WO2000010955A1 - Procede de fabrication d'acroleine a partir du propylene par reaction redox - Google Patents
Procede de fabrication d'acroleine a partir du propylene par reaction redox Download PDFInfo
- Publication number
- WO2000010955A1 WO2000010955A1 PCT/FR1999/002005 FR9902005W WO0010955A1 WO 2000010955 A1 WO2000010955 A1 WO 2000010955A1 FR 9902005 W FR9902005 W FR 9902005W WO 0010955 A1 WO0010955 A1 WO 0010955A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- propylene
- redox reaction
- solid composition
- acrolein
- carried out
- Prior art date
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- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims abstract description 58
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 40
- 238000006479 redox reaction Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000008247 solid mixture Substances 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 230000008929 regeneration Effects 0.000 claims description 11
- 238000011069 regeneration method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- -1 Propylene - Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000010405 reoxidation reaction Methods 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 5
- 239000011609 ammonium molybdate Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012808 vapor phase Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 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 3
- 239000007924 injection Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000000750 progressive effect Effects 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 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
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 230000018109 developmental process Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Definitions
- the present invention relates to the manufacture of acrolein from propylene by oxidation according to a redox reaction.
- the invention also relates to the use of a solid composition of mixed oxides as a redox system in said reaction.
- French Patent No. 2,093,773 describes the production of acrolein by catalytic oxidation of propylene in the vapor phase, with molecular oxygen, in the presence of a catalytic oxide whose composition of the catalytic elements, expressed in atomic ratio , is the following :
- This catalyst can be prepared by mixing aqueous solutions of ammonium molybdate and ammonium paratungstate, adding solutions of cobalt nitrate, iron nitrate and bismuth nitrate to the aqueous mixture, then adding an aqueous solution. of hydroxide or carbonate of an alkali metal, then colloidal silica as a source of silicon, by molding the substance obtained and calcining it at 350-600 "C in a stream of air.
- W + Mo being equal to 12.0 and Z representing an alkali or alkaline earth metal.
- the raw materials used to form the catalyst can be the oxides of the different metals, but also, as the case may be, nitrates, carbonates, hydroxides.
- salts of acids such as ammonium molybdate and ammonium tungstate are recommended.
- a catalyst according to this US patent is prepared by m e langeant aqueous solutions of ammonium molybdate respectively and ammonium paratungstate, adding solutions of cobalt nitrate e respectively, of iron nitrate and bismuth nitrate, then an aqueous solution of alkali metal hydroxide or carbonate, then colloidal silica as a source of silicon, concentrating the system by evaporation, adding a support if necessary, and following by evaporation, a mixture of the resulting substance and calcination at 350-600 ⁇ C .
- Japanese patent Showa 45-125 359 describes a process for the production of acrolein in the vapor phase by catalytic oxidation of propylene by air or oxygen, in the presence of a catalyst of formula:
- ⁇ Me is one of Sn, Zn, W, Cr, Mn and T.; and H is at least one of K, Rb and C s.
- this catalyst it is possible to add to an aqueous solution of a molybdenum compound (ammonium molybdate, molybdic acid or molybdenum oxide), aqueous solutions of compounds of Ni, Co, Fe, K (and / or Rb , Cs), Bi and Me, then add a support such as alumina, silicon carbide and silica (silica sol or silica gel), then heat the resulting mixture to dryness, calcine it to about 500 'C, and we transform it into pellets.
- a molybdenum compound ammonium molybdate, molybdic acid or molybdenum oxide
- aqueous solutions of compounds of Ni, Co, Fe, K (and / or Rb , Cs), Bi and Me then add a support such as alumina, silicon carbide and silica (silica sol or silica gel), then heat the resulting mixture to dryness, calcine it to about 500 'C, and we transform it into pellets.
- French Patent No. 2,534,904 describes a catalyst for the production of unsaturated aldehydes, in particular acrolein and methacrolein, by vapor phase oxidation of propylene, isobutylene or tertiary butanol with a gas containing molecular oxygen.
- This catalyst is represented by the general formula:
- A represents nickel and / or cobalt
- B represents one or more elements chosen from alkali and alkaline earth metals and thallium
- - C represents one or more elements chosen from phosphorus, arsenic, boron, antimony, tin, cerium, lead and. niobium;
- D represents one or more elements chosen from silicon, aluminum, zirconium and titanium; and - a, b, c, d, e, f, g, h and x represent the atomic proportions of the individual elements, and if d is taken equal to 12: 0.1 ⁇ a ⁇ 10; 0.5 ⁇ b ⁇ 10;
- - x is the quantity of oxygen bound to the other elements and depends on their oxidation states, the bismuth being introduced in the form of an oxide previously obtained by calcination between 600 and 900 ° C. of a mixture of a compound bismuth and a tungsten compound.
- the Applicant Company has now discovered that one can be f 1 polish acrolein by oxidation of propylene in gas ph ase in the absence of molecular oxygen by reacting propylene with a particular solid composition of mixed oxides, which acts as a redox system and provides the oxygen necessary for the reaction.
- the oxides of the different metals used in the composition of the mixed oxide of formula (I) can be used as raw materials in the preparation of this composition, but the raw materials are not limited to the oxides; as other raw materials, there may be mentioned: - in the case of molybdenum, ammonium molybdate and molybdic acid; in the case of bismuth, iron, cobalt and nickel, nitrates, carbonates and hydroxides, such as bismuth nitrate, ferric nitrate, cobalt nitrate, nickel nitrate; in the case of chromium, chromium nitrate; and - in the case of potassium, hydroxide, carbonate or potassium nitrate; and, in general, all the compounds capable of forming an oxide by calcination, namely metallic salts of organic acids, metallic salts of mineral acids, complex metallic compounds, organic metallic compounds, etc.
- the source of silicon is generally constituted by colloidal silica.
- the subject of the present invention is a process for the production of acrolein from propylene, a process according to which gaseous propylene is reacted with a solid composition of formula (I) as defined above, operating at a temperature of 200 to 600 "C, in particular from 250 to 450" C, under a pressure of 1.01 x 10 to 1.01 x 10 Pa (0.1 to 10 atmospheres), in particular from 5.05 x 10 4 to 5, 05 x 10 5 Pa (0.5 - 5 atmospheres) and with a residence time of 0.01 second to 90 seconds, in particular from 0.1 second to 30 seconds, in the absence of molecular oxygen, thus achieving the redox reaction (1) as indicated above.
- the propylene gas can be introduced as a mixture with an inert gas, such as nitrogen, and / or with water (water vapor).
- reaction (2) the solid composition undergoes a reduction and a progressive loss of its activity. This is why, once the solid composition has gone to the reduced state, the regeneration of said solid composition is carried out according to reaction (2):
- the solid composition regains initial activity and can be used in a new reaction cycle.
- the redox reaction (1) and the regeneration can be carried out in a two-stage device, namely a reactor and a regenerator which operate simultaneously and in which two charges of solid composition alternate periodically; the redox reaction (1) and the regeneration can also be carried out in the same reactor by alternating the reaction and regeneration periods.
- the preparation of the acrolein according to the invention is carried out according to a stoichiometric and non-catalytic reaction.
- x is the amount of oxygen bound to the other elements and depends on their oxidation states.
- the solution containing bismuth and that containing chromium are successively poured, with stirring, into the solution containing Co, Ni, Fe and K.
- the resulting solution is then poured, still with stirring, into the solution containing molybdenum.
- 23.7 g of colloidal silica (40% by mass) are then added thereto.
- the resulting mixture is heated to 80 ° C for 1.5 hours, then dried at 140 ° C for 12 hours.
- the solid obtained is calcined for 6 hours at 500 ° C. in air.
- the different metals are present in this solid in the atomic ratios as indicated in the title of this example.
- Example 1 After having carried out the reaction of Example 1 (b), the same solid is again subjected to four successive injections of propylene, under the same test conditions as in Example 1. The performances obtained are reported in Table 1 .
- Example 2 After the reducing treatment of Example 2, the solid is regenerated for 1 hour in air at 340 ° C., then replaced under a stream of helium. Four successive new injections of 2 x 10 -6 mole of propylene are sent to the solid, in order to conduct the redox reaction of the propylene and the solid. The performances obtained are reported in Table 2.
- Example 2 200 mg of a solid prepared according to Example 1 is loaded into a tubular reactor at 340 ° C., then it is swept by a continuous flow of 11.5 ml / min. of air. Five injections containing 2 x 10 mole of propylene are sent to the solid, which is here the catalyst for the reaction. Propylene is converted to 94.6% with selectivities for acrolein and acrylic acid of 75.2% and 3.2% respectively.
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR9913133-1A BR9913133A (pt) | 1998-08-21 | 1999-08-18 | Processo para fabricação de acroleìna a partir depropileno por reação redox |
CA002351632A CA2351632A1 (fr) | 1998-08-21 | 1999-08-18 | Procede de fabrication d'acroleine a partir du propylene par reaction redox |
MXPA01001869A MXPA01001869A (es) | 1998-08-21 | 1999-08-18 | Procedimiento para la fabricacion de acroleina a partir de propileno por reaccion de oxido-reduccion. |
EP99936749A EP1105364A1 (fr) | 1998-08-21 | 1999-08-18 | Procede de fabrication d'acroleine a partir du propylene par reaction redox |
AU51737/99A AU5173799A (en) | 1998-08-21 | 1999-08-18 | Method for making acrolein from propylene by redox reaction |
JP2000566229A JP2002523386A (ja) | 1998-08-21 | 1999-08-18 | レドックス反応によってプロピレンからアクロレインを製造する方法 |
KR1020017002102A KR20010079661A (ko) | 1998-08-21 | 1999-08-18 | 산화환원 반응에 의한 프로필렌으로부터 아크롤레인의제조 방법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9810598A FR2782512B1 (fr) | 1998-08-21 | 1998-08-21 | Procede de fabrication d'acroleine a partir du propylene par reaction redox et utilisation d'une composition solide d'oxydes mixtes comme systeme redox dans la dite reaction |
FR98/10598 | 1998-08-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000010955A1 true WO2000010955A1 (fr) | 2000-03-02 |
Family
ID=9529807
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1999/002005 WO2000010955A1 (fr) | 1998-08-21 | 1999-08-18 | Procede de fabrication d'acroleine a partir du propylene par reaction redox |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP1105364A1 (fr) |
JP (1) | JP2002523386A (fr) |
KR (1) | KR20010079661A (fr) |
CN (1) | CN1313844A (fr) |
AU (1) | AU5173799A (fr) |
BR (1) | BR9913133A (fr) |
CA (1) | CA2351632A1 (fr) |
FR (1) | FR2782512B1 (fr) |
ID (1) | ID29798A (fr) |
MX (1) | MXPA01001869A (fr) |
WO (1) | WO2000010955A1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103157483A (zh) * | 2011-12-13 | 2013-06-19 | 上海华谊丙烯酸有限公司 | 复合氧化物催化剂及其制造方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4341717A (en) * | 1973-03-08 | 1982-07-27 | The Standard Oil Company | Reactor for contacting gases and a particulate solid |
EP0169449A2 (fr) * | 1984-07-23 | 1986-01-29 | Mitsubishi Petrochemical Co., Ltd. | Procédé de régénération d'un catalyseur |
FR2725715A3 (fr) * | 1994-10-12 | 1996-04-19 | Basf Ag | Procede de deshydrogenation par voie d'oxydation catalytique de composes alkylaromatiques et paraffiniques |
EP0861819A1 (fr) * | 1997-02-27 | 1998-09-02 | Elf Atochem S.A. | Procédé de fabrication d'acroléine à partir du propylène par réaction redox |
WO1999003809A1 (fr) * | 1997-07-15 | 1999-01-28 | E.I. Du Pont De Nemours And Company | Oxydation perfectionnee en phase vapeur de propylene en acroleine |
-
1998
- 1998-08-21 FR FR9810598A patent/FR2782512B1/fr not_active Expired - Fee Related
-
1999
- 1999-08-18 CN CN99809915A patent/CN1313844A/zh active Pending
- 1999-08-18 ID IDW20010392A patent/ID29798A/id unknown
- 1999-08-18 WO PCT/FR1999/002005 patent/WO2000010955A1/fr not_active Application Discontinuation
- 1999-08-18 EP EP99936749A patent/EP1105364A1/fr not_active Withdrawn
- 1999-08-18 MX MXPA01001869A patent/MXPA01001869A/es not_active Application Discontinuation
- 1999-08-18 AU AU51737/99A patent/AU5173799A/en not_active Abandoned
- 1999-08-18 KR KR1020017002102A patent/KR20010079661A/ko not_active Application Discontinuation
- 1999-08-18 JP JP2000566229A patent/JP2002523386A/ja not_active Withdrawn
- 1999-08-18 BR BR9913133-1A patent/BR9913133A/pt not_active Application Discontinuation
- 1999-08-18 CA CA002351632A patent/CA2351632A1/fr not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4341717A (en) * | 1973-03-08 | 1982-07-27 | The Standard Oil Company | Reactor for contacting gases and a particulate solid |
EP0169449A2 (fr) * | 1984-07-23 | 1986-01-29 | Mitsubishi Petrochemical Co., Ltd. | Procédé de régénération d'un catalyseur |
FR2725715A3 (fr) * | 1994-10-12 | 1996-04-19 | Basf Ag | Procede de deshydrogenation par voie d'oxydation catalytique de composes alkylaromatiques et paraffiniques |
EP0861819A1 (fr) * | 1997-02-27 | 1998-09-02 | Elf Atochem S.A. | Procédé de fabrication d'acroléine à partir du propylène par réaction redox |
WO1999003809A1 (fr) * | 1997-07-15 | 1999-01-28 | E.I. Du Pont De Nemours And Company | Oxydation perfectionnee en phase vapeur de propylene en acroleine |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Section Ch Derwent World Patents Index; Class A41, AN 73-21080U, XP002101775 * |
Also Published As
Publication number | Publication date |
---|---|
CN1313844A (zh) | 2001-09-19 |
EP1105364A1 (fr) | 2001-06-13 |
FR2782512A1 (fr) | 2000-02-25 |
FR2782512B1 (fr) | 2000-09-15 |
AU5173799A (en) | 2000-03-14 |
KR20010079661A (ko) | 2001-08-22 |
MXPA01001869A (es) | 2002-04-08 |
ID29798A (id) | 2001-10-11 |
BR9913133A (pt) | 2001-10-30 |
CA2351632A1 (fr) | 2000-03-02 |
JP2002523386A (ja) | 2002-07-30 |
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