EP1631382A2 - Oxidation von propan zu acrylsäure unter verwendung von katalysatoren in einem gemisch kristalliner phasen - Google Patents
Oxidation von propan zu acrylsäure unter verwendung von katalysatoren in einem gemisch kristalliner phasenInfo
- Publication number
- EP1631382A2 EP1631382A2 EP04767168A EP04767168A EP1631382A2 EP 1631382 A2 EP1631382 A2 EP 1631382A2 EP 04767168 A EP04767168 A EP 04767168A EP 04767168 A EP04767168 A EP 04767168A EP 1631382 A2 EP1631382 A2 EP 1631382A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- propane
- catalyst
- mixture
- moo
- good selectivity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 239000001294 propane Substances 0.000 title claims abstract description 68
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 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 17
- 238000007254 oxidation reaction Methods 0.000 title claims description 14
- 230000003647 oxidation Effects 0.000 title claims description 13
- 238000000034 method Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007789 gas Substances 0.000 claims abstract description 24
- 230000003213 activating effect Effects 0.000 claims abstract description 20
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 18
- 239000011261 inert gas Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims description 23
- 238000002441 X-ray diffraction Methods 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 238000001228 spectrum Methods 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000008246 gaseous mixture Substances 0.000 claims description 3
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 72
- 239000007787 solid Substances 0.000 description 69
- 239000000243 solution Substances 0.000 description 46
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 239000010955 niobium Substances 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 25
- 229910052750 molybdenum Inorganic materials 0.000 description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 18
- 229910052787 antimony Inorganic materials 0.000 description 18
- 239000011733 molybdenum Substances 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 17
- 229910052714 tellurium Inorganic materials 0.000 description 17
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 16
- 229910052720 vanadium Inorganic materials 0.000 description 16
- 239000002253 acid Substances 0.000 description 15
- 229910052758 niobium Inorganic materials 0.000 description 15
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 235000006408 oxalic acid Nutrition 0.000 description 13
- 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 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 11
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 10
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- -1 molybdenum halides Chemical class 0.000 description 8
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000003708 ampul Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
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- 238000001354 calcination Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
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- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- SXFBQAMLJMDXOD-UHFFFAOYSA-N (+)-hydrogentartrate bitartrate salt Chemical compound OC(=O)C(O)C(O)C(O)=O.OC(=O)C(O)C(O)C(O)=O SXFBQAMLJMDXOD-UHFFFAOYSA-N 0.000 description 1
- AXIFGFAGYFPNFC-UHFFFAOYSA-I 2-hydroxy-2-oxoacetate;niobium(5+) Chemical compound [Nb+5].OC(=O)C([O-])=O.OC(=O)C([O-])=O.OC(=O)C([O-])=O.OC(=O)C([O-])=O.OC(=O)C([O-])=O AXIFGFAGYFPNFC-UHFFFAOYSA-I 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- GAGSVOVTFFOFFX-UHFFFAOYSA-D [Nb+5].[Nb+5].OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O Chemical compound [Nb+5].[Nb+5].OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O GAGSVOVTFFOFFX-UHFFFAOYSA-D 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 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
- 229910000379 antimony sulfate Inorganic materials 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 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 1
- 239000003153 chemical reaction reagent 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
- 238000010586 diagram Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
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- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
- C07C57/04—Acrylic acid; Methacrylic acid
-
- 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
- B01J23/28—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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0576—Tellurium; Compounds thereof
-
- 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
-
- 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
- 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
- B01J23/18—Arsenic, antimony or 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
- B01J23/16—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
- B01J23/20—Vanadium, niobium or tantalum
-
- 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 the selective oxidation of propane to acrylic acid, by using catalysts in a mixture of crystalline phases, as well as the preparation of these catalysts.
- Patent application JP 10-330343 describes catalysts useful for the preparation of nitriles by oxidation of an alkane in the gas phase. These crystal structure catalysts are represented by the formula Mo a VbSb c X x O n and defined by their lattice parameters and the diffraction angles (2 ⁇ ). The symbol X represents one or more metallic elements chosen in particular from Ti, Zr, b, Ta, Cr, W, Sn, etc.
- These catalysts are prepared by adding solutions or suspensions containing respectively a source of antimony and a source of vanadium, then addition of a solution or suspension containing a specific quantity of molybdenum and addition of element X in the form of powder or solution.
- the oxides of these elements or of derivatives such as ammonium metavanadate or ammonium paramolybdate are particularly indicated.
- the method leads to a precursor which is dried and calcined to give a compound of metal oxides.
- Two phases can be obtained during preparation: a phase with an orthorhombic mesh and a phase with a hexagonal mesh.
- the orthorhombic mesh phase being the expected phase.
- the catalytic performances can be improved by "successive treatments of washing of the catalyst mixture obtained which make it possible to obtain the orthorhombic phase alone.
- Patent application JP 7-232071 describes catalysts with a crystalline structure corresponding to a formula of the MoVTeX type. These catalysts are precalcined at 300 ° C. The X-ray diffraction lines indicated suggest the presence of an orthorhombic mesh structure.
- European patent application EP-A-608838 describes the preparation of an unsaturated carboxylic acid from an alkane according to a catalytic oxidation reaction in the vapor phase in the presence of a catalyst containing a mixed metal oxide comprising as essential components , Mo, V, Te, O, as well as at least one element chosen from the group consisting of niobium, tantalum, tungsten, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, antimony, bismuth, boron, indium and cerium, these elements being present in very precise proportions.
- European patent application EP-A-895809 and US patent 6,143,916 describe catalysts based on oxides comprising molybdenum, vanadium, niobium, oxygen, tellurium and / or antimony. These catalysts are used for the conversion of propane to acrylic acid, in the presence of molecular oxygen (examples 9 and 10 of European application).
- Example 9 describes the oxidation of propane using a catalyst of formula Mo 1 V 0 (33 Nbo, ⁇ Te 0) 22 O n from a gas stream composed of propane, oxygen and helium and a stream of water vapor.
- US Patent 6,143,916 describes crystalline forms of these catalysts.
- phase A a crystalline phase of catalyst based on tellurium or antimony and molybdenum, preferably of hexagonal mesh (hereinafter called phase A), conferring selectivity on the final mixture, in association with a crystalline phase of A catalyst capable of activating propane can give completely unexpected oxidation results from the viewpoint of activity and selectivity. A synergistic effect can be observed when using the mixture of these crystalline catalytic phases.
- the tellurium or antimony and molybdenum-based phase which confers selectivity on the final mixture, can advantageously be chosen from tellurium and / or molybdenum compounds or antimony and molybdenum compounds with a hexagonal crystal structure (phase A), or from Te 2 MoO 7 , or Te 0 , 2 MoO x .
- the crystalline catalyst phase intended to confer good selectivity either corresponds to the formula:
- the crystalline catalyst phase capable of activating propane is a phase of crystallized metallic mixed oxides, more particularly based on molybdenum and vanadium such as mixed molybdenum and vanadium oxides, such as a hexagonal phase (phase A) antimony and niobium, or an orthorhombic phase catalyst (hereinafter called phase B).
- phase A hexagonal phase
- phase B orthorhombic phase catalyst
- the combination of the crystalline phases of catalyst is carried out at a rate of 90/10 to 15/85 by weight relative to the total mixture, of the catalyst conferring a good selectivity / catalyst capable of activating propane.
- the catalyst conferring good selectivity / catalyst capable of activating propane Preferably from 90/10 to 50/50 by weight relative to the total mixture, and in a very particularly preferred manner from 70/30 to 50/50 by weight relative to the total mixture, of the catalyst conferring good selectivity / catalyst capable of activating propane.
- the subject of the present invention is a process for the preparation of acrylic acid from propane, in which a gaseous mixture comprising propane, steam, optionally an inert gas and / or oxygen is passed through.
- a gaseous mixture comprising propane, steam, optionally an inert gas and / or oxygen is passed through.
- the method according to the present invention consists in passing the above-mentioned gas mixture over a catalyst consisting of a combination of a catalyst of formula (I), (P), Te 2 MoO 7 or Te 0; 2 MoO x and of a crystalline catalyst phase of formula (D), (IT) or (II ").
- the preparation of acrylic acid from propane is carried out using a catalyst consisting of a combination of phases crystalline at a rate of 90/10 to 15/85 by weight relative to the total mixture, of the catalyst conferring good selectivity / catalyst capable of activating propane.
- a catalyst consisting of a combination of phases crystalline at a rate of 90/10 to 15/85 by weight relative to the total mixture, of the catalyst conferring good selectivity / catalyst capable of activating propane.
- a rate of 90/10 to 50/50 by weight and in a particularly preferred manner at a rate of 70/30 to 50/50 by weight relative to the total mixture, of the catalyst conferring good selectivity / catalyst capable of activating propane.
- the propane / molecular oxygen molar ratio in the starting gas mixture is greater than or equal to 0.5.
- a molecular ratio greater than or equal to 0.3 may also be advantageous.
- the present invention also relates to the use of a crystal structure of catalyst combination of formula (I) or (F), Te 2 MoO 7 or Te 0, 2 MoO x with crystalline structure of catalysts of formula (II), (IF) or (II ") capable of activating propane, for the preparation of acrylic acid from propane.
- the method according to the invention makes it possible to simultaneously obtain good selectivity for acrylic acid and significant conversion of propane.
- it can be easily implemented in a fixed bed, in a fluidized bed or in a transported bed and the injection of the reagents can be carried out at different points of the reactor, so that one is outside the zone of flammability while having a high propane concentration and, therefore, a high catalyst productivity. Unconverted propane can be recycled.
- the method according to the invention comprises the following steps:
- the process comprises repeating, in a reactor provided with the combination of catalysts, the cycle comprising the following successive stages:
- step 1) can be carried out in the form of multiple injections.
- the cycle comprises an additional stage which precedes or follows stage 1) and during which a gaseous mixture corresponding to that of stage 1 is injected but without molecular oxygen, the propane / molecular oxygen molar ratio then being calculated globally for step 1) and this additional step.
- the additional step precedes step 1) in the cycle.
- the propane / molecular oxygen molar ratio in the starting gas mixture is preferably greater than or equal to 0.5 or greater than or equal to 0.3
- the conversion of propane to acrylic acid by means of the catalyst is carried out by oxidation, probably according to the following concurrent reactions (A) and (B): - the conventional catalytic reaction (B ):
- the propane / water volume ratio in the starting gas mixture is not critical and can vary within wide limits.
- the proportion of inert gas which can be helium, krypton, a mixture of these two gases, or nitrogen, carbon dioxide, etc., is also not critical and may also vary within wide limits.
- reactions (A) and (B) are carried out at a temperature of 200 to 500 ° C, preferably 250 to 450 ° C, more preferably still, 350 to 400 ° C.
- the pressure in the reactor (s) is generally from 1.01.10 4 to 1.01.10 ° Pa (0.1 to 10 atmospheres), preferably from 5.05.10 4 to 5.05.10 5 Pa (0.5- 5 atmospheres).
- the residence time in the reactor is generally from 0.01 to 90 seconds, preferably from 0.1 to 30 seconds.
- crystallized catalysts of formulas (I), (F), Te 2 MoO 7 or Teo, 2 MoO x or of formulas (II), (II ') and (II ") can be prepared according to various processes such as by hydrothermal synthesis , by co-precipitation or by solid-solid reaction.
- the sources of the different metals used as raw materials are often oxides, but are not limited to oxides.
- molybdenum in the case of molybdenum, ammonium molybdate, ammonium paramolybdate, ammonium hepta-molybdate, molybdic acid, molybdenum halides or oxyhalides such as M0CI 5 , the compounds organometallic molybdenum such as molybdenum alkoxides such as
- Mo (OC 2 H 5 ) 5 molybdenyl acetylacetone; "in the case of tellurium, tellurium, telluric acid, TeO 2 ;
- antimony for example antimony oxide (antimony trioxide), in particular the variety Senarmontite, antimony sulfate
- One method of preparing the catalysts consists in mixing, with stirring, aqueous solutions of niobic acid, oxalic acid, ammonium heptamolybdate, ammonium metavanadate, telluric acid or antimony oxide, then preferably precalcine in air at around 300-320 ° C, and calcine under nitrogen at about 600 ° C.
- a process for preparing the catalysts consists in implementing the preparation of a solution of niobic acid and oxalic acid, the preparation of a solution of molybdenum, vanadium, tellurium or antimony , mixing of the 2 solutions giving rise to the formation of a gel, then drying of the gel obtained, precalcination and calcination.
- the catalyst can be prepared by implementing the following steps:
- the drying [for example of step 8)] can be carried out in an oven in a thin layer, by atomization, by lyophilization, by zeodratation, by microwave, etc .;
- the precalcination can be carried out under air flow at 280-300 ° C or under static air at 320 ° C, in a fluidized bed, in an oven rotating in a fixed so-called aerated bed, so that the catalyst grains are separated each other to prevent them from fusing during precalcination or possibly during calcination;
- the calcination is preferably carried out under very pure nitrogen and at a temperature in the region of 600 ° C., for example in a rotary kiln or in a fluidized bed and for a period which may be 2 hours.
- the precalcination is carried out:
- the precalcination is carried out: - at around 320 ° C under an air flow rate of less than 10 ml / min / g; or
- a solid-solid reaction is carried out by mixing the metal sources and then co-grinding until a homogeneous mixture is obtained.
- the solid is obtained after heating under reduced pressure at a temperature in the region of 600 ° C.
- the metal oxides or the metal itself are used as the source of metals. More preferably, the heating is carried out for an extended time (preferably 3 days to 1 week).
- the catalysts prepared according to the methods described above can each be in the form of grains generally from 20 to 300 ⁇ m in diameter, the grains of each of the associated catalysts being generally mixed before the implementation of the method according to the invention.
- the shaping can be carried out by spraying a gel or a suspension.
- the combination of catalysts can also be in the form of a solid catalytic composition composed of grains, each of which comprises both of the catalysts.
- the proportions of the constituents of the regeneration gas mixture are generally as follows (in molar ratios): oxygen / inert (He-Kr) / H 2 O (vapor) ⁇ 1 / 1-10 / 0-10,
- they are 1 / 1-5 / 0-5.
- the regeneration temperature is generally 250 to 500 ° C.
- the process is generally carried out until the reduction rate of the catalyst is between 0.1 and 10 g of oxygen per kg of catalyst. This reduction rate can be monitored during the reaction by the quantity of products obtained. The equivalent amount of oxygen is then calculated. It can also be followed by the exothermicity of the reaction. We can also follow the reduction rate by the amount of oxygen consumed in the regenerator.
- the regeneration which can be carried out under conditions of temperature and pressure identical to, or different from those of reactions (A) and (B), the catalysts regain initial activity and can be reintroduced into the reactors.
- Reactions (A) and (B) and regeneration (C) can be carried out in a conventional reactor, such as a fixed bed reactor, a fluidized bed reactor or a transported bed reactor.
- Reactions (A) and (B) and regeneration (C) can also be carried out in the same reactor by alternating the reaction and regeneration periods.
- the reactions (A) and (B) and the regeneration (C) are carried out in a reactor with a transported catalyst bed, in particular in a vertical reactor, the catalyst then preferably moving from the bottom to the top.
- the propylene produced and / or the unreacted propane are recycled (or returned) at the inlet of the reactor, that is to say that they are reintroduced at the inlet of the reactor, in mixture or in parallel with the starting mixture of propane, water vapor and, where appropriate, inert gas (ies).
- the present invention has the great advantage of combining very good selectivity for acrylic acid and good conversion of propane, due to the combination of the catalysts used and the synergistic effect provided.
- synergistic effect it can be seen, on the one hand, that each catalyst taken separately is less efficient than the combination of the catalyst capable of providing good selectivity with the catalyst capable of activating propane and, on the other hand, the selectivity observed is greater than the additive effect provided by the 2 catalysts taken in isolation, in almost all cases. This effect can be observed in particular in the tests which follow.
- the preparation is carried out by solid-solid reaction in a vacuum-sealed ampoule. 10.00 g of MoO 3 (Merck), 1.37 g of molybdenum metal (Alfa Aesar), 8.01 g TeO 2 (Alfa Aesar) and 3.04 g VO 5 (Riedel de Ha ⁇ n) are co-ground in a mortar agate for 15 minutes, until a homogeneous mixture is obtained. This mixture is introduced into a quartz bulb. The ampoule is then sealed under vacuum and heated to 600 ° C for one week. The solid recovered is analyzed by X-ray diffraction.
- the analysis confirms that the desired phase has been obtained, which corresponds to the hexagonal structure (diffractogram - Figure 1).
- the solid obtained has the chemical formula: MoV 0; 8 Teo, 6 ⁇ x , x being the quantity of oxygen corresponding to the oxidation state of the cations.
- phase A with tellurium and niobium of composition MoVp ⁇ Tep ⁇ Nbn iO x .
- the tellurium phase A containing niobium_a was obtained by co-precipitation.
- 5.00 g of ammonium heptamolybdate (Starck)) + 1.00 g of ammonium metavanadate (GFE) + 2.60 g of telluric acid (Fluka) + 25 ml of water are introduced into a beaker.
- the mixture is heated (70 ° C.) with stirring until a clear solution is obtained.
- 0.52 g of niobic acid (CBMM) + are introduced into a beaker.
- the mixture is heated until the solution clears (approximately 4 hours, temperature 70 ° C.), it is centrifuged (350O revolutions / min for 15 minutes) then the liquid phase is added to the solution containing Mo, V and Te. An orange gel is then obtained which is placed overnight in an oven at 110 ° C.
- the solid obtained is pre-calcined in air for 4 hours at 300 ° C (50 ml / min / g) and calcined for 2 hours at 600 ° C under nitrogen (50 ml / min / g).
- the solid obtained has the chemical formula: MoVo , 3 Te 0) 4 Nb 0) 1 O x .
- the solid recovered is analyzed by X-ray diffraction ( Figure 2).
- Antimony phase A is prepared like that of Example 1, but with the following constituents.
- the antimony-containing phase A containing niobium was obtained by co-precipitation.
- 7.00 g of ammonium heptamolybdate (Starck) + 1.39 g of ammonium metavanadate (GfE) are introduced into a beaker, the mixture is heated (80 ° C.) with stirring until a clear solution.
- 1.17 g Sb O 3 (Alfa Aesar) is then added and the mixture is left to stir for 4 hours without switching off the heating.
- 2 ml of H 2 O at 30% wt Alfa Aesar diluted in 10 ml of water are introduced, the solution then becomes clear orange.
- niobic acid ( ⁇ BMM) + 1.34 g of oxalic acid (Alfa Aesar) + 15 ml of water are introduced into a beaker.
- the mixture is heated until the solution clears (about 4 hours, temperature 70 ° C.), centrifuged (3500 rpm for 15 minutes) then the liquid phase is added to the solution containing Mo, V and Sb.
- a yellow gel is then obtained which is placed overnight in an oven at 110 ° C.
- the solid obtained is pre-calcined in air for 4 hours at 300 ° C.
- the solid obtained has the chemical formula: MoVo ) 3 Sb 0) 1 Nb 0; ⁇ Ow
- the Vo phase, 5 Mo ⁇ ! 9 ⁇ 5 was prepared by hydrothermal synthesis. 2.00 g of ammonium heptamolybdate (Starck), 1.33 g of VOSO 4 (Alfa Aesar) and 0.07g of NH 4 OH (28% by weight NH 3 ) are introduced with 50 ml of water into a 100ml Teflon jar. The mixture is left for 72 hours at 175 ° C. in an autoclave. The solid is then filtered, washed with distilled water, dried in an oven at 110 ° C and calcined under nitrogen at 600 ° C for 2 hours (50 ml / min / g).
- the solid obtained has a chemical formula of the Mo t V t O v type .
- the solid recovered is analyzed by X-ray diffraction ( Figure 5), it complies with JCPDS sheet 77-0649 (Joint Committee of Powder Diffraction Spectroscopy). This phase has been described by LM Plyasova et al., Kinetica i Kataliz, 31 (6), 1430-1434 (1990).
- the Te 2 MoO 7 phase was prepared by co-precipitation.
- a minimum of water (15 ml) 6.50 g of telluric acid (Fluka) and 2.50 g of ammonium heptamolybdate (Stark) are dissolved.
- the mixture is heated (80 ° C.) with stirring and allowed to evaporate until a white paste is obtained which is left to dry overnight in an oven at 110 ° C.
- the solid obtained is calcined for 2 hours at 470 ° C in air (50 ml / min / g).
- the solid obtained has the chemical formula:
- the solid recovered is analyzed by X-ray diffraction ( Figure 6), it complies with the JCPDS 70-0047 sheet. This phase has been described by A. Kaddouri et al., J. Therm. Anal. Cal, 66, 63-78 (2001).
- MoVTeNb catalyst containing a high concentration in phase B Into a 100 ml beaker are simultaneously introduced: 35 ml of distilled water + 7.78 g of ammonium heptamolybdate (Starck) + 1.70 g of ammonium metavanadate
- a niobic acid / oxalic acid solution with an oxalate / Nb ratio of 2.70 is prepared.
- the following are introduced into a 50 ml beaker: 10 ml of distilled water ⁇ 0.82 g of niobic acid (CBMM) + 1.67 g of oxalic acid (Alfa Aesar).
- CBMM niobic acid
- Alfa Aesar 1.67 g of oxalic acid
- an orange opaque gel is obtained which is placed in a crystallizer to be dried overnight in an oven at 110 ° C.
- the solid is pre-calcined in air at 300 ° C for 4 hours (50 ml / min / g) and then calcined in purified nitrogen at 600 ° C for 2 hours (50 ml / min / g)).
- the solid recovered is analyzed by X-ray diffraction. This shows a mixture of the hexagonal phase and the desired orthorhombic phase.
- the solid obtained has the chemical formula: Mo î Vo. ⁇ Teo. î oNbo. ⁇ O z and has a diffracto gram similar to that described by JMM Millet et al., Appl. Catal., 232, 77-92 (2002).
- the solid obtained is washed in a hydrogen peroxide solution (Alfa Aesar) at 30% wt diluted 2 times, for 4 hours, at room temperature.
- the solution is filtered and the recovered solid dried in an oven (110 ° C) and then calcined for 2 hours under nitrogen at 600 ° C (50 ml / min / g).
- the solid recovered is analyzed by X-ray diffraction (Figure 7). The analysis confirms that the desired phase has been obtained, which corresponds to the orthorhombic structure as described in the publication above with a small amount of hexagonal phase.
- the solid obtained has the chemical formula: M ⁇ V 0 . 26 Te 0 . 10 Nb 0 . 14 O z .
- MoVSbNh catalyst containing a high concentration in phase B In a flask, 1.99 g of ammonium metavanadate (GfE) and 45 ml of distilled water are introduced. The mixture is heated to reflux at 95 ° C. with stirring until a clear solution is obtained, then added: 1.24 g of antimony trioxide (Alfa Aesar) + 10.00 g of ammonium heptamolybdate (Starck ). The heating is left for 1 hour and it is placed under an argon sweep. A solution containing 2 ml of water is introduced oxygenated (Alfa Aesar) at 30% wt per 10 ml of water. A clear orange solution is then obtained.
- GfE ammonium metavanadate
- Starck ammonium heptamolybdate
- Alfa Aesar oxalic acid
- CBMM niobic acid
- the solid recovered is analyzed by X-ray diffraction. This shows a mixture of the hexagonal phase and the desired orthorhombic phase.
- the solid obtained has the chemical formula: MoVo ⁇ Sbo ⁇ sNbo ⁇ O w .
- the TeMo 5 O 16 phase was obtained by solid-solid reaction in a vacuum-sealed ampoule.
- 1.32 g of molybdenum metal (Alfa Aesar) and 6.65 g TeO (Alfa Aesar) are co-ground in an agate mortar for 15 minutes, until obtained d '' a homogeneous mixture.
- This mixture is introduced into a quartz bulb.
- the ampoule is then vacuum sealed and heated to 600 ° C for 72 hours.
- the solid recovered is analyzed by X-ray diffraction ( Figure 9), it complies with JCPDS sheet 70-0451.
- the analysis confirms that the desired phase has been obtained, which corresponds to the monoclinic structure having the chemical formula: MoTe 0j O x .
- Example 10 MoVTeNb containing a lot of phase B.
- a niobic acid / oxalic acid solution with an Ox / Nb ratio of 2.70 is prepared.
- the following are introduced into a 50 ml beaker: 10 ml of distilled water + 0.82 g of niobic acid (CBMM) + 1.67 g of oxalic acid (Alfa Aesar).
- CBMM niobic acid
- Alfa Aesar oxalic acid
- the mixture is heated to 70 ° C. with stirring until the starting solution clears up (about 4 hours).
- This solution is centrifuged (3500 rpm for 15 minutes) and then the liquid phase is introduced into the clear red solution containing molybdenum, vanadium and tellurium.
- an orange opaque gel is obtained which is placed in a crystallizer to be dried overnight in an oven at 110 ° C.
- the solid is pre-calcined in air at 300 ° C for 4 hours (50 mL / min / g) and then calcined in purified nitrogen at 600 ° C for 2 hours (50 mL / min / g)).
- the solid recovered is analyzed by X-ray diffraction. This shows a mixture of the hexagonal phase and the desired orthorhombic phase.
- the solid obtained has a diffractogram similar to that described in the publication JMM Millet, H. Roussel, A. Pigamo, JL Dubois, JC Jumas, Appl. Catal 232 (2002) 77-92, figure lb.
- the solid obtained has the chemical formula: MoV 0 , 3 Te 0; 2 Nb 0 , ⁇ .
- the solid obtained is washed in a solution of hydrogen peroxide (Alfa Aesar) at 30% diluted 2 times for 4 hours at room temperature.
- a niobic acid / oxalic acid solution with an Ox / Nb ratio of 2.70 is prepared.
- the following are introduced into a 50 ml beaker: 10 ml of distilled water + 0.82 g of niobic acid (CBMM) + 1.67 g of oxalic acid (Alfa Aesar).
- CBMM niobic acid
- Alfa Aesar oxalic acid
- the mixture is heated to 70 ° C. with stirring until the starting solution clears up (about 4 hours).
- This solution is centrifuged (3500 rpm for 15 minutes) and then the liquid phase is introduced into the clear red solution containing molybdenum, vanadium and tellurium.
- an orange opaque gel is obtained which is placed in a crystallizer to be dried overnight in an oven at 110 ° C.
- the solid is pre-calcined in air at 300 ° C for 4 hours (50 mL / min / g) and then calcined in purified nitrogen at 600 ° C for 2 hours (50 mL / min / g)).
- the solid recovered is analyzed by X-ray diffraction. This shows a mixture of the hexagonal phase and the desired orthorhombic phase.
- the solid obtained has a diffractogram similar to that described in the publication JMM Millet, H. Roussel, A. Pigamo, JL Dubois, JC Jumas, Appl. Catal 232 (2002) 77-92, figure lb.
- the solid obtained has the chemical formula: MoV 0j3 Te 0; 2 Nbo, ⁇ .
- the solid obtained is washed in a solution of hydrogen peroxide (Alfa Aesar) at 30% diluted 2 times for 4 hours at room temperature.
- the solution is filtered and the recovered solid " dried in an oven (110 ° C.) and then calcined for 2 hours under nitrogen at 600 ° C. (50 ml / min / g).
- the recovered solid is analyzed by X-ray diffraction. L analysis confirms that the desired phase, which corresponds to the orthorhombic structure as described in the above publication, is obtained with a small amount of hexagonal phase.
- the solid obtained has the chemical formula: CATALYTIOUE TEST:
- the pure phases thus prepared are tested as follows: 0.5 to 1.5 g of solid are loaded into a straight reactor with a fixed bed in Pyrex and the temperature rise (2.5 ° C / min) is carried out under nitrogen. When the desired temperature is reached, the reaction mixture is started: total flow rate of 30 ml / min (5% C 3 H 8 , 5% Ne, 10% O 2 , 45% H 2 O and 35% N 2 (% molars)) and the reactor is allowed to stabilize for 30 minutes. A 25 ml flask containing 5 ml of water is placed at the outlet of the reactor in order to allow the condensation of the organic compounds. For each temperature, the condensation time is 2 hours. The non-condensable products are analyzed online by a Chrompack chromatograph and the liquid effluents are analyzed after reaction on another Chrompack chromatograph.
- EXAMPLE 13 To carry out the tests of catalysts 10 and 11: tests Al, A2, AAl, AA2 under the same conditions as tests I and J of catalyst 7, a mass of 0.5 g was used for the tests Al and AAl, and a mass of 0.47 g was used for tests A2 and AA2. The results obtained are collated in Table 2. The results indicate a very good reproducibility of the performance of the catalysts.
- Table 1 Table of mechanical mixtures of the phases (mass of each solid in the mixture): Mass of the column solid (sohde C) + Mass of the Hgne solid (solid L). The letter indicated in the table corresponds to the reference of the example of the test.
- Examples B, C and E to K a mass m (specified in the table) of the solids prepared in Examples 2 to 9 is loaded into the reactor as in Example D, and the catalyst test is carried out as in example D.
- Examples L to Y and Z two masses im and m 2 of two different solids are mixed in an agate mortar for 15 min to obtain a homogeneous mixture. The mixture thus formed is loaded into a reactor as in Example D, then the catalyst test is carried out as in Example
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PCT/FR2004/001290 WO2004105938A2 (fr) | 2003-05-27 | 2004-05-25 | Oxydation du propane en acide acrylique par utilisation de catalyseurs en melange de phases cristallines |
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FR2878767B1 (fr) * | 2004-12-02 | 2007-07-13 | Arkema Sa | Preparation de catalyseurs a base de tantale pour l'oxydation selective du propane en acide acrylique |
CN101164694A (zh) | 2006-10-20 | 2008-04-23 | 德古萨股份公司 | 用于催化气相氧化的混合氧化物催化剂 |
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-
2003
- 2003-05-27 FR FR0306414A patent/FR2855516B1/fr not_active Expired - Fee Related
-
2004
- 2004-05-25 CN CNA2004800145734A patent/CN1795045A/zh active Pending
- 2004-05-25 JP JP2006530376A patent/JP2007502319A/ja active Pending
- 2004-05-25 KR KR1020057022486A patent/KR20060006971A/ko not_active Application Discontinuation
- 2004-05-25 WO PCT/FR2004/001290 patent/WO2004105938A2/fr active Application Filing
- 2004-05-25 EP EP04767168A patent/EP1631382A2/de not_active Withdrawn
- 2004-05-25 US US10/558,023 patent/US7683213B2/en not_active Expired - Fee Related
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FR2855516B1 (fr) | 2005-07-08 |
WO2004105938A2 (fr) | 2004-12-09 |
US7683213B2 (en) | 2010-03-23 |
KR20060006971A (ko) | 2006-01-20 |
US20060293538A1 (en) | 2006-12-28 |
WO2004105938A3 (fr) | 2005-06-02 |
FR2855516A1 (fr) | 2004-12-03 |
CN1795045A (zh) | 2006-06-28 |
JP2007502319A (ja) | 2007-02-08 |
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