用于氧化醇(特别是脂肪醇等)以获得其相应的羧酸的方法,该方法具有高产率并使用经济上可行的催化剂溶液。
发明内容
本发明涉及一种氧化具有式(I)的醇用于生产其相应的羰基化合物的方法
R-OH (I)
其中R表示任选地包含杂原子并且任选地包含取代基的饱和或不饱和的直链、支链或环状的C7-C50烃基,其中该氧化用氧气或含氧气体在包含至少一种金化合物和铜化合物的催化剂的存在下进行。
本发明还涉及一种容易通过如先前表述的方法获得的羰基化合物。
如由本发明的诸位发明人发现的,通过气态氧化剂的醇氧化可以借助于以上描述的催化剂实现高的产率和选择性与最小化的降解产物或废弃的有机溶剂。此外,该催化剂还容易回收并且再利用,使其是用于工业考虑的成本和环境可行的选项。
还似乎与单金属催化剂相比,在本发明的方法中使用的催化剂示出催化性能的增强并且在重复运行中提供良好的催化剂稳定性和可重用性。
本发明的其他特征、细节和优点将在阅读下面的说明书之后甚至更充分地显露。
定义
贯穿本说明,包括权利要求书,术语“包含一个/一种”应理解为是与术语“至少包含一个/一种”同义,除非另外指明,并且“在...之间”应理解为包含极限值。
如果通过援引方式并入本申请的任何专利、专利申请、以及公开物的披露内容与本申请的说明相冲突到了可能导致术语不清楚的程度,则本说明应该优先。
如在此使用的,术语“烃基”是指由碳原子和氢原子组成的基团,该基团可以是饱和或不饱和的,直链、支链或环状的,脂肪族或芳香族的。本发明的烃基可以是烷基、烯基、炔基、芳基、烷基芳基、芳基烷基、杂环基团、和/或烷基杂环基团。
如在此使用的,关于有机基团的术语“(Cn-Cm)”,其中n和m各自为整数,指示该基团每个基团可以含有从n个碳原子至m个碳原子。
如在此使用的,“烷基”基团包括具有一个或多个碳原子的饱和烃,包括直链烷基,如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基;环状的烷基(或“环烷基”或“脂环族的”或“碳环型的”基团),如环丙基、环戊基、环己基、环庚基、以及环辛基;支链烷基,如异丙基、叔丁基、仲丁基、以及异丁基;以及烷基取代的烷基,如烷基取代的环烷基以及环烷基取代的烷基。术语“脂肪族基团”包括其特征是直链或支链的有机部分,典型地具有在1与22之间的碳原子。在复杂结构中,这些链可以是支链的、桥联的、或交联的。脂肪族基团包括烷基、烯基和炔基。
如在此使用的,“烯基”或“烯基基团”是指脂肪族烃基,该脂肪族烃基可以是直链或支链的、含有至少一个碳-碳双键。烯基的实例包括,但不限于,乙烯基、丙烯基、正丁烯基、异丁烯基、3-甲基丁-2-烯基、正-戊烯基、庚烯基、辛烯基、癸烯基等。术语“炔基”是指具有至少一个碳碳三键的直链或支链烃基,如乙炔基。
术语“芳基”包括不饱和的且芳香族的环状烃以及不饱和的且芳香族的杂环(含有一个或多个环)。芳基还可以与脂环族环或不是芳香族的杂环稠合或桥连以便形成多环,例如四氢化萘。“亚芳基”是芳基的二价类似物。
术语“杂环基团”包括类似于碳环型基团的闭合环结构,其中在环中的一个或多个碳原子是除碳之外的元素,例如,氮、硫、或氧。杂环基团可以是饱和的或不饱和的。此外,杂环基团,例如吡咯基、吡啶基、异喹啉基、喹啉基、嘌呤基、和呋喃基,可以具有芳香族特征,在这种情况下,它们可以被称为“杂芳基”或“杂芳香族”基团。
芳基和杂环(包括杂芳基)也可以在一个或多个构成原子处被取代。杂芳香族和杂脂环族的基团的实例可以具有1至3个分开的或稠合的环,这些环具有每环3至约8个成员以及一个或多个N、O或S杂原子。总体上,术语“杂原子”包括除碳或氢之外的任何元素的原子,其优选实例包括氮、氧、硫、和磷。杂环基团可以是饱和的或不饱和的或芳香族的。
如在此使用的,术语“芳烷基”或“芳基烷基”是指被一个或多个芳基取代的烷基,例如像苯基甲基、苯基乙基、三苯基甲基。术语“烷基芳基”是指结合到芳基部分上的烷基部分。
应该指出,形成更大的化合物的一部分的化学部分可以在此使用通常符合它的名称进行描述,当它以单一分子或通常符合其基团的名称存在时。例如,术语“吡啶”和“吡啶基”当用来描述附接到其他化学部分上的部分时,符合相同含义。
如在此使用的醇包括伯醇和仲醇,优选伯醇。
被包括在本发明中的氧化醇用于生产其相应的羰基化合物的方法中的反应值得注意地包括从伯醇获得羧酸的方法、从伯醇获得醛的方法、以及从伯醇获得酮的方法。
如先前表述的,R表示任选地包含杂原子并且任选地包含取代基的饱和或不饱和的直链、支链或环状的C7-C50烃基。该基团然后可以任选地包含杂原子和/或取代基。优选地,R表示任选地包含杂原子(例如像氧、氮、硫或卤素)并且任选地包含取代基的饱和或不饱和的直链、支链或环状的C7-C50烃基。
取代基可以例如在下组中选择,该组由以下各项组成:烷基、烯基、芳基、含氧基团(如羟基)、羰基、醛、羧基、羧酸酯、酯、烷氧基、氢过氧基、醚或缩醛以及含氮基团(如胺或酰胺)。取代基可以优选地选自下组,该组由以下各项组成:-OR3、-CH3、-CH2CH3、
-COOH、-CONH2以及-COOR3,其中R3表示烷基或芳基。
该烃基可以例如被1、2或3个相同或不同的取代基取代。
经受根据本发明的方法的氧化的醇可以是具有式(II)的乙氧基化醇
R1(OCH2CHR2)nOCH2CH2OH (II)
其中:R1表示具有1至22个碳原子的烷基或具有1至22个碳原子的单不饱和或多不饱和的直链或支链烯基,任选地包含至少一个取代基和/或杂原子(如N或O);R2表示在单独分子中的氢原子或甲基或其混合物;并且n具有在2与20之间的平均数。
在式(II)中的R1优选地表示具有从3至22、更优选地从8至20并且最优选地从10至16个碳原子的烷基。对于R1给予特别优选的是甲基、丁基和月桂基,其中月桂基是进一步优选的。R1基团可以是被任何取代基取代的烷基,该任何取代基不会干扰羟基的氧化。例如,式(II)中的R1可以是被至少一个选自下组的取代基取代的烷基,该组由以下各项组成:-OR3、-CH3、-CH2CH3、-COOH、-CONH2以及-COOR3,其中R3表示烷基或芳基。
在式(II)中,单独分子上的R2基团可以是氢、甲基或其混合物。因此,示例性的具有式(II)的乙氧基化醇可以选自下组,该组由以下各项组成:直链乙氧基化物、直链丙氧基化物以及混合的乙氧基化物丙氧基化物,所有都是洗涤剂范围的乙氧基化醇。商业上,每分子具有平均3、7、9和12个乙氧基化物单元的洗涤剂范围的乙氧基化醇是可获得的。这些洗涤剂范围的乙氧基化物醇的制备是本领域众所周知的。
优选地,在具有式(II)的单独分子中n是从4至12、更优选地从4至9的整数。
特别地,当经受根据本发明的方法的氧化的醇是具有式(II)的乙氧基化醇时,本发明提供了一种用于通过氧化一种或多种具有式(II)的乙氧基化醇来生产具有式(III)的化合物和/或相应的质子化羧酸的方法
R1(OCH2CHR2)nOCH2COOB (III)
其中B是阳离子并且R1、R2和n具有以上给出的相同的含义。
优选地,平衡离子B是优选地选自由Li、Na、K、Rb和Cs组成的组的碱金属阳离子,其中Na和K是特别优选的。
在碱性介质中的氧化反应期间,首先形成具有式(III)的碱金属盐。为了生产游离醚羧酸(即,具有式(III)的化合物的质子化羧酸),可使所得具有式(III)的碱金属盐与酸反应。优选的酸是盐酸和硫酸。
经受根据本发明的方法的氧化的醇还可以是具有式(IV)的化合物
其中R’表示具有从4至25个碳原子的饱和直链或支链烷基或具有从4至25个碳原子的单不饱和或多不饱和的直链或支链烯基。
在根据本发明的方法的优选的具有式(IV)的化合物中,R’是具有从7至17个碳原子的饱和直链或支链烷基或者具有从7至17个碳原子的单不饱和或多不饱和直链或支链烯基,并且更优选是具有从9至14个碳原子的饱和直链烷基。
作为具有式(IV)的化合物的优选实例,可以提及下组,该组由以下各项组成:月桂酸单乙醇酰胺、肉豆蔻酸单乙醇酰胺、辛酸单乙醇酰胺、癸酸单乙醇酰胺、棕榈酸单乙醇酰胺、硬脂酸单乙醇酰胺和异硬脂酸单乙醇酰胺,其中月桂酸单乙醇酰胺是特别优选的。这里,还可能的是使用基于链部分的酰胺或这些酸单乙醇酰胺的混合物,优选椰油酸单乙醇酰胺。
特别地,当经受根据本发明的方法的氧化的醇是具有式(IV)的化合物时,本发明提供了一种用于通过氧化一种或多种具有式(IV)的酸单乙醇酰胺来生产具有式(V)的化合物和/或相应的质子化酰基甘氨酸的方法
其中B和R’具有以上给出的相同的含义。
在碱性介质中的氧化反应期间,首先形成具有式(V)的碱金属盐。为了生产游离醚酰基甘氨酸(即,具有式(V)的化合物的质子化羧酸),可使所得具有式(V)的碱金属盐与酸反应。优选的酸是盐酸和硫酸。
可替代地,在又另一个实施例中,该经受根据本发明的方法的氧化的醇选自下组,该组由以下各项组成:辛醇、1-癸醇、1-十二烷醇、1-十四烷醇、1-十六烷醇、1-十八烷醇、1-十八碳烯醇、异庚醇、环己醇、环戊醇、环辛醇、(1r,3r,5r,7r)-金刚烷-2-醇、噻吩-2-基甲醇、4-(羟甲基)苯酚、(E)-3-苯基丙-2-烯-1-醇、双环[2.2.1]庚-2-醇、2-羟基-5-丁基苄醇、异辛醇、异壬醇、异癸醇、十三烷醇和其混合物。
通过本发明的反应获得的羰基化合物可以值得注意地例如是羧酸或其盐、醛或酮。优选地,羧酸在下组中选择,该组由以下各项组成:聚氧乙烯(8-10)辛基醚羧酸、聚氧乙烯(3-10)月桂基醚羧酸、聚氧乙烯(3-10)聚氧乙烯(2-10)油烯基醚羧酸、聚氧乙烯苯基醚羧酸、丁酸、己酸、月桂酸、十二烷酸、癸酸和十六烷酸。优选地,醛在下组中选择,该组由以下各项组成:呋喃-2-甲醛、噻吩-2-甲醛、(2E,4E)-己-2,4-二烯醛、丁醛、辛醛、4-羟基苯甲醛、2-羟基-5-甲氧基苯甲醛和肉桂醛。优选地,酮在下组中选择,该组由以下各项组成:环己酮、环辛酮、环戊酮、苯乙酮、己-2-酮、(1r,3r,5r,7r)-金刚烷-2-酮、(E)-辛-3-烯-2-酮、4-乙基环己-1-酮、3-甲基环己-1-酮和3,5-二甲基环己-1-酮、双环[2.2.1]庚-2-酮。
如先前表述的,本发明的催化剂包含至少一种金化合物和铜化合物。
本发明的金化合物可以是金金属本身或包含金的任何化合物例如像金的盐或氧化物。金化合物优选地在下组中选择,该组由以下各项组成:金金属、氧化金、硝酸金、氯化金、乙酸金、乙酰丙酮金和氢氧化金。
优选地,该金化合物以颗粒形式存在,并且具有在纳米范围内的平均粒度,优选地从1至50nm并且更优选地从2至10nm。可以例如通过本领域中已知的透射电子显微镜(TEM)或动态光散射(DLS)、粉末X射线衍射(PXRD)、H2-O2滴定、CO或H2化学吸附方法来测量粒度。
本发明的铜化合物可以是铜金属本身或包含铜的任何化合物例如像铜的盐或氧化物。铜化合物优选地在下组中选择,该组由以下各项组成:铜金属、氧化铜(I)、氧化铜(II)、氧化铜(III)、硝酸铜、氯化铜、乙酸铜、乙酰丙酮铜、氢氧化铜、硫酸铜、和高氯酸铜。
优选地,该铜化合物以颗粒形式存在,并且具有在纳米范围内的平均粒度,优选地从1至50nm并且更优选地从2至10nm。可以例如通过本领域中已知的透射电子显微镜(TEM)或动态光散射(DLS)方法来测量粒度。
该金化合物与该铜化合物的摩尔比可以在2∶1至100∶1的范围内、优选地在3∶1至61∶1的范围内、更优选地在6∶1至40∶1的范围内。
优选地,本发明的催化剂是非均相催化剂。
进一步优选地,将这些金属化合物施用到载体上。优选的载体是活性炭和氧化物载体。示例性的氧化物载体包括二氧化钸、氧化锌、二氧化钛、氧化镁、氧化铁、氧化镧、二氧化硅和氧化铝或它们的混合物,其中二氧化钸和氧化锌是特别优选的。
氧化钸载体可以具有在350℃的温度下煅烧2小时后测量的包括在50m2/g与300m2/g之间、值得注意地在200m2/g与280m2/g之间的比表面积。“比表面积”值得注意地意指根据由在“The Journal ofAmerican Society[美国学会杂志],60,309(1938)”中描述的布鲁诺-埃梅特-特勒(BRUNAUER-EMMETT-TELLER)方法制定的ASTM D 3663-78标准通过氮吸附确定的B.E.T.比表面积。
氧化铈载体可以具有在400℃的温度下煅烧2小时后测量的至少200m2/g的比表面积。氧化钸载体可以具有在800℃的温度下煅烧2小时后测量的至少15m2/g、值得注意地在20m2/g与60m2/g之间的比表面积。
氧化铈载体可以具有在800℃的测量温度下2小时的大于0.1cm3/g、优选地大于0.15cm3/g、值得注意地在0.15cm3/g与0.25em3/g之间的孔体积。根据ASTM D4284-83标准用水银测孔仪或者使用等温氮吸附法(以上认定的B.E.T.方法)测量孔体积,该孔体积对应于具有小于60nm直径的孔。
这些氧化钸值得注意地在EP 300852和EP 388567公开物中进行了描述。
这些氧化钸载体可以通过煅烧氢氧化高钸获得,其中在煅烧前使该氢氧化铈经受溶剂热处理。
这些氧化钸载体可以值得注意地根据以下方法获得,该方法由以下步骤组成:
-通过使钸盐的溶液和碱反应制备氢氧化高钸,可能在氧化剂的存在下,其中该碱的量是使得该反应介质的pH是大于7;分离所获得的沉淀物,并且可能洗涤该沉淀物;
-将该氢氧化高铈以悬浮形式置于水中或可分解碱的水溶液中;
-将其在密闭室内加热到分别低于所述介质的临界温度和临界压力的温度和压力;
-将该反应混合物冷却并且使其达到大气压力;
-分离以这种方式处理过的氢氧化高钸;然后
-煅烧该处理过的氢氧化高钸。
氧化钸颗粒还可以包含值得注意地以按氧化物的重量计包括在1%与40%之间的比例、优选地以按氧化物的重量计包括在1%与20%之间的比例的除氧化钸外的至少一种稀土元素氧化物、碱土金属氧化物、过渡金属元素氧化物、后过渡金属元素氧化物或类金属元素氧化物。
稀土元素(REE)或稀土金属是周期表中的十七种化学元素集合(意指十五种镧系元素加上钪和钇)中的一种。优选地,这些稀土元素氧化物在下组中选择,该组由以下各项组成:氧化镧(La2O3)、氧化镨(Pr6O11)、氧化钕(Nd2O3)和氧化钇(Y2O3)。
过渡金属元素氧化物可以是例如ZrO2和TiO2。后过渡金属元素氧化物可以是例如Al2O3、CuO和ZnO。类金属元素氧化物可以是例如SiO2。碱土金属氧化物可以是例如BaO。
本发明的优选的混合氧化物在下组中选择,该组由以下各项组成:CeO2-ZrO2、CeO2-SiO2、CeO2-Pr2O3、以及CeO2-ZrO2-La2O3。
由氧化钸载体构成并且包含至少一种金化合物和铜化合物的催化剂可以通过若干种已知的方法获得,例如像吸附、沉积-沉淀、浸渍或共沉淀、值得注意地始润浸渍。可以使用若干种金和铜化合物或者金和铜化合物前体。
合适的催化剂载体的浸渍值得注意地在Y-F.Han等人.Journal of Catalysis[催化杂志]224(2004)60中提及。
这些催化剂的活化或再活化可能涉及煅烧步骤和/或在氢气中的还原步骤。值得注意地,改性催化剂的活化可能涉及在空气或O2中在100℃-500℃下持续1-24小时的煅烧步骤以及在氢气中在相同的温度下持续1-6小时的还原步骤。还有可能通过在100℃-500℃下在氢气流中的还原来活化本发明的催化剂。还可能通过用硼氢化钠、抗坏血酸钠、柠檬酸或肼的原位还原来活化或再活化本发明的催化剂。
氧化铈上的金化合物的浓度可以包括在按重量计0.1%与10%之间、优选按重量计从0.5%至4%。
氧化钸上的铜化合物的浓度可以包括在按重量计0.005%与6%之间、优选按重量计从0.01%至3%。
本发明的催化剂与该醇的重量比可以包括在0.04与0.20之间、优选地包括在0.06与0.13之间。
根据本发明的方法的氧化反应通常在30℃与100℃之间、优选地在40℃与90℃之间的温度下进行。
反应压力通常高于大气压力,尽管较高的压力也是可能的,值得注意地包括在3巴和20巴之间。
反应时间通常在1小时与30小时之间、优选地在3小时与20小时之间。
本发明的方法优选地在水性介质中进行。为了本发明的目的,术语“水性介质”是指一种介质,该介质含有该介质的总数的至少50摩尔百分比并且优选至少80摩尔百分比的液体水。确切地,根据本发明的水性介质可以是均相或非均相介质,如包含水相的双相或多相体系。
进一步优选地,本发明的方法在含有碱化合物的水性介质中进行。所述碱化合物可以选自碳酸盐、氢氧化物和氧化物,并且优选地选自具有式BOH的氢氧化物,其中B是如以上定义的。
在该氧化反应期间的pH优选地是在9与15之间、更优选地在10与14之间。任选地,在整个氧化反应中通过添加碱化合物将均匀的pH值维持在给定范围内。
根据本发明,用氧气或含氧气体(如值得注意地空气、O2-N2和O2-Ar)进行该氧化。
在该反应结束时,这些羰基化合物可以通过已知方法(如中和和溶剂萃取)来分离。
本发明还涉及一种组合物,该组合物包含至少一种具有式(I)的醇以及包含至少一种金化合物和铜化合物的催化剂
R-OH (I)
其中R表示任选地包含杂原子并且任选地包含取代基的饱和或不饱和的直链、支链或环状的C7-C50烃基。
所提供的以下实例是为了说明本发明的优选的实施例并且无意对其范围进行限制。在本发明范围内的其他方面、优点和修改对于本发明所属领域的技术人员将是显然的。
实验部分
催化剂的制备
使用以下程序在氧化铈上吸附金和铜纳米颗粒:将氯化金(III)三水合物(0.082g,HAuCl43H2O,Mw=393.83,Au 49.0%)和一定量的氯化铜(II)二水合物(分别1∶0.1或1∶0.5的Au:Cu摩尔比,CuCl22H2O,Mw=170.48,CuCl22H2O99%)在去离子水中的350mL水溶液添加至2.0g氧化钸(CeO2,来自苏威公司(Solvay)的Actalys HSA20SP)在去离子水中的20mL水溶液中。将所得浆料在室温下连续搅拌1小时。向其中滴加硼氢化钠(0.13g,Mw=37.83,NaBH498%)在去离子水中的5mL水溶液。将由此产生的Au-Cu/CeO2固体过滤并用数升去离子水洗涤,直到通过AgNO3测试没有检测到痕量的氯化物,并且然后在真空下冷冻干燥24小时。通过化学分析和透射电子显微镜(TEM)分析干燥的Au-Cu/CeO2固体,以确定CeO2载体上的金和铜纳米颗粒的含量和尺寸。商业CeO2上的金和铜的实际含量分别是1.1wt%Au、0.11wt%Cu以及1.0wt%Au、0.063wt%Cu。
除了添加Cu源之外,根据以上方法制备了1%的Au/CeO2催化剂。
催化剂测试:使用各种催化剂氧化乙氧基化醇
将从前面的实例中获得的催化剂用于氧化乙氧基化醇,其在高压分批反应器中进行。确切地,将49.2mg的1wt%Au/CeO2催化剂添加到含有55.1mg(1.9mmol)NaOH的24wt%聚氧乙烯月桂醚(从萨索尔公司(Sasol)获得的AEO 7,具有494.7的Mw)的2.6g水溶液中,给出以混合物的1.1的NaOH/醇摩尔比以及500的醇/金属摩尔比。用氧气将该反应器加压至12巴的压力并且然后密封。将该混合物在温和搅拌(600-800rpm)下加热至80℃的反应温度持续4h。通过1H NMR和13C NMR分析并且量化该反应器中的最终产物,根据如表1中提供的数据,发现聚氧乙烯月桂醚转化为聚氧乙烯月桂醚羧酸钠。
表1
T.O.N意指产物/金的摩尔比。
然后,似乎双金属Au/Cu催化剂的活性超过了单金属Au催化剂的活性。此外,似乎与单金属Au催化剂相比,在重复运行中的双金属Au/Cu催化剂稳定性和可重用性更高,并且维持高的产物产率。
Claims (12)
1.一种氧化具有式(II)的乙氧基化醇用于生产其相应的羰基化合物的方法
R1(OCH2CHR2)nOCH2CH2OH (II)
其中:R1表示具有1至22个碳原子的烷基或具有2至22个碳原子的单不饱和或多不饱和的直链或支链烯基,任选地包含至少一个取代基和/或杂原子;R2表示在单独分子中的氢原子或甲基或其混合物;并且n具有在2与20之间的平均数,其中该氧化用氧气或含氧气体在包含至少一种金化合物和铜化合物的催化剂的存在下进行,
其中:金化合物是金金属,金的盐、氧化物或氢氧化物,铜化合物是铜金属、铜的盐、氧化物或氢氧化物。
2.如权利要求1所述的方法,其中R1选自由甲基、丁基和月桂基组成的组。
3.如权利要求1所述的方法,其中R1是被至少一个选自下组的取代基取代的烷基,该组由以下各项组成:-OR3、-CH3、-CH2CH3、-COOH、-CONH2以及-COOR3,其中R3表示烷基或芳基。
4.如权利要求1至3中任一项所述的方法,该方法通过氧化一种或多种具有式(II)的乙氧基化醇用于生产具有式(III)的化合物和/或相应的质子化羧酸
R1(OCH2CHR2)nOCH2COOB (III)
其中B是阳离子。
5.如权利要求4所述的方法,进一步包括使这些具有式(III)的化合物与酸反应。
6.如前述权利要求1所述的方法,其中将该催化剂施用在选自活性炭和氧化物载体的载体上。
7.如权利要求6所述的方法,其中该载体是选自氧化锌、氧化镁、二氧化钸和氧化铝的氧化物载体。
8.如前述权利要求1所述的方法,其中在该氧化反应期间的pH是在9与15之间。
9.如前述权利要求1所述的方法,其中该氧化反应在30℃与100℃之间的温度下发生。
10.如前述权利要求1所述的方法,其中金化合物在下组中选择,该组由以下各项组成:金金属、氧化金、硝酸金、氯化金、乙酸金、乙酰丙酮金和氢氧化金。
11.如前述权利要求1所述的方法,其中铜化合物在下组中选择,该组由以下各项组成:铜金属、氧化铜(I)、氧化铜(II)、氧化铜(III)、硝酸铜、氯化铜、乙酸铜、乙酰丙酮铜、氢氧化铜、硫酸铜、和高氯酸铜。
12.一种组合物,该组合物包含具有式(II)的醇以及包含至少一种金化合物和铜化合物的催化剂
R1(OCH2CHR2)nOCH2CH2OH (II)
其中:R1表示具有1至22个碳原子的烷基或具有2至22个碳原子的单不饱和或多不饱和的直链或支链烯基,任选地包含至少一个取代基和/或杂原子;R2表示在单独分子中的氢原子或甲基或其混合物;并且n具有在2与20之间的平均数,
其中:金化合物是金金属,金的盐、氧化物或氢氧化物,铜化合物是铜金属、铜的盐、氧化物或氢氧化物。
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CN107848937A (zh) | 2018-03-27 |
EP3297985A4 (en) | 2019-01-02 |
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