CN1184808A - 乙酸乙烯酯的生产方法 - Google Patents
乙酸乙烯酯的生产方法 Download PDFInfo
- Publication number
- CN1184808A CN1184808A CN97126479A CN97126479A CN1184808A CN 1184808 A CN1184808 A CN 1184808A CN 97126479 A CN97126479 A CN 97126479A CN 97126479 A CN97126479 A CN 97126479A CN 1184808 A CN1184808 A CN 1184808A
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- China
- Prior art keywords
- palladium
- catalyst
- catalyzer
- carrier
- mentioned arbitrary
- Prior art date
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- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 46
- 230000008569 process Effects 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000003054 catalyst Substances 0.000 claims abstract description 73
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 42
- 239000007789 gas Substances 0.000 claims abstract description 33
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 150000002941 palladium compounds Chemical class 0.000 claims abstract description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000005977 Ethylene Substances 0.000 claims abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 20
- 238000007598 dipping method Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910052737 gold Inorganic materials 0.000 claims description 9
- 239000010931 gold Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-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
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- -1 Halogen palladium salt Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-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
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-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
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 230000002829 reductive effect Effects 0.000 description 12
- 238000001035 drying Methods 0.000 description 10
- 230000000977 initiatory effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 235000011056 potassium acetate Nutrition 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 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 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000006424 Flood reaction Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004111 Potassium silicate Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002344 gold compounds Chemical class 0.000 description 2
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 2
- 229910052913 potassium silicate Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 240000006409 Acacia auriculiformis Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- NDQKGYXNMLOECO-UHFFFAOYSA-N acetic acid;potassium Chemical compound [K].CC(O)=O NDQKGYXNMLOECO-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- LPPHVGKXKXBSRU-UHFFFAOYSA-N gold 2-methylpropanoic acid Chemical compound [Au].CC(C(=O)O)C LPPHVGKXKXBSRU-UHFFFAOYSA-N 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 229940076131 gold trichloride Drugs 0.000 description 1
- OTCKNHQTLOBDDD-UHFFFAOYSA-K gold(3+);triacetate Chemical compound [Au+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OTCKNHQTLOBDDD-UHFFFAOYSA-K 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 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 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- PAYGMRRPBHYIMA-UHFFFAOYSA-N sodium;trihydrate Chemical compound O.O.O.[Na] PAYGMRRPBHYIMA-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/007—Esters of unsaturated alcohols having the esterified hydroxy group bound to an acyclic carbon atom
- C07C69/01—Vinyl esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
- C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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Abstract
一种乙酸乙烯酯的生产方法包括将乙烯、乙酸和含氧气体与由包含步骤:(a)用钯化合物浸渍催化剂载体,(b)将钯化合物基本上转化为金属钯,和(c)在高于500℃的温度下烧结载体上的钯的方法制备得到的载体上的钯催化剂接触。
Description
本发明是关于用乙烯、乙酸和含氧气体与载体上的钯催化剂接触生产乙酸乙烯酯的方法。
用于生产乙酸乙烯酯的载体上的钯催化剂的制备一般包括用钯化合物浸渍适当的载体,然后将钯化合物基本上转化为金属钯。
在例如,US3822308,US4048096,US5185308,US5332710,CA2128162,US4087622,CA2128154,CA2128161和US5422329中描述了外壳浸渍催化剂的制备方法。
在如US3743607,BG1333449,US3939199,US4668819,EP330853,EP403950,EP431478和CA2071698中描述了非外壳型催化剂的制备方法。
US5336802中描述了钯-金催化剂预处理的方法,其中催化剂在氧化剂如空气存在下,在温度至少足够氧化部分钯的条件下被加热;排出氧化剂并通入惰性气体如氮气;然后催化剂在温度高达500℃,在还原剂如氢或乙烯存在下被再次加热。其中描述的方法用标称含有1%钯和0.5%金的常规催化剂来具体说明。
现已发现,用于乙酸乙烯酯生产的载体上的钯催化剂的活性随着催化剂的使用而下降。如果催化剂的活性导致产率下降到工业上不能接受的程度,就必须再生和/或替换催化剂。乙酸乙烯酯催化剂的钝化在Chem.Eng.Technol.17(1994)112-118中被Abel等人描述。
仅仅增加催化剂中钯的含量来延长催化剂的寿命存在某些问题,因为对于工业规模的安全和/或可控操作而言,例如,由于工厂的有限的转移热能力,催化剂的初始活性也许太高。
因而尚需要一个克服了上述问题,用于乙酸乙烯酯生产的载体上的钯催化剂的制备方法。
于是,本发明提供了生产乙酸乙烯酯的方法,该方法包括将乙烯、乙酸和含氧气体与载体上的钯催化剂接触,该催化剂的制备包括下列步骤:(a)用钯化合物浸渍催化剂载体,(b)将钯化合物基本上转化为金属钯,和(c)在高于500℃的温度下烧结载体上的钯。
本发明通过在高于500℃温度下烧结载体上的钯来解决上述技术难题。
不希望被任何理论所限制,但相信烧结步骤导致钯金属颗粒的增长,从而降低催化剂的初始活性。这样,用本发明的方法可制备得到具有高钯浓度、工业上又能接受的初始活性的催化剂,这样的催化剂比常规的催化剂具有更长的工业使用寿命。烧结步骤还可以增加二氧化硅载体的平均孔径大小。业已发现,本发明的催化剂不易受过量浓度的助催化剂如乙酸钾的不利影响。
烧结步骤(c)优选使用还原气体进行,但也可以在氧化气体或惰性气体中进行。合适的还原气体是氢或一氧化碳。合适的氧化气体是氧。它们可以被惰性气体稀释。单独使用或与氧化气体或还原气体一起使用的合适的惰性气体是氮气、二氧化碳和氦气。烧结步骤的合适温度是从高于500℃至1000℃,优选650-1000℃。烧结步骤优选的时间是1~24小时。如果使用氧化气体,则催化剂随后需要被还原。在烧结之前,加热期间(为了安全)以及冷却过程中(低于100℃,更优选低于60℃),催化剂可以用惰性气体吹洗以防止钯的任何再分散。可以使用任何适合的或可行的加热和冷却速率。工业规模的烧结步骤(c)可以在能够满足上述工艺条件的塔或容器中进行,操作中催化剂可用气流搅拌,可以使用螺旋转加热炉。在实验室规模,只要气-固接触是充分的(需要考虑长度/直径),就可以使用电加热炉中水平或垂直安装的管。气流可能需要预热。烧结步骤的时间和温度是相关的,温度越高,所需时间越短。本领域技术人员可以修改这些参数来满足操作规模。一般,烧结步骤(c)导致钯金属颗粒直径从3-4nm增大到8-15nm。
将步骤(b)中钯化合物基本转化为金属钯可以通过紧跟其后的烧结步骤(c)之前的还原步骤完成,并且两个操作步骤可以在相同的设备中进行。
本发明催化剂的制备方法可以用于制备在流化床或固定床中生产乙酸乙烯酯的均匀浸渍的或外壳浸渍的催化剂。
本发明的催化剂的制备方法可以制备具有高钯浓度的催化剂,例如以催化剂的总重量为基准,钯含量大于0.5%(重量),优选大于1%(重量)的催化剂。对于流化床操作,钯的浓度可以高达5%(重量),对于固定床操作高达10%(重量)。如果用传统的方法制备具有高钯浓度的载体上的钯催化剂,其初始活性将会很高并且,甚至可能太高以至于如果将它用于工业规模将是不安全的和/或不可控制的。然而,当用本发明的方法制备,所得催化剂的初始活性与用传统方法制备的催化剂的初始活性相比是降低了,但是高钯浓度导致了工业上可接受的活性,并且延长了催化剂的寿命。
为了制备外壳浸渍的和均匀浸渍的催化剂,合适的催化剂载体可以包括多孔二氧化硅、氧化铝、二氧化硅/氧化铝、二氧化钛、二氧化锆或碳,优选二氧化硅。载体可适当地具有每克载体0.2-3.5ml的孔体积、每克载体5~800m2的表面积和0.3~1.5g/ml的表观堆积密度。对于用于固定床工艺的催化剂,载体大小一般为3~9mm。对于用于固定床工艺的催化剂,载体一般是楔形的、片状的、压出物状的、丸状的或任何合适的形状。用于流化床工艺的催化剂,载体一般具有粒子大小的分布是例如至少60%的催化剂粒子具有小于200微米的粒径,优选至少50%的催化剂粒子具有小于105微米的粒径和不超过40%的催化剂粒子具有小于40微米的粒径。
步骤(a)中载体优选用适当溶剂中的钯化合物浸渍。适当的溶剂可以是水、羧酸例如乙酸、苯、甲苯、醇例如甲醇或乙醇、腈例如乙腈或苄腈、四氢呋喃或氯化溶剂如二氯甲烷。优选的溶剂是水和/或乙酸。载体适当地用乙酸钯、硫酸钯、硝酸钯、氯化钯或含卤钯盐如H2PdCl4、Na2PdCl4或K2PdCl4浸渍。优选的水溶性化合物是Na2PdCl4。优选的可溶于乙酸的钯化合物是乙酸钯。
载体的浸渍可以通过与钯化合物的溶液接触并浸渍、浸泡或喷淋进行。浸渍可以在一个或多个步骤或一个连续过程中进行。载体通过用滚动、旋转、摇动或相似的操作与浸渍用的钯溶液接触来形成均匀浸渍。浸渍一般在室温下进行。可以使用升温操作,例如选用乙酸中的乙酸钯时,温度可以高达120℃,优选高达100℃,更优选高达60℃。小心进行浸渍以避免载体的分裂或磨耗。载体可以用浸渍溶液填充5~100%的孔体积。
除了钯化合物外,在步骤(a)中载体还可以用金、铜和/或镍的化合物,优选用金化合物浸渍,这些化合物在步骤(b)中与钯化合物一起转化为金属并与以金属钯颗粒形式存在的钯形成混合物和/或合金。合适的金化合物包括氯化金、四氯金酸(HAuCl4)、NaAuCl4、KAuCl4、二甲基乙酸金、乙酰金酸钡或乙酸金,优选HAuCl4。这些助催化剂的用量为在成品催化剂中含有0.1-10%(重量)的各种助催化剂金属。
除了钯和选择性使用的金、铜和/或镍外,载体还可以在制备过程中的任何适合阶段用一种或多种I主族、II主族、镧系或过渡金属,优选钙、钡、钾、钠、铁、锰、镍、锑和/或镧的盐浸渍,其在成品催化剂中以盐,优选乙酸盐的形式存在,一般选用钾。这些化合物的合适的盐是乙酸盐或氯化物,但是也可以使用任何可溶性盐。这些助催化剂的用量为在成品催化剂中含有0.1~15%(重量),优选3-9%(重量)的各种助催化剂金属。
任选干燥浸渍过的载体,并且如果需要更高的钯或助催化剂的负载量,只要溶剂中盐的溶解度允许,则浸渍步骤可以重复2次或多次。干燥步骤可以在高达120℃,优选高达100℃,并最优选在60℃进行。干燥步骤可以在室温和减压条件下进行。干燥步骤中可用空气、氮气、氦气、一氧化碳或任何合适的惰性气体。催化剂可以通过气流进行滚动、旋转或搅拌以帮助干燥。
为了制备外壳浸渍催化剂,湿的或干的浸渍过的载体通过摇动、滚动、旋转、混合等等与碱溶液接触。在滚动、旋转、混合等过程中,碱溶液也可以通过喷淋到浸渍过的载体上使用。碱可以是I族或II族的氢氧化物、碳酸盐或硅酸盐。典型的实施例是氢氧化钠、硅酸钠、氢氧化钾、硅酸钾、氢氧化钡。由于操作中有适当的时间延迟,碱溶液用于一个或多个步骤中。沉积步骤的温度常常是室温,但也能增加到100℃。可用任何可溶解原料的溶剂,优选水。碱应与浸渍过的载体接触适当的时间以便使金属盐沉积在外壳上。这常常需要超过1个小时,优选8~24小时。由于沉淀需要最佳的碱含量而且常常要求过量,所以采用的碱含量一般是产生金属盐氢氧化物所需理论含量的1.8倍。
浸渍过的载体可以经洗涤除去阴离子杂质,例如硝酸盐、硫酸盐和通常的卤化物。为了除去氯离子,应用去离子水洗涤,直至硝酸银试验显示无氯离子的存在。阴离子杂质含量应降至最低。阳离子杂质含量应降至最低,例如干燥催化剂中钠的含量低于0.5wt%,优选低于0.2wt%。低含量的杂质可能会残留,杂质含量绝对为零是不必要的。在工业规模上,可以用间歇洗涤。为了加快过程,可使用热水。而且,离子交换溶液(如乙酸钾)能用来置换氯离子和钠。可以选择制备所用试剂以避免使用氯化物和钠,例如,用硅酸钾代替钠盐。
步骤(b)中钯化合物转化为金属可以在上述任选的洗涤步骤之前或之后进行,这取决于所用试剂。可以使用液体还原剂例如肼水溶液、甲醛、甲酸钠、甲醇或醇类,优选肼水溶液。还原反应也可以用气体如一氧化碳、氢气和乙烯进行。这些气体可用惰性气体如氮气、二氧化碳或氦气稀释。一般,气体的还原作用在温升为100-500℃进行,直至原料被还原。一般,在液体还原剂中的还原作用于室温下进行,但也可使用高达100℃的温度。
在钯化合物转化为金属后,将其如本文中所述进行烧结。烧结步骤(c)可以跟随在步骤(b)之后,在还原气体中进一步加热催化剂至高于500℃。然后如前文所描述的那样用助催化剂盐浸渍所得物料。
用本领域的已知方法,将乙烯、乙酸和含氧气体与按照本发明的催化剂制备方法制得的载体上钯催化剂相接触。从而,反应物可以在温度为145-195℃,压力为1~20atm条件下在固定床或流化床中与催化剂相接触。用本领域公知的常规方法回收乙酸乙烯基酯产物。
下面参照图1至3和下面的实施例以及实验详细说明本发明。图1是根据本发明的一些可能的催化剂制备方法的图解表示法。图2是两种产率即按本发明制备的催化剂的产率与不是按本发明制备的催化剂的产率作为时间函数的对比图。图3是比较助催化剂乙酸钾的含量对根据本发明制备的催化剂的活性的影响及其对不是根据本发明制备的催化剂的活性的影响的曲线图。
参照图1,均匀(非外壳)型催化剂可以通过用钯盐和任选任选助催化剂浸渍载体,随后进行干燥并还原金属的步骤制备。然后按照本发明,在烧结之前任选洗涤和干燥物料,最后任选用助催化剂如钾、钠、铬或钡的乙酸盐浸渍。
为了制备外壳型催化剂,可以将用钯和任选助催化剂如金浸渍过的载体任选进行干燥。然后沉淀金属,再将物料经过或者(i)还原为金属,洗涤并干燥;或者(ii)洗涤,干燥随后还原为金属。接着按照本发明烧结物料,之后用助催化剂如钾、钠、铬或钡的乙酸盐浸渍。实施例1
根据本发明制备的催化剂A具有1.8%的钯(重量)、0.8%的金(重量)和7%的乙酸钾(重量)的理论组成(即在制备过程中不允许任何损失)。1、载体的浸渍
将15g的KA160二氧化硅载体球(4-6mm,SudChemie)加入到1.0264g的四氯化钯(III)酸钠三水合物(Johnson Matthey)和0.2655g的氯金酸三水合物在9.1g的去离子水中的溶液中。硅载体被一次性加入并摇动混合物直至溶液均匀吸收。然后在室温下将浸渍过的载体保持覆盖2小时。2、钯和金的化合物在载体上的沉淀
将1.7g五水合硅酸钠(Fisons)在18g水中的溶液加到由步骤1得到的浸渍过的载体中。稍稍摇动混合物数次,时间为15分钟以避免形成结块,然后静置过夜。3、将钯和金基本还原为金属状态
用5g 55%的水合肼(Aldrich)处理由步骤2得到的物料上层的水相。4、载体上化合物的洗涤
将水相倾析出,用大约50ml的水将步骤3所得物料洗涤四次,每次洗涤后都进行倾析。所得物料转入安装了活塞的玻璃柱中并用约1升/12小时的去离子水洗涤直至硝酸银试验呈阴性。物料在鼓风炉中于60℃干燥过夜并冷却。5、钯(和金)的烧结
将步骤4所得载体上的钯物料转入水平安装的加热炉中并装入用石英棉和KA160载体(事先彻底干燥)作衬垫的石英管的中央填充空隙空间。石英管衬垫放置于钢管中并且与供气管相连。加热炉温度以10℃/min上升到150℃,在恒定的氮气气流条件下保持该温度2小时。以60/小时的气时空速通入氢气流并停止通入氮气流。炉温以30℃/min上升到800℃,保持该温度11小时。此后在氢气流条件下将所得物料冷却至室温。在卸料之前再次通入氮气流并停止通入氢气流。6、乙酸金属盐的浸渍
用溶解在8.8g水中的1.16g无水乙酸钾(Aldrich)溶液浸渍步骤5所得干燥的物料。轻轻摇动混合物直至液体被吸收。所得物料在60℃再次干燥过夜。实施例2(对比实施例)
根据省略了烧结步骤5的实施例1的方法制备催化剂B。实施例3(对比实施例)
根据省略了烧结步骤5的实施例1的方法制备催化剂C并降低金属负载得到与实施例1中制备的催化剂具有相同初始活性的催化剂C。在微型反应器中的催化剂试验
用下述的一般程序在微型反应器中进行上文制得的催化剂试验。使用被60ml的1mm的玻璃珠稀释并装载于内径为10-11mm的不锈钢管中的催化剂丸(制备如上所述,含量说明见表1),在7.8barg和150℃的条件下进行试验。于7.8barg压力下投入催化剂,并在氮气流中在160℃的条件下加热3小时,然后置于150℃的乙烯气流中。将乙酸蒸汽和乙烯混合并通过催化剂至少50分钟。将21%的氧在氦气中的混合物逐渐加到原料气中,同时维持催化剂床最高温度为150℃。催化剂热点保持在150℃。反应混合物的最终体积组成为乙烯∶乙酸∶氧气∶氦气=53.1∶10.4∶7.7∶28.6,且总气时空速为3850hr-1。用联机气相色谱每隔1小时分析汽相中的产物气流。
催化剂活性按每小时每升催化剂生产的乙酸乙烯酯的克数(时空产率,STY)计算且催化剂的选择性以转化成产物的乙烯百分数计算。所报道的数据以在达到全氧含量后的17至22小时之间测得的活性及选择性的平均值为基准。
催化剂A、B和C的活性的比较结果列于表1。
表1
表1中催化剂A和B的活性的比较表明烧结步骤(步骤5)导致了催化剂A活性降低。这一点与钯颗粒大小的增大以及钯金属表面积的减小相符合。与催化剂A和B相比较,用较低的金属负载量制备催化剂C,选择金属负载量使催化剂C与催化剂A具有相同的初始活性。因此可以预计催化剂A和C有相似的初始操作性能。如果钯颗粒的增大和钯金属表面积的减小是初始活性降低的原因,则可以预计与催化剂C相比,催化剂A将会在一个较长的时期内维持产率不变。实施例7和8说明了这一点。在较大反应器中的催化剂试验
催化剂 | 装载于微型反应器中的催化剂(g) | 活性(每升催化剂每小时产生的乙酸乙烯酯克数) | 选择性(%) | |
实施例4 | A | 2.5 | 715 | 92.4 |
实施例5(对比实施例) | B | 2.0 | 1381 | 90.7 |
实施例6(对比实施例) | C | 2.5 | 718 | 93.4 |
催化剂A和C在较大管状反应器中的试验如下。77.5g的催化剂A(实施例7)和77.5g的催化剂C(对比实施例8)分别装入两个6英尺反应管中。这两个管均放在相同的流化床砂浴器中。砂浴温度可控且每个管具有各自的气/液进料及产物处理系统。以1106ml/min的速度(标准温度压力下)通入氮气流,以2590ml/min的速度(标准温度压力下)通入乙烯气流。将砂浴器和反应管加热至150℃且反应器压力上升到115psig。以155g/hr的流量将乙酸(含有2wt%水)通入蒸发器中并与氮气和乙烯混合。将13g/hr小流量的乙酸(含2wt%水,0.0285wt%乙酸钾)引入预热带与主气流一起蒸发。几个小时后,以153ml/min(标准温度压力下)的速度通入氧气。用联机气相色谱分析产物流并浓缩得到乙酸乙烯酯、乙酸和水的液态粗产品,排放剩余气体并用联机气相色谱从中取样分析。监测使用两种催化剂得到的乙酸乙烯酯产物。随着催化剂的失活,将氧气进料逐渐增加到425ml/min的最大值(标准温度压力下)以便从一开始保持一个恒定的产率。达到全氧气流且总气时空速为2261hr-1时(标准温度压力下),气体进料的体积组成是乙烯∶乙酸∶水∶氧气∶氮气=49.7∶19.6∶1.3∶8.2∶21.2。一旦达到全氧进气率,通过逐渐增加砂浴温度从约150℃至160℃以进一步保持催化剂A的恒定产率。由于两个反应管处于相同的砂浴中,所以随着催化剂C的更快的失活其产率下降到低于催化剂A的产率。图2显示的是作为生产无数的函数的催化剂A和C的正规日产量。图2清楚的表明,尽管两种催化剂的初始生产能力相似,但是在生产5天后,对比催化剂C的生产率低于本发明的催化剂A的生产率。研究两种催化剂的生产率的斜率可知催化剂A的生产率维持在大约1而催化剂C的产量则随时间缓慢下降最终达到0.7的生产率。接近试验终点时,通过调整氧进气量和/或砂浴温度,检测以催化剂C为基准的催化剂A的生产率。由图2可见产量上下地变化且催化剂A始终比催化剂C具有较高的生产率。尽管它们的初始活性非常相似,但催化剂A与催化剂C相比仍显示了较慢的失活速度。实施例9-使用微型反应器的其他催化剂试验
除了将所用试剂的量用系数9按比例换算外,按照实施例1的方法制备另外两批催化剂。经洗涤和干燥步骤后,将每批催化剂准确分为9等份并用目标负载量为wt%的乙酸钾浸渍(见表2)。按照实施例1至3的方法试验这些催化剂样品。图3显示了这些催化剂样品达到的活性并将它与US5179056中报道的相应的催化剂活性进行比较(按照US5179056中描述的方式外推得到催化剂样品的活性)。图3显示根据本发明的催化剂在钾的最低含量为约1.5wt%时生效,而对于US5179056中的催化剂在钾含量约为2.5wt%时达到最大活性。对于本发明的催化剂,当钾含量在约1.5-5wt%时,助催化剂的影响基本稳定。对于US5179056中的催化剂其活性随助催化剂负载量的增加而降低。
表 2
乙酸钾的目标重量(wt%) | X射线荧光分析钾的重量(wt%) | 活性(克乙酸乙烯酯/小时/升催化剂) | 选择性(%) | 按US5179056中的方式外推得到的活性 | US5179056中的活性 |
0 | 0.12 | 11 | 1 | 13 | |
1 | 0.5 | 147 | 74.5 | 142 | |
2 | 0.87 | 385 | 89.1 | 382 | |
3 | 1.17 | 548 | 91 | 556 | |
3 | 1.2 | 554 | 90.3 | 570 | |
4 | 1.54 | 710 | 92 | 687 | 688 |
5 | 1.86 | 745 | 92.5 | 735 | 731 |
5 | 1.9 | 752 | 91.4 | 738 | 735 |
6 | 2.1 | 729 | 92.8 | 749 | 751 |
7 | 2.6 | 750 | 91.8 | 757 | 759 |
8 | 2.8 | 764 | 92.8 | 757 | 748 |
9 | 3.2 | 771 | 93.1 | 757 | 706 |
9 | 3.3 | 778 | 91.5 | 757 | 691 |
10 | 3.6 | 745 | 93.3 | 757 | 639 |
11 | 3.8 | 776 | 92.1 | 757 | 599 |
14 | 4.8 | 719 | 93.3 | 757 | |
15 | 5.1 | 759 | 93 | 757 | |
15 | 5.2 | 743 | 91.8 | 757 |
这表明按照本发明制备的催化剂更能容许过剩的乙酸钾助催化剂浓度。
Claims (12)
1、一种乙酸乙烯酯的生产方法,包括将乙烯、乙酸和含氧气体与由包括下列步骤的方法制备得到的载体上的钯催化剂相接触:
(a)用钯化合物浸渍催化剂载体,
(b)将钯化合物基本上转化为金属钯,
(c)在高于500℃的温度下烧结载体上的钯。
2、根据权利要求1的方法,其中催化剂载体用选自在水、羧酸、苯、甲苯、醇、腈、四氢呋喃或氯化溶剂中的钯化合物浸渍。
3、根据权利要求2的方法,其中溶剂是水和/或乙酸。
4、根据上述任一权利要求的方法,其中钯化合物是乙酸钯、硫酸钯、硝酸钯、氯化钯或含卤钯盐。
5、根据权利要求4的方法,其中钯化合物是乙酸钯。
6、根据上述任一权利要求的方法,其中步骤(b)是通过钯化合物和选自肼水溶液、甲醛、甲酸钠、醇、一氧化碳、氢或乙烯的液态或气态还原剂相接触进行。
7、根据上述任一权利要求的方法,其中步骤(c)是在650~1000℃的温度范围内进行。
8、根据上述任一权利要求的方法,其中步骤(c)是在气体中进行。
9、根据上述任一权利要求的方法,其中钯催化剂包含至少0.5%(重量)的钯,以催化剂的总重量为基准。
10、根据上述任一权利要求的方法,其中催化剂载体包含多孔二氧化硅、氧化铝、二氧化硅/氧化铝、二氧化钛、二氧化锆或碳。
11、根据上述任一权利要求的方法,其中在步骤(a)中钯载体用金、铜和/或镍的化合物,一种或多种I主族、II主族、镧系或过渡金属的盐浸渍。
12、根据上述任一权利要求的方法,其中乙烯、乙酸和含氧气体与催化剂在温度为145-195℃之间,压力为1~20大气压条件下接触。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1314490C (zh) * | 2003-04-23 | 2007-05-09 | 中国石油化工股份有限公司 | 用于合成醋酸乙烯酯的催化剂的制备方法 |
CN101014561B (zh) * | 2003-05-02 | 2012-04-04 | 万罗赛斯公司 | 将碳氢化合物转化为氧化物或腈的方法 |
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NO975057D0 (no) | 1997-11-03 |
CA2219966A1 (en) | 1998-05-04 |
AR010544A1 (es) | 2000-06-28 |
RU2197472C2 (ru) | 2003-01-27 |
NZ329092A (en) | 1998-01-26 |
GB9622911D0 (en) | 1997-01-08 |
CN1153755C (zh) | 2004-06-16 |
MY120308A (en) | 2005-10-31 |
CA2219966C (en) | 2006-02-07 |
SA98190191A (ar) | 2005-12-03 |
KR19980042071A (ko) | 1998-08-17 |
USRE37744E1 (en) | 2002-06-11 |
TW411329B (en) | 2000-11-11 |
US5990344A (en) | 1999-11-23 |
DE69711320T2 (de) | 2002-07-25 |
ES2175286T3 (es) | 2002-11-16 |
NO975057L (no) | 1998-05-05 |
BR9709477B1 (pt) | 2008-11-18 |
KR100535736B1 (ko) | 2006-06-22 |
US6492299B1 (en) | 2002-12-10 |
EP0839793B1 (en) | 2002-03-27 |
ID18766A (id) | 1998-05-07 |
EP0839793A1 (en) | 1998-05-06 |
JP4137204B2 (ja) | 2008-08-20 |
JPH10139727A (ja) | 1998-05-26 |
DE69711320D1 (de) | 2002-05-02 |
SG63770A1 (en) | 1999-03-30 |
ZA979733B (en) | 1999-04-29 |
BR9709477A (pt) | 2000-05-02 |
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