CN1216846C - 制备丙烯酸的改进方法 - Google Patents
制备丙烯酸的改进方法 Download PDFInfo
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- CN1216846C CN1216846C CN018225128A CN01822512A CN1216846C CN 1216846 C CN1216846 C CN 1216846C CN 018225128 A CN018225128 A CN 018225128A CN 01822512 A CN01822512 A CN 01822512A CN 1216846 C CN1216846 C CN 1216846C
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- Prior art keywords
- catalyzer
- propenal
- reaction zone
- acrylic acid
- vinylformic acid
- Prior art date
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 16
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 7
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 5
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910052797 bismuth Inorganic materials 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ORSLXQZSKCIHDH-UHFFFAOYSA-N prop-2-enal;prop-2-enoic acid Chemical compound C=CC=O.OC(=O)C=C ORSLXQZSKCIHDH-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
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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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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
-
- 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
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8871—Rare earth metals or actinides
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- 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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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种制备丙烯酸的方法，该方法包括丙烯和氧(优选空气形式的氧)在反应区内、在高温下反应制备丙烯酸和丙烯醛，所述反应区具有以下式为特征的催化剂：AaBbCcCadFeeBifMo12Ox，其中A＝Li、Na、K、Rb和Cs中的一种或多种；B＝Mg、Sr、Mn、Ni、Co和Zn中的一种或多种；C＝Ce、Cr、Al、Sb、P、Ge、Sn、Cu、V和W中的一种或多种；和a＝0.01-1.0；b和e＝1.0-10；c＝0-5.0，优选为0.05-5.0，特别优选为0.05-4.0，和x是通过存在的其它各元素的化合价要求所确定的数。
Description
发明背景
本发明涉及制备丙烯酸的改进方法。目前，丙烯酸是用两步法来生产的。首先，用以适当元素促进的含铁、铋和钼的混合金属氧化物催化剂将丙烯氧化成丙烯醛，然后在单独的反应器中用第二种催化剂将丙烯醛进一步氧化成丙烯酸。一般地，用适当元素促进的含铁、铋和钼的氧化物的催化剂易用于将丙烯选择性氧化为丙烯醛(即制备丙烯酸的两步法中的第一步)。用于所述第一步的适当类型的催化剂的例子可参见美国专利4,162,234和4,280,929(转让给本申请的受让人)。
在两步法的第二步中，用第二种催化剂将丙烯醛氧化为丙烯酸。总有这种情况：丙烯醛转化为丙烯酸的选择性低于100％。然而，在两步法的第一步中形成的丙烯酸通过第二反应器而没有分解。因此，使用这样的催化剂是有利的：该催化剂在第一反应器中在将丙烯氧化为丙烯醛的过程中产生显著更多量的丙烯酸，从而在两步法中得到更高产率的丙烯酸。
在相关的专利申请美国序列号08/923,878中(1997年9月2日提交，已转让给本发明的受让人)中，公开了用于制备丙烯腈和氰化氢的新的催化剂。具体公开的催化剂包含用多种金属促进的铁、钼和铋的混合金属氧化物，其可用于制备丙烯腈，同时得到显著更高产率的副产物氰化氢。本申请发现，共同未决申请08/923,878的催化剂不仅能用于制备丙烯酸的两步法的第一步中，而且在该方法的第一步中会得到料想不到的高产率的丙烯酸。在第一步中丙烯酸的这一高产率使得在该两步法中获得更高的丙烯酸总产率。
发明概述
本发明的主要目标是提供一种制备丙烯酸以及将丙烯选择性氧化成丙烯醛的新方法。
本发明的其它目标和优点将在随后的描述中部分阐述，其一部分根据描述是显然的或者可通过实施本发明而获悉。借助于在所附权利要求中特别指出的手段及组合，可了解并实现本发明的目标和优点。
为达到上述目标并符合本发明的目的(如这里所体现并描述的)，本发明的方法包括丙烯和氧(优选含氧气体如空气形式的氧)在反应区内、在高温下(例如200-600℃)反应制备丙烯酸和丙烯醛，所述反应区含有以下式为特征的催化剂：
AaBbCcCadFeeBifMo12Ox
其中A＝Li、Na、K、Rb和Cs中的一种或多种
B＝Mg、Sr、Mn、Ni、Co和Zn中的一种或多种
C＝Ce、Cr、Al、Sb、P、Ge、Sn、Cu、V和W中的一种或多种，和a＝0.01-1.0；b和e＝1.0-10
c＝0-5.0，优选为0.05-5.0，特别优选为0.05-4.0
d和f＝0.05-5.0，和x是通过存在的其它各元素的化合价要求所确定的数。
在本发明的优选实施方案中，选择A为锂、钠、钾和铯中的一种或多种，特别优选是铯和钾。
在另一个优选实施方案中，B选自镁、锰、镍和钴或其混合物。
在另一个优选实施方案中，C选自铈、铬、锑、磷、锗、钨或其混合物，特别优选是铈、铬、磷和锗。
在本发明的另一个优选实施方案中，a可以是约0.05-0.9，特别优选是0.1以上至0.7。
在本发明的其它优选实施方案中，b和e可以是约1-10。在本发明进一步的优选实施方案中，c、d和f可以是约0.05-4，特别优选是0.1-3。
本发明进一步的优选实施方案包括从第一反应区采出丙烯酸和丙烯醛，至少将丙烯醛和氧引入含有第二催化剂的第二反应区，以使丙烯醛和氧在高温下反应制备丙烯酸，并且从第二反应区采出丙烯酸。在第二步中可使用任何适合的能将丙烯醛制成丙烯酸的催化剂。例如，美国专利3,840,595(在此引入作为参考)所述的典型的第二阶段催化剂(例如62％ Sb3Sn3V3W1.2Mo12Ox·38％ SiO2)就适用于实施本发明。
在本发明另一个优选实施方案中，从丙烯制丙烯酸和丙烯醛的第一反应在流化床反应器中进行，从丙烯醛制丙烯酸的第二反应在固定床反应器中进行。
本发明的催化剂可以负载使用或无负载使用。优选将催化剂负载在二氧化硅、氧化铝或氧化锆或其混合物上，特别优选负载在二氧化硅上。
发明详述
可通过本领域技术人员公知的多种制备催化剂的方法中的任何一种来制备本发明的催化剂。例如，通过将各种成分共沉淀来制备催化剂。然后可将共沉淀的物质干燥并研磨成适当的大小。另一选择，可将共沉淀物制浆并按照传统方法喷雾干燥。如本领域中众所周知的，可将催化剂挤成颗粒状或在油中形成矛(spear)状。另一选择，可将各催化剂组分与载体混合成浆液，随后干燥，或者可将它们浸渍在二氧化硅或其它载体上。制备催化剂的详细步骤参见美国专利5,093,299、4,863,891和4,766,232(已转让给本发明的受让人)，这些专利在此引入作为参考。
一般地，催化剂的A组分可作为氧化物或作为在焙烧时能产生该氧化物的盐的形式加入催化剂。优选使用易于获得并易于溶解的盐如硝酸盐作为将A元素引入催化剂的手段。
铋可作为氧化物或作为在焙烧时能产生该氧化物的盐的形式引入催化剂。优选易于分散但在热处理时形成稳定氧化物的水溶性盐。引入铋的特别优选的来源是已经溶于硝酸溶液的硝酸铋。
为将铁组分引入催化剂，人们可使用任何一种在焙烧时能产生氧化物的铁化合物。正如其它元素的情况一样，因为水溶性盐易于均匀地分散在催化剂内部而优选它们。最优选硝酸铁。
也可使用硝酸盐将钴、镍和镁引入催化剂。然而，可将镁以在热处理时能产生氧化物的不溶性碳酸盐或氢氧化物引入催化剂。
可从任何钼氧化物如二氧化钼、三氧化钼、五氧化钼或七氧化钼引入催化剂的钼组分。然而，优选使用可水解或可分解的钼盐作为钼的来源。最优选的原料是七钼酸铵。
磷可以碱金属盐或碱土金属盐或铵盐引入催化剂，但是优选作为磷酸引入。钙是本发明催化剂中的必要成分，可通过预形成钼酸钙或通过浸渍或通过本领域已知的其它方式将其加入。(通常作为硝酸钙与其它硝酸盐一起加入。)
本发明涉及在将丙烯氧化为丙烯醛的过程中制备丙烯酸的方法，其包括氧和丙烯在反应区中和以下列实验式为特征的催化剂接触反应以制备丙烯酸和丙烯醛：
AaBbCcCadFeeBifMo12Ox
其中A＝Li、Na、K、Rb和Cs中的一种或多种
B＝Mg、Sr、Mn、Ni、Co和Zn中的一种或多种
C＝Ce、Cr、Al、Sb、P、Ge、Sn、Cu、V和W中的一种或多种，和a＝0.01-1.0；b和e＝1.0-10
c＝0-5.0，优选为0.05-5.0，特别优选为0.05-4.0
d和f＝0.05-5.0，和x是通过存在的其它各元素的化合价要求所确定的数。优选反应在200-500℃、优选300-400℃的温度下进行。
可如下制备本发明的催化剂：将七钼酸铵的水溶液与硅溶胶混合，向该水溶液中加入含其它元素的化合物的浆液，干燥该溶液，脱氮并焙烧。可将催化剂在110-350℃的温度下喷雾干燥。脱氮的温度可以是100-450℃。最终，在400-700℃的温度下进行焙烧。
本发明进一步的优选实施方案包括采出第一反应区中制得的丙烯酸和丙烯醛，至少将丙烯醛和氧(优选空气是氧源)引入在高温下包含适用于将丙烯醛转变为丙烯酸的第二催化剂的第二反应区，以将丙烯醛转变为丙烯酸，并且从第二反应区采出丙烯酸。用于将丙烯醛转变为丙烯酸的适合的催化剂描述在先前引用的美国专利3,840,595中，该专利在此引入作为参考。用于第二反应区的催化剂的具体例子包括Mo9V2W1Cu1Sn0.4Ox；Mo10W1V3Sb2Cu1Nb2Ox；Mo12V3W1.2Cu2Ti0.5Ox；Mo9V2W1Cu1.5Sn0.4P1Ox；Mo12V3W1.2Cu2Sn0.5Ox和Sb3Sn3V3W1.2Mo12Ox。这些催化剂负载在惰性载体如氧化铝、氧化锆或二氧化硅上，优选负载在二氧化硅上。一般地，负载的催化剂含70-75wt％的活性相和25-30wt％的惰性载体。
在下面阐述的本发明的实施例仅仅是用来说明的。
在下面的每一个实施例中，所述方法都是在以下条件下进行：在40cc流化床反应器中；0.05-0.10wwh；进料混合物为1C3 ＝/1.7O2/9.3N2/3H2O；360℃；15psig。
表I
| 实施例序号 | 催化剂组成 | ％C3 ＝转化率 | ％丙烯醛 | ％丙烯酸 | 丙烯醛+丙烯酸 |
| 1 | 对比实施例：Cs0.1K0.1Ni6.2Mg2.5Fe4Bi0.5Ce0.5Mo14.8Ox | 93.4 | 67.6 | 14.4 | 82.0 |
| 2 | 实施例：Cs0.1K0.1Ni6.2Mg2.5Fe4Bi0.5Ce0.5Ca0.75Mo15.6Ox | 97.1 | 67.3 | 17.6 | 84.9 |
| 3 | Cs0.1K0.1Co6.2Mg2.5Fe4Bi0.5Ce0.5Ca0.75Mo15.6Ox | 97.3 | 74.4 | 14.1 | 88.5 |
| 4 | Cs0.1K0.1Co3.1Mg2.25Ni3.1Fe4Bi0.5Ce0.5Ca1.0Mo15.6Ox | 98.0 | 67.7 | 18.6 | 86.3 |
| 5 | Cs0.1K0.1Ni6.2Mg2.5Fe2.0Bi0.5Ca0.75Mo12.8Ox | 98.1 | 65.3 | 20.8 | 86.1 |
Claims (8)
1.一种制备丙烯酸的方法，该方法包括使丙烯和氧在第一反应区内、在高温下反应制备丙烯酸和丙烯醛，所述反应区含有以下式为特征的第一催化剂：
AaBbCcCadFeeBifMo12Ox其中A＝Li、Na、K、Rb和Cs中的一种或多种；
B＝Mg、Sr、Mn、Ni、Co和Zn中的一种或多种；
C＝Ce、Cr、Al、Sb、P、Ge、Sn、Cu、V和W中的一种或多种；
和a＝0.01-1.0；b和e＝1.0-10；
c＝0-5.0；
d和f＝0.05-5.0；和x是通过存在的其它各元素的化合价要求所确定的数。
2.权利要求1的方法，其还包括至少将来自第一反应区的丙烯醛和氧引入包含第二催化剂的第二反应区，以将丙烯醛转变成丙烯酸。
3.权利要求1的方法，其中A选自锂、钠、钾和铯中的一种或多种。
4.权利要求3的方法，其中B选自镁、锰、镍和钴或其混合物。
5.权利要求4的方法，其中C选自铈、铬、磷和锗或其混合物。
6.权利要求5的方法，其中a是0.05-0.9。
7.权利要求6的方法，其中b和e为2-9。
8.权利要求7的方法，其中c、d和f为0.1-4。
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2001/003606 WO2002062741A1 (en) | 2001-02-05 | 2001-02-05 | Improved method for the manufacture of acrylic acid |
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| CN1489568A CN1489568A (zh) | 2004-04-14 |
| CN1216846C true CN1216846C (zh) | 2005-08-31 |
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| EP (1) | EP1358147A1 (zh) |
| JP (1) | JP2004522757A (zh) |
| KR (1) | KR100711044B1 (zh) |
| CN (1) | CN1216846C (zh) |
| BR (1) | BR0116860A (zh) |
| CA (1) | CA2437256C (zh) |
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| JPS584691B2 (ja) * | 1977-11-07 | 1983-01-27 | 宇部興産株式会社 | メタクロレインの製造方法 |
| US5218146A (en) * | 1987-05-27 | 1993-06-08 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Process for production of acrylic acid |
| US5840648A (en) * | 1997-09-02 | 1998-11-24 | The Standard Oil Company | Catalyst for the manufacture of acrylonitrile and hydrogen cyanide |
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2001
- 2001-02-05 MX MXPA03006957A patent/MXPA03006957A/es not_active Application Discontinuation
- 2001-02-05 EP EP01905424A patent/EP1358147A1/en not_active Withdrawn
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- 2001-02-05 JP JP2002562702A patent/JP2004522757A/ja active Pending
- 2001-02-05 WO PCT/US2001/003606 patent/WO2002062741A1/en active Application Filing
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| EP1358147A1 (en) | 2003-11-05 |
| KR20030076655A (ko) | 2003-09-26 |
| WO2002062741A1 (en) | 2002-08-15 |
| CA2437256A1 (en) | 2002-08-15 |
| JP2004522757A (ja) | 2004-07-29 |
| MXPA03006957A (es) | 2004-05-24 |
| BR0116860A (pt) | 2004-01-13 |
| CA2437256C (en) | 2009-04-14 |
| CN1489568A (zh) | 2004-04-14 |
| KR100711044B1 (ko) | 2007-04-24 |
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