WO2000053555A1 - Verfahren der heterogen katalysierten gasphasenoxidation von propan zu acrolein und/oder acrylsäure - Google Patents
Verfahren der heterogen katalysierten gasphasenoxidation von propan zu acrolein und/oder acrylsäure Download PDFInfo
- Publication number
- WO2000053555A1 WO2000053555A1 PCT/EP2000/001632 EP0001632W WO0053555A1 WO 2000053555 A1 WO2000053555 A1 WO 2000053555A1 EP 0001632 W EP0001632 W EP 0001632W WO 0053555 A1 WO0053555 A1 WO 0053555A1
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- WIPO (PCT)
- Prior art keywords
- reaction
- temperature
- reaction zone
- propane
- catalyst
- Prior art date
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000001294 propane Substances 0.000 title claims abstract description 30
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 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 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 230000003647 oxidation Effects 0.000 title claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 83
- 239000000203 mixture Substances 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 239000012495 reaction gas Substances 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 229910052721 tungsten Inorganic materials 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 229910052776 Thorium Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000001354 calcination Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- -1 preferably Co Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000003868 ammonium compounds Chemical class 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
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 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
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 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
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- IZYSFFFJIOTJEV-UHFFFAOYSA-P diazanium;dioxido(dioxo)tungsten Chemical compound [NH4+].[NH4+].[O-][W]([O-])(=O)=O IZYSFFFJIOTJEV-UHFFFAOYSA-P 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 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
- 230000001788 irregular Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J37/04—Mixing
-
- 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
-
- 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
Definitions
- the present invention relates to a process of heterogeneously catalyzed gas phase oxidation of propane to acrolein and / or acrylic acid, in which a reaction gas starting mixture containing> 50 vol.% Propane,> 10 vol.% 0 and 0 to 40 vol Temperature leads over a fixed bed catalyst, which consists of two spatially successive reaction zones A, B arranged catalyst beds A, B, the active mass of the catalyst bed A located in reaction zone A at least one multimetal oxide of the general formula I
- M 1 Co, Ni, Mg, Zn, Mn and / or Cu,
- the active composition of the catalyst bed B located in the reaction zone B is at least one multimetal oxide of the general formula II
- ⁇ i W, V and / or Te
- ⁇ 2 alkaline earth metal, Co, Ni, Zn, Mn, Cu, Cd, Sn and / or Hg
- X 3 Fe, Cr and / or Ce
- X ' a number which is determined by the valency and frequency of the elements in II other than oxygen
- reaction gas starting mixture flows through the catalyst beds A, B in the sequence “first A”, “then B”.
- reaction gas starting mixture at a temperature of 325 to 480 or 450 ° C, preferably at 350 to 420 ° C and particularly preferably at 350 to 400 ° C over the fixed bed catalyst consisting of the catalyst beds A, B. respectively. Furthermore, it is stated in the abovementioned documents that the catalyst beds A, B normally have identical temperatures.
- the object of the present invention was therefore to provide a process as described at the outset with improved selectivity in the formation of valuable products.
- a process for the heterogeneously catalyzed gas-phase oxidation of propane to acrolein and / or acrylic acid in which a> 50 Vol .-% of propane,> 10 vol .-% 0 2 and 0 to 40 Vol .-% inert gas-containing starting reaction gas mixture at elevated Temperature leads over a fixed bed catalyst, which consists of two spatially successive reaction zones A, B arranged catalyst beds A, B, the active mass of the catalyst bed A located in reaction zone A at least one multimetal oxide of the general formula I
- M 1 Co, Ni, Mg, Zn, Mn and / or Cu, preferably Co, Ni and / or
- Mg particularly preferably Co and / or Ni
- M 2 W, V, Te, Nb, P, Cr, Fe, Sb, Ce, Sn and / or La, preferably Sn, W, P, Sb and / or Cr, particularly preferably W, Sn and / or Sb
- a 0.5 to 1.5, preferably 0.7 to 1.2, particularly preferably 0.9 to 1.0
- b 0 to 0.5, preferably> 0 to 0.5 and particularly preferred
- the active composition of the catalyst bed B located in the reaction zone B is at least one multimetal oxide of the general formula II
- X 1 W, V and / or Te, preferably W and / or V
- X 2 alkaline earth metal, Co, Ni, Zn, Mn, Cu, Cd, Sn and / or Hg, preferably Co, Ni, Zn and / or Cu, particularly preferably Co, Ni and / or Zn
- X 3 Fe, Cr and / or Ce, preferably Fe and / or Cr
- X 4 P, As, Sb and / or B, preferably P and / or Sb
- X 5 alkali metal, Tl and / or Sn, preferably K and / or Na
- X 6 rare earth metal, Ti, Zr, Nb, Ta, Re, Ru, Rh, Ag, Au, AI,
- Ga, In, Si, Ge, Th and / or U preferably Si, Zr, Al, Ag,
- a ' 0.01 to 8, preferably 0.3 to 4 and particularly preferably 0.5 to 2
- b' 0.1 to 30, preferably 0.5 to 15 and particularly preferably
- the reaction gas starting mixture flows through the catalyst beds A, B in the sequence "first A", "then B", found, which is characterized in that the temperature of the reaction zone A is 380 to 480 ° C and the temperature of the Reaction zone B is on the one hand> 300 ° C and on the other hand is at least 20 ° C below the temperature of reaction zone A.
- the temperature of a reaction zone is understood here to mean the temperature of the catalyst bed in the reaction zone when the process is carried out in the absence of a chemical reaction. If this temperature is not constant within the reaction zone, 5 the term temperature of a reaction zone here means the number average of the temperature of the catalyst bed along the reaction zone.
- the temperature of reaction zone A in the process according to the invention is preferably 400 to 450 ° C.
- the temperature of reaction zone B is preferably at least 10 40 ° C. below the temperature of reaction zone A.
- the temperature of reaction zone B is 320 to 380 ° C. and particularly preferably 330 to 370 ° C.
- Multimetal oxides I which are preferred according to the invention are therefore 15 of the general formula I '
- x a number which is determined by the valency and frequency of the elements in I 'other than 25 oxygen.
- Multimetal oxides I which are particularly preferred according to the invention are those of the general formula I "
- such multimetal oxides I, I '35 and I are advantageous as active compositions, their average pore diameters ⁇ 0.09 ⁇ m and> 0.01 ⁇ m and their specific surface area
- the aforementioned average pore diameter is particularly preferably> 0.02 ⁇ m and ⁇ 0.06 ⁇ m.
- the aforementioned multimetal oxide compositions at the aforementioned average pore diameters 45 simultaneously have a specific surface area of __ 15 m 2 / g or of __ 25 m 2 / g.
- the said specific The surface area of the multimetal oxide compositions according to the invention is ⁇ 50 m 2 / g.
- the specific surface area 0 means the specific surface area determined according to DIN 66133 by means of the mercury intrusion method (measuring range: 1 ⁇ m to 3 nm pore diameter).
- the mean pore diameter is defined in this document as four times the ratio of the total pore volume to the specific surface area 0 determined according to the aforementioned mercury intrusion method.
- Multimetal oxides II preferred according to the invention are those of the general formula II '
- the reaction gas starting mixture to be used for the process according to the invention advantageously comprises __ 30% by volume, preferably ⁇ 20% by volume and particularly preferably ⁇ 10% by volume or ⁇ 5% by volume of inert gas.
- the reaction gas starting mixture can also comprise no inert gas.
- Inert gas is understood here to mean those gases whose conversion when passing through the fixed bed catalyst to be used according to the invention is ⁇ 5 mol%.
- the propane content of the reactant to be used according to the invention is generally ongas starting mixture at 90 vol.% or ⁇ 85 vol.%, often at ⁇ 83 or ⁇ 82 or ⁇ 81 or ⁇ 80 vol.%.
- the content of molecular oxygen in the reaction gas starting mixture can be up to 35% by volume in the process according to the invention. It is advantageously at least 15% by volume or 20% by volume or at least 25% by volume.
- Reaction gas starting mixtures which are favorable according to the invention contain> 65% by volume and ⁇ 90% by volume of propane and
- the reaction gas starting mixture contains essentially no further components apart from the components mentioned.
- suitable multimetal oxides I as active compositions to be used according to the invention can be prepared in a simple manner by generating an intimate, preferably finely divided, dry mixture of suitable stoichiometry from suitable sources of their elemental constituents, and this at temperatures of 450 to 1000, preferably 450 to 700, frequently 450 to 600 or 550 to 570 ° C calcined.
- the calcination can take place both under inert gas and under an oxidative atmosphere, such as air or mixtures of inert gas and oxygen, and also under a reducing atmosphere, for example under mixtures of inert gas, oxygen and NH 3 , CO and / or H 2 .
- the calcination time can range from a few minutes to a few hours and usually decreases with increasing calcination temperature.
- the calcination can be carried out in a simple manner by placing the active mass precursor in a rotating container, heating the container to the calcination temperature and letting the corresponding gas mixture flow through it.
- a rotating tube furnace or a rotating round quartz flask can be considered as a rotating container.
- the preparation of the active material precursor is, for example possible by one of THE APPROPRIATE sources of the elemental constituents of the desired Mul - timetalloxids produces an aqueous solution and spray dried, the spray outlet temperatures expedient 100 • amounted to 150 ° C.
- Halides, nitrates, formates, oxalates, citrates, acetates, carbonates, ammonium complexes, and ammonium compounds are the main sources for the elemental constituents of the multimetal oxy-active compounds (I). Salts and / or hydroxides into consideration (compounds such as NH0H, (NH) 2 C0 3 , NH 4 N0 3 , NHCH0 2 , CH 3 COOH, NHCH 3 C0 2 and / or ammonium oxalate, which become completely gaseous at the latest during the later galvanizing escaping compounds disintegrate and / or decompose can also be incorporated into the precursor to be calcined).
- Salts and / or hydroxides into consideration compounds such as NH0H, (NH) 2 C0 3 , NH 4 N0 3 , NHCH0 2 , CH 3 COOH, NHCH 3 C0 2 and / or ammonium oxalate, which become completely gas
- the intimate mixing of the starting compounds for the production of multimetal oxide compositions I can take place in dry or in wet form. If it is carried out in dry form, the starting compounds are expediently used as finely divided powders and are subjected to calcination after mixing and, if appropriate, compaction. However, the intimate mixing is preferably carried out in wet form. Usually, the starting compounds are mixed together in the form of an aqueous solution and / or suspension. Particularly intimate dry mixtures are obtained when only sources of the elementary constituents in dissolved form are used. Water is preferably used as the solvent. The aqueous mass obtained is then dried.
- Particularly suitable starting compounds for Mo, V, W and Nb are their oxo compounds (molybdates, vanatates, tungstates and niobates) and the acids derived from them. This applies in particular to the corresponding ammonium compounds (ammonium molybdate, ammonium vanadate, ammonium wolf ramate).
- the multimetal oxide materials I can be used for the process according to the invention both in powder form and in the form of certain catalyst geometries, the shaping being able to take place before or after the final calcination.
- solid catalysts can be produced from the powder form of the active composition or its uncalcined precursor composition by compression to the desired catalyst geometry (e.g. by tableting, extrusion or extrusion), where appropriate auxiliaries such as e.g. Graphite or stearic acid can be added as a lubricant and / or molding aid and reinforcing agent such as microfibers made of glass, asbestos, silicon carbide or potassium titanate.
- auxiliaries such as e.g. Graphite or stearic acid can be added as a lubricant and / or molding aid and reinforcing agent such as microfibers made of glass, asbestos, silicon carbide or potassium titanate.
- Suitable unsupported catalyst geometries are e.g.
- Solid cylinder or hollow cylinder with an outer diameter and a length of 2 to 10 mm.
- a wall thickness of 1 to 3 mm is appropriate.
- the full catalyst can of course also have a spherical geometry, the spherical diameter being 2 to 10 mm.
- Precursor mass can also be made by application to preformed inert catalyst supports.
- the coating of the carrier body for Production of the shell catalysts is generally carried out in a suitable rotatable container, as is known, for example, from DE-A 2909671 or from EP-A 293859.
- the powder mass to be applied can expediently be moistened and dried again after application, for example by means of hot air.
- the layer thickness of the powder mass applied to the carrier body is expediently selected in the range from 50 to 700 ⁇ m, preferably in the range from 150 to 500 ⁇ m. Of course, the layer thickness can also be 150 to 250 ⁇ m.
- porous or non-porous aluminum oxides silicon dioxide, thorium dioxide, zirconium dioxide, silicon carbide or silicates such as magnesium or aluminum silicate can be used as carrier materials.
- the carrier bodies can have a regular or irregular shape, with regularly shaped carrier bodies with a clearly formed surface roughness, e.g. Balls or hollow cylinders are preferred. It is suitable to use essentially non-porous, rough-surface, spherical supports made of steatite, the diameter of which is 1 to 8 mm, preferably 3 to 5 mm.
- multimetal oxide compositions II With regard to the production of the multimetal oxide compositions II, what has been said for the multimetal oxide compositions I applies. However, the calcination temperature used is usually 350 to 650 ° C.
- Particularly preferred multimetal oxide compositions II are the multimetal oxide compositions I disclosed in EP-B 575897, in particular their preferred embodiment variants. They are characterized in that multimetal oxides are initially formed from subsets of the elementary constituents and are used as an element source in the further course of production.
- DE-C 2830765 discloses a preferred variant of a two-zone tube bundle reactor which can be used according to the invention.
- the two-zone tube bundle reactors disclosed in DE-C 2513405, US-A 3147084, DE-A 2201528 and DE-A 2903582 are also suitable for carrying out the according to the invention
- the fixed bed catalyst to be used according to the invention is in the simplest way in the metal tubes of a tube bundle reactor and two temperature media, generally salt melts, which are essentially spatially separated from one another, are guided around the metal tubes.
- the tube section over which the respective salt bath extends represents a reaction zone. That is, in the simplest way each reaction tube of the tube bundle reactor contains the two catalyst beds A, B to be used according to the invention (for example, directly or separated by an inert layer) arranged in succession and a salt bath A flows around the section of the tubes in which the catalyst bed A is located and a salt bath B flows around the Section of the tubes in which the catalyst bed B is located.
- the two salt baths can in relative to the flow direction of the reaction gas mixture flowing through the reaction tubes
- reaction zone A Direct current or countercurrent through the space surrounding the reaction tubes.
- a cocurrent flow can also be used in reaction zone A and a counterflow (or vice versa) in reaction zone B.
- the reaction gas starting mixture is advantageously fed to the catalyst feed preheated to the reaction temperature.
- the contact tubes are usually made of ferritic steel and typically have a wall thickness of 1 to 3 mm. Their inner diameter is usually 20 to 30 mm, often 22 to 26 mm.
- the number of contact tubes accommodated in the tube bundle container is at least 5,000, preferably at least 10,000.
- the number of contact tubes accommodated in the reaction container is often
- Tube bundle reactors with a number of contact tubes above 40,000 are rather the exception.
- the contact tubes are normally arranged homogeneously distributed within the container, the distribution being expediently chosen such that the distance between the central inner axes from the closest contact tubes (the so-called contact tube division) is 35 to 45 mm (cf. e.g. EP-B 468290).
- Fluid temperature media are particularly suitable as the heat exchange medium.
- the flow rate within the two required heat exchange medium circuits is selected such that the temperature of the heat exchange medium increases from 0 to 15 ° C. from the entry point into the reaction zone to the exit point from the reaction zone. That is, the aforementioned ⁇ T can be 1 to 10 ° C or 2 to 8 ° C or 3 to 6 ° C according to the invention.
- the entry temperature of the heat exchange medium into reaction zone A is normally 380 to 480 ° C., frequently 400 to 450 ° C.
- the entry temperature of the heat exchange medium into reaction zone B is normally on the one hand> 300 ° C. and on the other hand is normally at least 20 ° C. below the entry temperature of the heat exchange medium entering reaction zone A.
- the entry temperature of the heat exchange medium into reaction zone B is preferably at least 40 ° C. below the entry temperature of the heat exchange medium entering reaction zone A.
- the entry temperature of the heat exchange medium into reaction zone B is advantageously from 320 to 380 ° C. and particularly preferably from 330 to 370 ° C.
- the two reaction zones A, B can also be implemented in spatially separated tube bundle reactors. If necessary, an intercooler (which can be filled with inert material) can be installed between the two reaction zones. It goes without saying that the two reaction zones A, B can also be designed as a fluidized bed.
- the working pressure in the process according to the invention is generally> 0.5 bar.
- the reaction pressure will not exceed 100 bar, ie 0.5 to 100 bar.
- the reaction pressure is expediently often> 1 to 50 or> 1 to 20 bar.
- the reaction pressure is preferably> 1.25 or> 1.5 or> 1.75 or> 2 bar. Often the upper limit of 10 bar or 20 bar is not exceeded. In many cases the reaction pressure will be 3 to 4 bar.
- the reaction pressure can also be 1 bar (the above statements regarding the reaction pressure apply in general to the process according to the invention).
- the loading is advantageously chosen so that the residence time of the reaction gas mixture over the two catalyst beds is 0.5 to 20 seconds, preferably 1 to 10 seconds, particularly preferably 1 to 4 seconds and often 3 seconds.
- the ratio of the bulk volumes of the two catalyst beds A, B is advantageously 1:10 to 10: 1, preferably 1: 5 to 5: 1 and particularly preferably 1: 2 to 2: 1, often 1: 1.
- Propane and / or propene and / or inert gas contained in the product mixture of the process according to the invention can be separated off and recycled into the gas phase oxidation according to the invention.
- the process according to the invention can be followed by a further heterogeneously catalyzed oxidation stage, as are known for the heterogeneously catalyzed gas phase oxidation of acrolein to acrylic acid (for example from EP-A 700893), into which the product mixture of the process according to the invention, optionally with the addition of further molecular oxygen.
- unreacted propane, propene and / or acrolein and / or inert gas can again be separated off and recycled into the gas phase oxidation.
- Air as well as air depleted in nitrogen or pure oxygen are generally considered as oxygen sources for the process according to the invention.
- the acrolein and / or the acrylic acid formed can be separated off from the product gas mixtures in a manner known per se.
- the propane conversion achieved with the process according to the invention is __ 5 mol% or> 7.5 mol%. However, normally no propane conversions> 20 mol% are achieved.
- the method according to the invention is particularly suitable for continuous implementation. If necessary, additional molecular oxygen can be injected at the level of the catalyst bed B. Otherwise, turnover, selectivity and retention time, unless otherwise stated, are defined in this document as follows: Mole number of propane converted
- the heating was carried out at a heating rate of 75 ° C./h from room temperature 35 (25 ° C.) to 175 ° C.
- the temperature was then maintained at 175 ° C. for 1 h and then the temperature was increased from 175 ° C. to 185 ° C. at a heating rate of 40 ° C./h. This temperature was then maintained for 3 hours.
- the temperature was then increased to 40,300 ° C. at a heating rate of 38 ° C./h and maintained for 2 h.
- the precursor mass obtained in this way was admixed with 3% by weight of graphite, based on its weight, and processed into fully catalytic converter cylinders of geometry 5 mm ⁇ 3 mm (outside diameter ⁇ height) with a side pressure resistance of 90.7 N (pressing pressure: 8600 N; Rotary tableting machine, Hörn company, type RP / 16H). 580 g of these full-cylinder tablets were calcined in an air-flowed muffle furnace (60 l internal volume, air flow 500 l / h) as follows:
- the mixture was first heated from room temperature (25 ° C) to 550 ° C. This temperature was then maintained for 6 hours.
- the lateral compressive strength of the calcined multimetal oxide full cylinders was 105.9 N. They were comminuted and, as a catalytically active multimetal oxide mass I of stoichiometry C ⁇ o / 95 MoO x, the grain fraction with a grain size diameter of 0.6 to 1.2 mm was separated off by sieving.
- the average diameter of the pores of the active composition was 30 nm and the specific surface area was 13.2 m 2 / g.
- the spray drying took place in a counter-rotating spray tower at a gas inlet temperature of 300 ⁇ : 10 ° C and a gas outlet temperature of 100 zh 10 ° C.
- the spray powder obtained was then calcined at a temperature in the range from 780 to 810 ° C. (in a rotary kiln through which air flows (1.54 m 3 internal volume, 200 Nm 3 air / h)). It is essential for the exact setting of the calcination temperature that it has to be based on the desired phase composition of the calcination product.
- the phases W0 3 (monoclinic) and Bi 2 W 2 0 9 are desired, the presence of ⁇ -Bi 2 W0 6 (Russelite) is undesirable.
- the preparation must be repeated and the calcination temperature within the specified temperature range until the reflex disappears.
- the preformed calcined mixed oxide thus obtained was ground so that the X 50 value (see FIG. Ullmann's Encyclopedia of Industrial Chemistry, 6 th Edition (1998), Electronic Release, Chapter 3.1.4 or DIN 66141) was the resulting particle size 5 .mu.m .
- the millbase was then finely ground with 1% by weight (based on the millbase). Partial Si0 2 (vibrating weight 150 g / 1; X 50 value of the Si0 2 particles was 10 ⁇ m, the BET surface area was 100 m 2 / g).
- a solution A was prepared by dissolving 213 kg of ammonium heptamolybdate in 600 l of water at 60 ° C. while stirring and the resulting solution while maintaining the 60 ° C. and stirring with 0.97 kg of an aqueous potassium hydroxide solution (46.8% by weight) at 20 ° C. . -% KOH) added.
- a solution B was prepared by entering 116.25 kg of an aqueous iron nitrate solution (14.2% by weight of Fe) at 60 ° C. in 262.9 kg of an aqueous cobalt nitrate solution (12.4% by weight of Co). Solution B was then pumped continuously into solution A over a period of 30 minutes while maintaining the 60 ° C. The mixture was then stirred at 60 ° C for 15 minutes. Then the resulting aqueous mixture was 19.16 kg of a silica gel (46.80% by weight Si0 2 , density: 1.36 to 1.42 g / ml, pH 8.5 to 9.5, alkali content max. 0, 5% by weight) and then stirred for a further 15 minutes at 60 ° C.
- a silica gel 46.80% by weight Si0 2 , density: 1.36 to 1.42 g / ml, pH 8.5 to 9.5, alkali content max. 0, 5% by weight
- spray drying was carried out in counter-current in a turntable spray tower (gas inlet temperature: 400zh 10 ° C, gas outlet temperature: 140 ⁇ 5 ° C).
- the resulting spray powder had a loss on ignition of approximately 30% by weight (3 hours at 600 ° C.).
- the starting mass 1 was compared with the starting mass 2 for a multimetal oxide active mass of stoichiometry
- Muffle furnace with air flowing through it was first heated from room temperature (25 ° C) to 190 ° C at a heating rate of 180 ° C / h. This temperature was maintained for 1 h and then increased to 210 ° C with a heating rate of 60 ° C / h. The 210 ° C was again maintained for 1 h before it was increased to 230 ° C at a heating rate of 60 ° C / h. This temperature was also maintained for 1 hour before it was increased again to 265 ° C. at a heating rate of 60 ° C./h. The 265 ° C was then also maintained for 1 h. Thereafter, the mixture was first cooled to room temperature, essentially completing the decomposition phase. The mixture was then heated to 465 ° C. at a heating rate of 180 ° C./h and this calcination temperature was maintained for 4 hours.
- a reaction tube (V2A steel; 2.5 cm wall thickness; 8.5 mm inner diameter; electrically heatable in sections) with a length of 1.4 m is placed from bottom to top on a contact chair initially over a length of 48.7 cm with quartz chips (number-average large diameter 1 to 2 mm) and then loaded with the multimetal oxide active composition II over a length of 21.3 cm and then with the multimetal oxide active composition I over a length of 21.3 cm before the loading over a length of 48.7 cm with Quartz grit (number-average large diameter 1 to 2 mm) is completed (the quartz grit is essentially inert and serves, for example, to heat the reaction gas starting mixture to the reaction temperature).
- the reaction tube charged as above is charged with a reaction gas starting mixture having a pressure of 2.7 bar and consisting of 80 vol.% Propane and 20% vol.% Oxygen from top to bottom.
- the dwell time is set to 1.8 s.
- the pressure loss across the reaction tube is 0.2 bar.
- the temperature of the reaction tube is set as follows by means of hollow cylindrical, electrically heated aluminum blocks in contact with the reaction tube:
- a comparison of the design variants (i), (ii) shows the superiority of the procedure according to the invention with regard to the formation of valuable products.
- a reaction tube (V2A steel; 2.5 cm wall thickness; 8.5 mm inner diameter; electrically heatable in sections) with a length of 1.4 m was first built from bottom to top on a contact chair over a length of 35 cm with quartz chips (number-average large diameter 1 to 2 mm) and then over a length of 21.3 cm with the multimetal oxide active material II and then afterwards over a length of 19 cm with quartz chips (number-average large diameter 1 to 2 mm) and then over a length of 21.3 cm charged with the multimetal oxide active material I before the loading was completed over a length of 43.4 cm with quartz chips (number-average large diameter 1 to 2 mm) (the quartz chips are essentially inert and serve, for example, to heat the reaction gas starting mixture to the reaction temperature ).
- the reaction tube charged as above was charged with a reaction gas starting mixture having a pressure of 2.7 bar and consisting of 80 vol.% Propane and 20% vol.% Oxygen from top to bottom.
- the dwell time was on 1.8 s set.
- the pressure drop across the reaction tube was 0.2 bar.
- the temperature of the reaction tube was set as follows by means of hollow cylindrical, electrically heated aluminum blocks in contact with the reaction tube:
- reaction tube length 70 cm first 405 ° C, then up to the contact tube end 365 ° C.
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR0008824-2A BR0008824A (pt) | 1999-03-10 | 2000-02-28 | Processo para a oxidação em fase gasosa de um propano a acroleìna e/ou a ácido acrìlico sob catálise, heterogênea |
EP00910721A EP1159243A1 (de) | 1999-03-10 | 2000-02-28 | Verfahren der heterogen katalysierten gasphasenoxidation von propan zu acrolein und/oder acrylsäure |
JP2000603996A JP2002539099A (ja) | 1999-03-10 | 2000-02-28 | プロパンのアクロレイン及び/又はアクリル酸への不均一系触媒気相酸化法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19910507.3 | 1999-03-10 | ||
DE19910507A DE19910507A1 (de) | 1999-03-10 | 1999-03-10 | Verfahren der heterogen katalysierten Gasphasenoxidation von Propan zu Acrolein und/oder Acrylsäure |
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WO2000053555A1 true WO2000053555A1 (de) | 2000-09-14 |
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PCT/EP2000/001632 WO2000053555A1 (de) | 1999-03-10 | 2000-02-28 | Verfahren der heterogen katalysierten gasphasenoxidation von propan zu acrolein und/oder acrylsäure |
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EP (1) | EP1159243A1 (de) |
JP (1) | JP2002539099A (de) |
CN (1) | CN1343189A (de) |
BR (1) | BR0008824A (de) |
DE (1) | DE19910507A1 (de) |
WO (1) | WO2000053555A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003201260A (ja) * | 2001-12-04 | 2003-07-18 | Rohm & Haas Co | アルカンからオレフィン、不飽和カルボン酸および不飽和ニトリルを調製するための改良されたプロセス |
EP1460053A1 (de) * | 2001-12-27 | 2004-09-22 | Mitsubishi Chemical Corporation | Verfahren zur katalytischen dampfphasenoxidation und verfahren zur herstellung von (meth)acrolein oder (meth)acrylsäure |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1193240A1 (de) * | 2000-09-29 | 2002-04-03 | Rohm And Haas Company | Rückführungsverfahren in der Herstellung von ungesättigten Carbonsäuren aus Alkanen |
KR100807972B1 (ko) * | 2005-08-10 | 2008-02-28 | 주식회사 엘지화학 | 아크릴산 선택성이 높은 복합 금속 산화물 촉매 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19622331A1 (de) * | 1996-06-04 | 1997-12-11 | Basf Ag | Verfahren der heterogen katalysierten Gasphasenoxidation von Propan zu Acrolein |
DE19807079A1 (de) * | 1998-02-20 | 1999-08-26 | Basf Ag | Verfahren der heterogen katalysierten Gasphasenoxidation von Propan zu Acrolein und/oder Acrlysäure |
-
1999
- 1999-03-10 DE DE19910507A patent/DE19910507A1/de not_active Withdrawn
-
2000
- 2000-02-28 CN CN00804785.5A patent/CN1343189A/zh active Pending
- 2000-02-28 WO PCT/EP2000/001632 patent/WO2000053555A1/de not_active Application Discontinuation
- 2000-02-28 JP JP2000603996A patent/JP2002539099A/ja not_active Withdrawn
- 2000-02-28 BR BR0008824-2A patent/BR0008824A/pt not_active IP Right Cessation
- 2000-02-28 EP EP00910721A patent/EP1159243A1/de not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19622331A1 (de) * | 1996-06-04 | 1997-12-11 | Basf Ag | Verfahren der heterogen katalysierten Gasphasenoxidation von Propan zu Acrolein |
DE19807079A1 (de) * | 1998-02-20 | 1999-08-26 | Basf Ag | Verfahren der heterogen katalysierten Gasphasenoxidation von Propan zu Acrolein und/oder Acrlysäure |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003201260A (ja) * | 2001-12-04 | 2003-07-18 | Rohm & Haas Co | アルカンからオレフィン、不飽和カルボン酸および不飽和ニトリルを調製するための改良されたプロセス |
EP1460053A1 (de) * | 2001-12-27 | 2004-09-22 | Mitsubishi Chemical Corporation | Verfahren zur katalytischen dampfphasenoxidation und verfahren zur herstellung von (meth)acrolein oder (meth)acrylsäure |
EP1460053A4 (de) * | 2001-12-27 | 2006-03-22 | Mitsubishi Chem Corp | Verfahren zur katalytischen dampfphasenoxidation und verfahren zur herstellung von (meth)acrolein oder (meth)acrylsäure |
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BR0008824A (pt) | 2002-01-15 |
CN1343189A (zh) | 2002-04-03 |
JP2002539099A (ja) | 2002-11-19 |
DE19910507A1 (de) | 2000-09-14 |
EP1159243A1 (de) | 2001-12-05 |
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