TWI229665B - Process for the production of acetic acid - Google Patents
Process for the production of acetic acid Download PDFInfo
- Publication number
- TWI229665B TWI229665B TW088115202A TW88115202A TWI229665B TW I229665 B TWI229665 B TW I229665B TW 088115202 A TW088115202 A TW 088115202A TW 88115202 A TW88115202 A TW 88115202A TW I229665 B TWI229665 B TW I229665B
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- Taiwan
- Prior art keywords
- catalyst
- patent application
- scope
- acetic acid
- item
- Prior art date
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 81
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000005977 Ethylene Substances 0.000 claims abstract description 32
- 239000012530 fluid Substances 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 19
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 11
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910052787 antimony Inorganic materials 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- -1 oxidized hammer Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000011964 heteropoly acid Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000011133 lead Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000011135 tin Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 239000004005 microsphere Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052745 lead Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052770 Uranium Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-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
- 238000004821 distillation Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 6
- 229910000449 hafnium oxide Inorganic materials 0.000 claims 4
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- 229910000831 Steel Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000012535 impurity Substances 0.000 claims 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical class [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 claims 1
- 239000010959 steel Chemical class 0.000 claims 1
- 239000002253 acid Substances 0.000 description 19
- 238000011049 filling Methods 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000010955 niobium Substances 0.000 description 7
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 7
- 239000011651 chromium Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 230000002079 cooperative effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical class 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 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical class [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 229910052716 thallium Inorganic materials 0.000 description 3
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- CNRAKGUYRGEPFS-UHFFFAOYSA-N P(O)(O)(O)=O.[Mo].[W] Chemical compound P(O)(O)(O)=O.[Mo].[W] CNRAKGUYRGEPFS-UHFFFAOYSA-N 0.000 description 2
- DKSYRQMNUCTEAY-UHFFFAOYSA-N P(O)(O)(O)=O.[V].[W] Chemical compound P(O)(O)(O)=O.[V].[W] DKSYRQMNUCTEAY-UHFFFAOYSA-N 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- NFFRXEFGTCBHKT-UHFFFAOYSA-N [Si](O)(O)(O)O.[W].[Mo] Chemical compound [Si](O)(O)(O)O.[W].[Mo] NFFRXEFGTCBHKT-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- OHAVYOCBYILSBZ-UHFFFAOYSA-M dihydroxyboron;hydroxy(dioxo)tungsten Chemical compound O[B]O.O[W](=O)=O OHAVYOCBYILSBZ-UHFFFAOYSA-M 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000013529 heat transfer fluid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- JIWHQPLZKGSAJE-UHFFFAOYSA-N B(O)(O)O.[W].[Mo] Chemical compound B(O)(O)O.[W].[Mo] JIWHQPLZKGSAJE-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910003244 Na2PdCl4 Inorganic materials 0.000 description 1
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical compound [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 description 1
- FYBPWXOTHCOQJN-UHFFFAOYSA-N [Mo].[Sm] Chemical compound [Mo].[Sm] FYBPWXOTHCOQJN-UHFFFAOYSA-N 0.000 description 1
- TTZGICPOSYHERT-UHFFFAOYSA-N [Si](O)(O)(O)O.[Mo] Chemical compound [Si](O)(O)(O)O.[Mo] TTZGICPOSYHERT-UHFFFAOYSA-N 0.000 description 1
- RRSWMKXTVMDBHD-UHFFFAOYSA-N [Si](O)(O)(O)O.[V].[W] Chemical compound [Si](O)(O)(O)O.[V].[W] RRSWMKXTVMDBHD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical class [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002706 dry binder Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 210000000003 hoof Anatomy 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- VOGXWIXFACVZHK-UHFFFAOYSA-N molybdenum phosphoric acid vanadium Chemical compound [Mo][V].OP(O)(O)=O VOGXWIXFACVZHK-UHFFFAOYSA-N 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229940073020 nitrol Drugs 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011591 potassium Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical compound [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 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
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/12—Acetic acid esters
- C07C69/14—Acetic acid esters of monohydroxylic compounds
- C07C69/145—Acetic acid esters of monohydroxylic compounds of unsaturated alcohols
- C07C69/15—Vinyl acetate
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- 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
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
-
- 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
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
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- 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
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/686—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with molybdenum
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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
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- Oil, Petroleum & Natural Gas (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
1229665 A7
{ i 請 先- 閱 讀. 背_ 之 注 項 再 填 本 頁
訂 a
I229665 A7 ^〜------___-___ 五、發明說明（2 ) 所欲。 吾等現發現催化劑磨損之問題對於流體化床系統可經 由使用微球狀顆粒催化劑材料克服之。 因此，本發明提供一種製備乙酸之方法，該方法包含 於流體化床反應器内且於微球狀顆流體化顆粒固態氧化催 化劑存在中使乙烧及/或乙稀與含分子氧之氣體接觸，其 中至少90%之該催化顆粒係少於3〇〇微米。 本發明提供一種於流體化床反應器中經由使用特殊顆 粒催化材料製備乙酸之方法。使用此特定之催化劑可克服 先前於流體化床方法中遭遇之操作問題。 本發明方法需要一種微球狀顆催化劑。其需要至少 90%之該催化顆粒係少於300微米，較佳係至至95%之該 催化顆粒係少於300微米。適當者，顆粒大小之分佈可為 如下所述： 0-20微米 0.30重量％ 20-44微米 0-60重量％ 44-88微米 10-80重量％ 88-106微米 10-80重量％ >106微米 0-40重量％ >300微米 0-5重量％ 經濟部智慧財產局員工消費合作社印製 適當者，催化劑之密度係0.5至5g/cm3，較佳係1至3 g/cm3 ’ 特別係 1.5至2 g/cm3。 催化劑被用於流體化床反應器，較佳係催化劑顆粒係 磨損催化劑。 5 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1229665 A7
經濟部智慧財產局員工消費合作社印製 五、發明說明（3 ) 適用於流體化床方法中之用以轉化乙烷之催化劑係傳 統之乙燒催化劑，但此等催化劑需以微球狀顆形式使用之 〇 ^ ^之催化劑包含一種包含翻之催化劑組成物，例如 M〇aXbYc，
其中 ’ X係 Cr，Mn，Nb，Ta，Ti，V及/或 W Y係 Bi，Ce，Co, Cu，Fe，K，Mg，Ni，P, Pb，Sb，Si， sn，T1及/或U，且較佳係Sb，Ce及/或U a係1 b係0.05至1.0，且 c係0至2，且較佳係0.05至1.0，但對於c〇，Ni 及/或Fe之c之總值係少於0.5 相等適當者係ModReeWgXY之催化組成物 其中，A=ModReewf， X=Cr，Mn，Nb，Ta，Ti，V及/或W，較佳係Mn，Nb，V 及/或W， Y=Bi，Ce，Co, Cu，Fe，K，Mg，Ni，P，Pb5 Sb，Si，Sn，ΤΙ
及/或U，較佳係Sb，Ce及/或U a=l， b=0至2，較佳係0.05至1.0 c=0至2，較佳係〇·〇〇1至ΐ·〇，且更佳係〇 (^至丨〇， 但對於Co, Ni及/或Fe之c之總值係少於0.5， d+e+f=a 5 d係0或大於0， 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 6 (請先閱讀背面之注意事項再填寫本頁) 訂i'_ A7
I229665 五、發明說明（4 ) e係大於0，且 f係0或大於0。 亦可能者係MoaPdbReeXdYe之催化組成物，
其中 ’ X=Cr，Mn，Nb，B，Ta，Ti，VA^W
Y=Bi，Ce，Co，Cu5Te，Fe，Li，K，Na，Rb5Be，Mg，Ca，Sr，Ba， Ni，P，Pb，Sb，Si，Sn，TlW*U a，b，c及d表示相對應兀素之克原子比例，其中 a=l,b>0, c>0, d=〇.〇5至2且e=0至3 〇 進一步適合之催化劑係MoaPdbXcYd 其中X表示一或多個選自Cr，Mn，Nb，ta，TI，V及W之元素 Y表示一或多個選自 B，Al，Ga，In，Pt，Zn，Cd，Bi，Ce， Co, Rh，Ir，Cu，Ag，Au，Fe，Ru，Os，K，Rb，Cs，Mg， Ca，Sr, Ba，Zr，Hf，Ni，Pb，Sb，Si5 Sn，T1及U 之元 素， a，b，c及d表示相對應元素之克原子比例， 其中 a=l; b>0; c>0且(1=0-2。 進一步適當之氧化物催化劑係MoaWbAgeIrdXeYf，
其中，X係元素Nb及V Y係一或多個選自 Cr，Mn，Ta，Ti，B，Al, Ga，In, Pt， Zn，Cd，Bi，Ce，Co, Rh，Ir，Cu，Ag，Au，Fe，Ru，〇s，K， Rb，Cs，Mg，Ca，Sr，Ba，Zr，Hf，Ni，P，Pb，Sb，Si，Sn，Tl， U，Re及Pci之元素； a，b，c，d，e及f表示元素之克比例，如此， 1 本紙張尺度適用_A4 _21Q x 297 H } - 7 — (請先閱讀背面之注意事項再填寫本頁) 【裝--------：訂—.-------. 經濟部智慧財產局員工消費合作社印製 !229665 A7 B7 五 經濟部智慧財產局員工消費合作社印製 、發明說明（ 0<a$ l，〇$b<l 且 a+b=l 0<(c+d)^0.1
〇<e^ 2 JL 0^f^2 使乙烧轉化成乙酸之較佳催化劑係M〇AgVNb。 若供料包含乙烯及含分子氧之氣體，適用於本發明 方法之催化劑包含金屬把及雜多酸或其鹽之組成物。雜多 酸可含有一個雜原子或一或多個多原子。雜原子適當地可 為磷、矽、硼、鋁、鍺、鈦、錯、鈽、鈷、鉻或硫。多原 子適當者可為鉬、繞、鈒、銳或组。 雜多目欠之例子可包含石夕嫣酸、碟嫣酸、碟鉬酸、石夕|目 酸、鎢鉬磷酸、鎢鉬矽酸、鎢釩磷酸、鎢釩矽酸、鉬釩磷 酸、鉬鈒矽酸、硼鎢酸、硼鉬酸、鎢鉬硼酸、鉬鋁酸、鎢 銘酸、鉬鎢鋁酸、鉬鍺酸、鎢鍺酸、鉬鎢鍺酸、鉬鈦酸、 嫣鈦酸、鉬鎢鈦酸、鈽鉬酸、鈽鎢酸、鈽鉬鎢酸、鉬鈷酸 、嫣姑酸、鉬嫣銘酸、填峨酸酸、碎峨酸酸及、碎组酸。 其間’特別佳者係矽鎢酸、填鎢酸、鱗鉬酸、矽鉬酸、鎢 翻磷酸、磷鉬酸、矽鉬酸、鎢鉬磷酸、鎢鉬矽酸、鎢釩磷 酸、鎢鈒矽酸、鉬飢矽酸、硼鎢酸、硼鉬酸及硼鉬鎢酸。 雜多酸之鹽可為金屬或類鹽，其中藉由縮合二或多個 無機氧酸形成之氫原子或酸係部份或完整地以一或多個金 屬或類陽離子取代。其間雜多酸之氫原子被其取代之金屬 係選自長型式週期表之第1(1A)，2(2A)，11(1B)及13(3B)族 之金屬，諸如，鹼金屬、鹼土金屬、銅、銀、金、鋁、鎵 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） (請先閱讀背面之注意事項再填寫本頁) . 8 1229665 經濟部智慧財產局員工消費合作社印製 A7 — *-----—---— _ 五、發明說明（6 ) 、銦及鉈。作為類鹽之例子，其可為衍生自銨或胺之銨鹽 。於雜多酸中，特別佳者係鋰、鈉、鉀、鉋、鎂、鋇、銅 、金及鎵e之鹽，但最佳之例子係磷鎢酸之鋰、鈉及銅之 鹽及矽鎢酸之銅鹽。 催化劑組成物中之鈀對雜多酸之比例適當者係丨克原 子：0.025至500克分子，較佳係1克原子：〇丨至牝❽克分 子。 催化劑組成物亦可適當地包含選自週期表第Σ Β,ΚΒ， VB及VIB族之金屬。適當之金屬包含銅、銀、錫、鉛、 銻、鉍、硒及碲。若金屬存在，鈀對雜多酸對金屬之比例 適當者係1克原子：0.025至500克分子：〇.〇〇5至1〇克原子 ，較佳係1克原子：心丨至#^克分子·· 〇 〇1至5克原子。 由乙烯及含氧氣體製備乙酸之較佳催化劑係三組份系 統，包含·（1)金屬鈀，（2)磷鎢酸，矽鎢酸或磷鎢酸之鋰 、鈉及銅鹽及矽鎢酸之鈉及銅鹽之至少一者；及（3)絲、 石西及蹄之至少一者。 適當者，轉化乙烷及/或乙烯之催化劑包含黏結金屬 ’其可為石夕石、氧化鈦、氧化紹、氧化錯或其等之混合物 。適當者，黏合金屬係以催化劑組成物之至少1〇 濃度存在之。 催化劑組成物可以任何傳統上用於製備流體化床催化 劑之方法製備。對於乙烷氧化催化劑，催化劑可適當地藉 由噴灑乾燥黏合材料（例如，矽石溶膠）、元素之錯合物 或化合物（例如，氧化物）及水之漿液而製備。催化 本紙張尺度適用中國國家標準GNS)A4規格（210 x 297公爱） ：—·------裝— (請先閱讀背面之注意事項再填寫本頁) I. 9 1229665 濟 慧 局 員 工 消 費 五、發明說明（ 津可藉由加熱至300與800。〇間之溫度燒結 ，適當者係於空 孔或氧中進行1分鐘至24小時。較佳者，空氣或氧係自由 流動。 對於製備乙稀氧化催化劑，諸如，把雜多酸催化劑， -可以傳統方法製備之。適當者，催化劑可藉由使把化合 物及金屬化合物溶於適當溶劑中而製備之。載體或黏合金 f可被添加至溶液。所形成之溶液可被乾燥以提供此催化 ^另外催化劑可藉由添加沈澱介質沈澱。所形成之化 合物藉由諸如氫或肼之還原劑適當還原之。另外，催化 7藉由喷灑乾燥所欲撐體製備之。然後，㈣藉由濕化 f添加肛乾燥所形成之化合物。乾燥後之產物可以適當 還原劑還原之。 供料氣體包含乙院及/或乙烯。乙烧及乙烯可以實 上純的形式或與氮、甲烧、二氧化碳或水（流體形式， 可以主要量存在，例如，大於5體積％)混合使用之。 等氣體可以新的氣體添加，或以循環氣態流體引入。氫 二氧化碳、C3/C4之燒及烯亦可以少量存在之，例如， 於5體積％。 含，子氧之氣體可為空氣或相較於空氣為較多或較少 之分子氧之空氣，例如，^。適當之氣體可為，例如， 適當稀釋劑（例如，氮）稀釋之氧。 選擇性地’水（水蒸氣）可與乙燒及/或乙婦及含分 子氧之氣體供應至反應器。 此方法-般係㈣〇至5(H)t之溫度範圍進行之，較佳 劑 濕 之 訂 質 其 此 少 以 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公董 10 .
I
五、發明說明（8 ) I229665 係 140至400°C。 壓力適當者可為大氣壓或超大氣壓，例即，丨至咒巴 ，較佳係1至30巴。 於較佳實施例中，本發明之方法可為諸如描述於，例 如，國際專利公” WO觸测之製備乙酸及/或乙酸乙 烯醋之整體方法之第一步驟，該案之内容在此被併入以供 參考。因此’依據此實施例’提供一種製備乙酸及/或乙 酸乙烯酯之整體方法，其包含之步驟係： ⑷於第-反應區域内，於用以活化使乙烯氧化成乙酸及/ 或使乙烷轉化成乙酸及乙稀（如前所述者）者之催化 劑存在中，使包含乙烯及/或乙烷及選擇性之蒸氣之供 料與含分子氧之氣體接觸，以製備第一產物流體，其 包含乙酸、水及乙烯（未反應之乙烯及/或共同生產之 乙烯）及選擇性之乙烷、一氧化碳、二氧化碳及/或氮 :及 (b)於第二反應區内於額外之乙烯及/或乙酸存在或缺乏中 ，使包含至少為乙酸、及乙烯及選擇性之水·乙烷、 一乳化峡、二氧化碳及/或氮之至少一者之第一氣態產 物流體之一部份與含分子氧之氣體於用以活化乙酸乙 烯醋之生產之催化劑存在中接觸，以產生第二產物流 體，其包含乙酸乙烯酯、水、乙酸及選擇性之水。 較佳者，整體方法進一步包含之步驟係： (C)藉田蒸餾使得自步驟（1})之產物流體分離成包含乙酸乙 烯δ旨及水之頂部分德物及包含乙酸之底部分鶴物；及 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） —：—·------裝— (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 11 1229665 A7 "^-------B7______ 五、發明說明（9 ) ()(1)回收自步驟（c)分離之底部份館物之乙酸，及於部份 (請先閱讀背面之注意事項再填寫本頁) 或70王刀離水後選擇性地循環步驟（c)之共沸分餾物至 步驟（C)， 或⑻自步驟（C)分離之共彿分鶴物回收乙酸乙稀醋及 選擇性地使步驟⑷分離之底部分鶴物循環至步驟⑻， 或（111)自步驟（c)中分離之底部分餾物回收乙酸及自步 驟（c)回收之頂部共沸分餾物回收乙酸乙烯酯。 本發明之催化劑及方法現將進一步以下列範例例示之 0 催化劑之製備 (1)乙烷氧化反應# 經濟部智慧財產局員工消費合作社印製 流體化床乙烷氧化反應催化劑包含數種加入拉抗磨損 之以矽石為基準之微球狀顆之流體化床撐體之元素。微球 催化劑係藉由喷灑乾燥包含矽石溶膠、鉬酸銨、乙酸銀、 飢酸銨、氣化鈮及草酸及水之混合物之漿液製備之，產生 目標催化劑組成物Mo^AgawVQ.18Nb。 .09。然後，微球於400 °C間之空氣中燒結以分解鹽且對催化劑產生強度（抗磨損） 。最終催化劑中之上述元素之比例係5〇重量％。最終催化 劑中之矽石之比例係50重量％。 催化劑性皙 顆粒大小分佈 0-20微米 0-30重量％ 20-44微米 0-60重量％ 44-88微米 10-80重量％ 12 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7B7 五、發明說明（10) 88-106微米 10-80重量％ >106微米 〇-4〇重量％ >300微米 〇-5重量％ 密度 〇.5-3.0g/cm2 所製得之催化劑被發現具有組成為MoG.73Ag0.01 V〇.i8Nb。。8預燒結。 (2)乙烯氧化反應之催化劑
Na2PdCl4 (1.5829克）被溶於去離子水（20克），然後反 浸潰（添加固體至溶液）於喷灑乾燥之矽石撐體（29.99克 ’ 17500-39B，平均70微米直徑）。所形成之固體於室溫及 壓力乾燥16小時。NH2NH2水合物（3.33克）被添加至去離子 水（80克）。乾燥之固體被緩慢添加至肼溶液。混合物於室 溫及壓力靜置16小時且偶而產生旋流。溶液被吸濾以使固 體與濾液分離，然後以去離子水（4x125毫升）清洗，其後 當測試氣化物存在時，濾液產生負結果。固體於室溫及壓 力乾燥40小時’產生還原之鈀催化劑中間產物。KSe〇4 (0.246克）被溶於去離子水（2〇克）且反浸潰於還原之鈀催化 劑中間產物固體，其於室溫及壓力乾燥16小時。 H4Si〇4」2W〇3.xH2〇(9.45克）被溶於去離子水且反浸潰於 乾燥固體上，然後於6〇°C再次乾燥40小時。所形成之催化 劑於使用前藉由於200°C加熱4小時活化之。 乙酸之製備 40亳升之流體化床非均質反應器於容器内於8巴時操 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 x 297公髮） (請先閱讀背面之注咅？事項再填寫本頁) .- 經濟部智慧財產局員工消費合作社印製 13 I229665 A7
五、發明說明（η ) 經濟部智慧財產局員工消費合作社印製 作之’藉此，熱轉移流體被循環。反應劑以蒸氣相經由燒 結疋件供應至反應器之底部以使催化劑流體化。自作為主 要氣體供料之相同來源提供質流控制之額外之氧及/或1 至反應器。壓力藉由反應器之一般出口上之後壓力控制閥 保持之。反應器之溫度藉由循環以Haake浴加熱之熱傳流 體保持。數點熱偶測量反應器溫度。此反應器被用於用以 自乙烧及/或乙烯及含氧氣體製備乙酸之一系列之流體化 床實驗測試。反應條件如第1及2表所示。 出口流體組成之線上氣體色譜法分析能使製備乙酸之 空間時間產量計算被算出。此分析不包含乙烯之共同生產 之計算。 對於每一流體化床實驗，反應器被注以催化劑或催化 劑/稀釋劑’然後於氮氣加壓下密封且測試之。一旦於穩 定之反應溫度及壓力時，反應物流體被序列地引入（烴、 条氣、氧），每一次使流體化床穩定化。一旦於穩定操作 條件時’實驗操作 > 丨2小時，經由線上氣體色譜法分析能 以每1/2小時收集之。 *非浸潰噴灌乾燥之石夕石 由第3及4表之結果可看出乙酸係使用流體化顆粒催化 劑自乙烷及乙烯製備之。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 14 (請先閱讀背面之注意事項再填寫本頁)
裝--------？訂i,-------線I 1229665 A7 B7 五、發明說明（l2 ) 第1表：乙烷氧化成乙酸之反應條件 範例 1 2 3 反應溫度°c 190.00 200.00 215.00 壓力巴 8.00 8.00 8.00 催化劑重量（g) 28.495 28.495 28.495 稀釋劑重量（g) 無 無 無 乙烷莫耳％ 48.53 48.53 48.53 氧莫耳％ 27.17 27.17 27.17 氮莫耳％ 6.59 6.59 6.59 水莫耳％ 17.72 17.71 17.72 總流量(毫升/分） 425.90 425.90 425.90 第2表··乙烯氧化成乙酸之反應條件 範例 5 6 反應溫度°C 160.00 160.00 壓力巴 8.00 8.00 催化劑重量（g) 14.29 29.50 稀釋劑重量（g) 12.21 無 乙烷莫耳％ 39.93 39.47 氧莫耳％ 6.63 6.56 氮莫耳％ 24.91 24.63 水莫耳％ 28.53 29.35 總流量（毫升/分） 357.04 361.18 (請先閱讀背面之注意事項再填寫本頁)
一裝---------訂-—·-------線I 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 15 1229665 A7 B7 五、發明說明（13 ) 結果 ： 表：乙烷氧化成乙酸之空間時間產量（AcOH)計算 範例1 流體上之時數 11.5 12 13.5 15 17 17.5 20.5 21.5 STY 149.20 77.55 135.5 5 132.1 9 145.0 5 112.7 8 159.9 2 141.2 1 範例2 流體上之時數 32.5 34.5 35.5 36 38 39 41 43.5 44.5 46 STY 191.81 216.0 7 136.5 2 216.5 7 190.6 9 229.2 0 199.1 7 156.2 9 207.5 7 166,2 8 範例3 流體上之時數 1 2 3 4 9 12 14 17 22 STY 328.11 321.7 5 326.3 2 297.1 4 「354.4 0 331.1 9 337.3 4 300.2 0 317.7 9 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 弟L4表：乙烯氧化成乙酸之空間時間產量（AcOH)計算 範例5 流體上之時數 1 3 5 9 11 13 STY 91.40 65.62 85.63 66.07 45.21 65.7[ 範例6 流體上之時數 1 3 5 7 11 13 STY 258.52 184.96 149.04 142.73 102.20 115.80 16 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）
Claims (1)
- 1229665 年 93.12.22 六、申請專利範圍 第881152G2號專射請㈣料利範圍修正本__ 1. -種製備乙酸之方法，該方法包含於一流體床反應器内 於一微球狀顆流體化顆粒固態氧化催化劑存在下使乙 烧及/或乙婦與含分子氧之氣體接觸，其中至少9〇〇/〇 之該催化劑顆粒係小於3〇〇微朱。 2·如申請專利範圍第"之方法，其中至少娜之該催化 劑顆粒係小於3〇〇微米。 3·如申請專利範圍第旧之方法，其中乙烧係與—包含雜 之催化劑接觸。 4.如申請專利範圍第3項之方法，其中該催化劑係 MoaWbAgcIrdXeYf， 其中’ X係元素Nb及V γ係一或多個選自 Cr，Mn，Ta，Ti，B，A1，Ga，In，pt， Zn’ Cd，Bi，Ce，C。，Rh，Ir，Cu，Ag5 Au，Fe，Ru，〇s，k， Rb，Cs，Mg，Ca，Sr，Ba，Zr，Hf，Ni，P，Pb，Sb，Si，Sn，T1， U，Re及Pd之元素； a，b，c，d，e及f表示元素之克比例，如此， 〇<a$l，〇$b<l 且 a+b=l 0<(c+d)$ 0.1 〇<e$ 2且 〇^f^2。 5·如申請專利範圍第丨項之方法，其中乙烯係與一包含金 屬絶之催化劑組成物及_雜多酸或其鹽接觸。 6.如申請專利範圍第5項之方法，其中該催化劑組成物包 17 1229665 六、申請專利範圍 ~- 含選自週期表第IB，IVB，VB及VIB族之金屬。 7.如申請專利範圍第6項之方法，苴中兮 乃杰/、甲忒金屬係選自銅、 銀、錫、鉛、銻、鉍、硒及碲。 8·如申請專利範圍第5項之方法，其中該催化劑包含⑴ 金屬鈀，（2)磷鎢酸、矽鎢酸或其鋰鈉或鋼鹽之至少一 者，（3)絲、砸及碎之至少一者。9·如申請專利範圍第丨項之方法，其中該催化劑包含一選 自矽石、氧化鈦、氧化鋁、氧化锆或其混合物之黏合金 屬’其濃度係該催化劑組成物之至少丨〇重量％。 10·如申請專利範圍第1項之方法，其係於13〇至5〇〇。〇之溫 度進行之。 11 ·如申请專利範圍第1項之方法，其係於1至5 〇巴之壓力下 進行之。 12· —種用以製備乙酸及/或乙酸乙烯酯之整體方法，其包 含：(a) 於一第一反應區域内，在一用於使乙烯氧化成乙酸 及/或使乙烷氧化成乙酸之微球狀顆流體化顆粒固 態氧化反應催化劑存在下，其中至少90%之該催化 劑顆粒係小於300微米，使一包含乙烯及/或乙烷及 選擇性之蒸氣之供料與含分子氧之氣體接觸，以製 備一第一產物流體，該第一產物流體包含乙酸、水 及乙烯（未反應之乙烯及/或共生產之乙烯）及選擇 性之乙烧、一氧化碳、二氧化碳及/或氮；及 (b) 於一第二反應區内，於額外之乙烯及/或乙酸存在或 -18 - 1229665 六、申請專利範圍 缺乏中，使包含至少乙酸及乙烯及選擇性之水、乙 烧、一氧化碳、二氧化碳及/或氮之一或多者之第一 氣態產物流體之至少一部份與一含分子氧之氣體於 一用於以活化乙酸乙烯酯之生產之催化劑存在下接 觸，以產生一第二產物流體，該第二產物流體包含 乙酸乙烯酯、水、乙酸及選擇性之乙稀。 13 ·如申請專利範圍第12項之方法，其包含進一步之步驟係 (c)藉由蒸餾使得自步驟（b)之產物流體分離成一包含 乙酸乙烯酯及水之頂部共沸分餾物及一包含乙酸之 底部分餾物；及 (d)(i)自於步驟（c)中所分離之底部分餾物回收乙酸，及 選擇性地使步驟（c)中所分離之該共沸分餾物在部 伤或元全將水分離後再循環至步驟（c)， 或（η)自步驟（c)中所分離之該共沸分餾物回收乙酸 乙烯酯及選擇性地使步驟(c)中所分離之該底部 分餾物循環至步驟（b)， 或㈣自步驟⑷中所分離之該底部錢物回收乙酸 及自於步驟⑷所回收之該頂部共沸分德物回收 乙酸乙稀酯。 Η•如申請專利範圍第3項之方法，其中該催㈣包含1 自石夕石' 氧化鈦、氧化紹、氧化錄或其混合物之黏合金 屬’其濃度係該催化劑組成物之至少忉重量％。 15.如申請專利範圍第4項之方法，其中該催化劑包含一選 19 1229665 六、申請專利範圍 自矽石、氧化鈦、氧化鋁、氧化鍅或其混合物之黏合金 屬，其濃度係該催化劑組成物之至少1〇重量％。 16·如申請專利範圍第5項之方法，其中該催化劑包含一選 自矽石氧化鈦、氧化鋁、氧化鍅或其混合物之黏合金 屬，其濃度係該催化劑組成物之至少1〇重量％。 R如申請專利範圍第6項之方法，其中該催化劑包含一選 自矽石、氧化鈦、氧化鋁、氧化鍅或其混合物之黏合金 屬，其濃度係該催化劑組成物之至少丨〇重量％。 18.如申請專利範圍第7項之方法，其中該催化劑包含一選 自矽石、氧化鈦、氧化鋁、氧化錘或其混合物之黏合金 屬’其濃度係該催化劑組成物之至少丨〇重量％。 19·如申請專利範圍第8項之方法，其中該催化劑包含一選 自矽石、氧化鈦、氧化鋁、氧化鍅或其混合物之黏合金 屬’其濃度係該催化劑組成物之至少丨〇重量％。
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| EP (1) | EP1109772B8 (zh) |
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| GB0223681D0 (en) * | 2002-10-10 | 2002-11-20 | Bp Chem Int Ltd | Catalyst and process |
| UA79540C2 (uk) * | 2003-01-27 | 2007-06-25 | Бп Кемікалз Лімітед | Каталітична композиція окиснення, її одержання та спосіб селективного окиснення |
| CN1938085B (zh) * | 2004-03-29 | 2011-05-25 | 昭和电工株式会社 | 用于制备含氧化合物的钯、钨和锆基催化剂，该催化剂的制备方法和利用该催化剂制备含氧化合物的方法 |
| AU2011201715B8 (en) * | 2010-04-15 | 2014-08-21 | China Petroleum & Chemical Corporation | A process for selective oxidative dehydrogenation of a hydrogen-containing co mixed gas |
| US20140275619A1 (en) | 2013-03-15 | 2014-09-18 | Celanese International Corporation | Process for Producing Acetic Acid and/or Ethanol By Methane Oxidation |
| EP2988865A2 (en) | 2013-04-24 | 2016-03-02 | Saudi Basic Industries Corporation | High productivity catalyst for alkane oxidation to unsaturated carboxylic acids and alkenes |
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| JP2018127398A (ja) * | 2015-05-12 | 2018-08-16 | 株式会社ダイセル | 酸化反応用リアクター、及び酸化物の製造方法 |
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| CN115433957B (zh) * | 2022-10-12 | 2024-07-16 | 深圳先进技术研究院 | 过渡金属复合铜基催化剂、其制备方法及应用 |
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| Publication number | Publication date |
|---|---|
| SA99200719B1 (ar) | 2006-09-25 |
| AU5636699A (en) | 2000-03-27 |
| DE69929894D1 (de) | 2006-04-20 |
| RU2233832C2 (ru) | 2004-08-10 |
| ID28495A (id) | 2001-05-31 |
| JP2011105771A (ja) | 2011-06-02 |
| UA67799C2 (uk) | 2004-07-15 |
| EP1109772A1 (en) | 2001-06-27 |
| RS49815B (sr) | 2008-08-07 |
| MY129272A (en) | 2007-03-30 |
| GB9819221D0 (en) | 1998-10-28 |
| NO20011086L (no) | 2001-05-04 |
| WO2000014047A1 (en) | 2000-03-16 |
| EP1109772B8 (en) | 2006-05-03 |
| CN1316984A (zh) | 2001-10-10 |
| ATE317840T1 (de) | 2006-03-15 |
| KR100635891B1 (ko) | 2006-10-18 |
| BR9913426A (pt) | 2001-10-23 |
| NO327227B1 (no) | 2009-05-18 |
| US7081549B2 (en) | 2006-07-25 |
| CN1231442C (zh) | 2005-12-14 |
| KR20010074946A (ko) | 2001-08-09 |
| TR200100661T2 (tr) | 2001-07-23 |
| US20040030184A1 (en) | 2004-02-12 |
| EP1109772B1 (en) | 2006-02-15 |
| ES2255758T3 (es) | 2006-07-01 |
| DE69929894T2 (de) | 2006-07-27 |
| JP2002524436A (ja) | 2002-08-06 |
| NO20011086D0 (no) | 2001-03-02 |
| YU17001A (sh) | 2003-02-28 |
| CA2341555A1 (en) | 2000-03-16 |
| CA2341555C (en) | 2009-11-10 |
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